Structure of Atom: Unit 2

STRUCTURE OF ATOM 29
UNIT 2
STRUCTURE OF ATOM
The rich diversity of chemical behaviour of different elements

Objectives 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 time
electron, proton and neutron and
of early Indian and Greek philosophers (400 B.C.) who
their characteristics;
were of the view that atoms are the fundamental building
• describe Thomson, Rutherford blocks of matter. According to them, the continued
and Bohr atomic models; subdivisions of matter would ultimately yield atoms which
• understand the important would not be further divisible. The word ‘atom’ has been
featur es of the quantum derived from the Greek word ‘a-tomio’ which means
mechanical model of atom; ‘uncut-able’ or ‘non-divisible’. These earlier ideas were
mere speculations and there was no way to test them
• understand natur e of experimentally. These ideas remained dormant for a very
electromagnetic radiation and long time and were revived again by scientists in the
Planck’s quantum theory; 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 explain
Heisenberg uncertainty principle;
the law of conservation of mass, law of constant
• define an atomic orbital in terms composition and law of multiple proportion very
of quantum numbers; successfully. However, it failed to explain the results of
• state aufbau principle, Pauli many experiments, for example, it was known that
exclusion principle and Hund’s substances like glass or ebonite when rubbed with silk
rule of maximum multiplicity; and or fur get electrically charged.
In this unit we start with the experimental
• write the electronic configurations observations made by scientists towards the end of
of atoms. nineteenth and beginning of twentieth century. These
established that atoms are made of sub-atomic particles,
i.e., electrons, protons and neutrons — a concept very
different from that of Dalton.
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30 CHEMISTRY
2.1 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 other”. Fig. 2.1(a) A cathode ray discharge tube
2.1.1 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
suggested the particulate nature of Fig. 2.1(b) A cathode ray discharge tube with
electricity. perforated anode
In mid 1850s many scientists mainly
Faraday began to study electrical discharge The results of these experiments are
in partially evacuated tubes, known as summarised below.
cathode ray discharge tubes. It is depicted (i) The cathode rays start from cathode and
in Fig. 2.1. A cathode ray tube is made of move towards the anode.
glass containing two thin pieces of metal, (ii) These rays themselves are not visible but
called electrodes, sealed in it. The electrical their behaviour can be observed with the
discharge through the gases could be help of certain kind of materials
observed only at very low pressures and at (fluorescent or phosphorescent) which
very high voltages. The pressure of different glow when hit by them. Television picture
gases could be adjusted by evacuation of the tubes are cathode ray tubes and
glass tubes. When sufficiently high voltage television pictures result due to
is applied across the electrodes, current fluorescence on the television screen
coated with certain fluorescent or
starts flowing through a stream of particles
phosphorescent materials.
moving in the tube from the negative electrode
(iii) In the absence of electrical or magnetic
(cathode) to the positive electrode (anode).
field, these rays travel in straight lines
These were called cathode rays or cathode
(Fig. 2.2).
ray particles. The flow of current from
(iv) In the presence of electrical or magnetic
cathode to anode was further checked by
field, the behaviour of cathode rays are
making a hole in the anode and coating the
similar to that expected from negatively
tube behind anode with phosphorescent charged particles, suggesting that the
material zinc sulphide. When these rays, after cathode rays consist of negatively
passing through anode, strike the zinc charged particles, called electrons.
sulphide coating, a bright spot is developed (v) The characteristics of cathode rays
on the coating [Fig. 2.1(b)]. (electrons) do not depend upon the
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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 its
Thus, we can conclude that electrons are original path increases with the increase
basic constituent of all the atoms. in the voltage across the electrodes, or the
strength of the magnetic field.
2.1.2 Charge to Mass Ratio of Electron By carrying out accurate measurements on
In 1897, British physicist J.J. Thomson the amount of deflections observed by the
measured the ratio of electrical charge (e) to electrons on the electric field strength or
the mass of electron (me ) by using cathode ray magnetic field strength, Thomson was able to
tube and applying electrical and magnetic field determine the value of e/me as:
perpendicular to each other as well as to the
e
path of electrons (Fig. 2.2). When only electric
m e = 1.758820 × 10 C kg (2.1)
11 –1
field is applied, the electrons deviate from their

path and hit the cathode ray tube at point A Where me is the mass of the electron in kg and
(Fig. 2.2). Similarly when only magnetic field e is the magnitude of the charge on the electron
is applied, electron strikes the cathode ray tube in coulomb (C). Since electrons are negatively
at point C. By carefully balancing the electrical charged, the charge on electron is –e.
and magnetic field strength, it is possible to
bring back the electron to the path which is 2.1.3 Charge on the Electron
followed in the absence of electric or magnetic R.A. Millikan (1868-1953) devised a method
field and they hit the screen at point B. known as oil drop experiment (1906-14), to
Thomson argued that the amount of deviation determine the charge on the electrons. He found
of the particles from their path in the presence the charge on the electron to be
of electrical or magnetic field depends upon: – 1.6 × 10–19 C. The present accepted value of
electrical charge is – 1.602176 × 10–19 C. The
(i) the magnitude of the negative charge on
mass of the electron (me) was determined by
the particle, greater the magnitude of the
combining these results with Thomson’s value
charge on the particle, greater is the
of e/me ratio.
interaction with the electric or magnetic
field and thus greater is the deflection.
(ii) the mass of the particle — lighter the
particle, greater the deflection. = 9.1094×10–31 kg (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 modified
In this method, oil droplets in the form of
cathode ray tube led to the discovery of canal
mist, produced by the atomiser, were allowed
rays carrying positively charged particles. The
to enter through a tiny hole in the upper plate
characteristics of these positively charged of electrical condenser. The downward motion
particles are listed below. of these droplets was viewed through the
(i) Unlike cathode rays, mass of positively telescope, equipped with a micrometer eye
charged particles depends upon the piece. By measuring the rate of fall of these
nature of gas present in the cathode ray droplets, Millikan was able to measure the
tube. These are simply the positively mass of oil droplets. The air inside the
charged gaseous ions. chamber was ionized by passing a beam of
X-rays through it. The electrical charge on
(ii) The charge to mass ratio of the particles
these oil droplets was acquired by collisions
depends on the gas from which these with gaseous ions. The fall of these charged
originate. oil droplets can be retarded, accelerated or
(iii) Some of the positively charged particles made stationary depending upon the charge
carry a multiple of the fundamental unit on the droplets and the polarity and strength
of electrical charge. of the voltage applied to the plate. By carefully
(iv) The behaviour of these particles in the measuring the effects of electrical field
strength on the motion of oil droplets,
magnetic or electrical field is opposite to
Millikan concluded that the magnitude of
that observed for electron or cathode electrical charge, q, on the droplets is always
rays. an integral multiple of the electrical charge,
The smallest and lightest positive ion was e, that is, q = n e, where n = 1, 2, 3... .
obtained from hydrogen and was called
proton. This positively charged particle was
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
α-particles. When electrically neutral particles
having a mass slightly greater than that of
protons were emitted. He named these
particles as neutrons. The important
properties of all these fundamental particles
are given in Table 2.1.
Fig. 2.3 The Millikan oil drop apparatus for
2.2 ATOMIC MODELS
measuring charge ‘e’. In chamber, the
Observations obtained from the experiments forces acting on oil drop are:
mentioned in the previous sections have gravitational, electrostatic due to
suggested that Dalton’s indivisible atom is electrical field and a viscous drag force
composed of sub-atomic particles carrying when the oil drop is moving.
positive and negative charges. The major
problems before the scientists after the • to explain the formation of different kinds
discovery of sub-atomic particles were: of molecules by the combination of different
• to account for the stability of atom, atoms and,
• to compare the behaviour of elements in • to understand the origin and nature of the
terms of both physical and chemical characteristics of electromagnetic radiation
properties, absorbed or emitted by atoms.
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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 century
particles in an atom. Although some of these different kinds of rays were discovered,
models were not able to explain the stability of besides those mentioned earlier. Wilhalm
atoms, two of these models, one proposed by Röentgen (1845-1923) in 1895 showed
J.J. Thomson and the other proposed by that when electrons strike a material in
Ernest Rutherford are discussed below. the cathode ray tubes, produce rays
2.2.1 Thomson Model of Atom which can cause fluorescence in the
fluorescent materials placed outside the
J. J. Thomson, in 1898, proposed that an atom
cathode ray tubes. Since Röentgen did not
possesses a spherical shape (radius
know the nature of the radiation, he
approximately 10–10 m) in which the positive
named them X-rays and the name is still
charge is uniformly distributed. The electrons
carried on. It was noticed that X-rays are
are embedded into it in such a manner as to
give the most stable electrostatic arrangement produced effectively when electrons strike
(Fig. 2.4). Many different names are given to the dense metal anode, called targets.
this model, for example, plum pudding, raisin These are not deflected by the electric and
pudding or watermelon. This model can be magnetic fields and have a 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).
Henri Becqueral (1852-1908)
observed that there are certain elements
Fig.2.4 Thomson model of atom which emit radiation on their own and
visualised as a pudding or watermelon of named this phenomenon as
positive charge with plums or seeds (electrons) radioactivity and the elements known
embedded into it. An important feature of this as radioactive elements. This field was
model is that the mass of the atom is assumed developed by Marie Curie, Piere Curie,
to be uniformly distributed over the atom. Rutherford and Fredrick Soddy. It was
Although this model was able to explain the observed that three kinds of rays i.e., α,
overall neutrality of the atom, but was not β- and γ-rays are emitted. Rutherford
consistent with the results of later experiments. found that α-rays consists of high energy
Thomson was awarded Nobel Prize for physics particles carrying two units of positive
in 1906, for his theoretical and experimental charge and four unit of atomic mass. He
investigations on the conduction of electricity concluded that α- particles are helium
by gases.
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34 CHEMISTRY
nuclei as when α- particles combined with represented in Fig. 2.5. A stream of high energy
two electrons yielded helium gas. β-rays α–particles from a radioactive source was
are negatively charged particles similar to directed at a thin foil (thickness ∼ 100 nm) of
electrons. The γ-rays are high energy gold metal. The thin gold foil had a circular
radiations like X-rays, are neutral in fluorescent zinc sulphide screen around it.
nature and do not consist of particles. As Whenever α–particles struck the screen, a tiny
regards penetrating power, α-particles are flash of light was produced at that point.
the least, followed by β-rays (100 times The results of scattering experiment were
that of α–particles) and γ-rays (1000 times quite unexpected. According to Thomson
of that α-particles). model of atom, the mass of each gold atom in
the foil should have been spread evenly over
2.2.2 Rutherford’s Nuclear Model of Atom the entire atom, and α– particles had enough
energy to pass directly through such a uniform
Rutherford and his students (Hans Geiger and distribution of mass. It was expected that the
Ernest Marsden) bombarded very thin gold foil particles would slow down and change
with α–particles. Rutherford’s famous
directions only by a small angles as they passed
α –particle scattering experiment is
through the foil. It was observed that:
(i) most of the α–particles passed through
the gold foil undeflected.
(ii) a small fraction of the α–particles was
deflected by small angles.
(iii) a very few α–particles (∼1 in 20,000)
bounced back, that is, were deflected by
nearly 180°.
On the basis of the observations,
A. Rutherford’s scattering experiment Rutherford drew the following conclusions
regarding the structure of atom:
(i) Most of the space in the atom is empty as
most of the α–particles passed through
the foil undeflected.
(ii) A few positively charged α–particles were
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 α–particles.
B. Schematic molecular view of the gold foil (iii) Calculations by Rutherford showed that
the volume occupied by the nucleus is
Fig. 2.5 Schematic view of Rutherford’s negligibly small as compared to the total
scattering experiment. When a beam volume of the atom. The radius of the
of alpha (α) particles is “shot” at a thin atom is about 10–10 m, while that of
gold foil, most of them pass through nucleus is 10–15 m. One can appreciate
without much effect. Some, however, this difference in size by realising that if
are deflected.
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a cricket ball represents a nucleus, then The total number of nucleons is termed as
the radius of atom would be about 5 km. mass number (A) of the atom.
On the basis of above observations and mass number (A) = number of protons (Z )
conclusions, Rutherford proposed the nuclear + number of
model of atom. According to this model: neutrons (n) (2.4)
(i) The positive charge and most of the mass
2.2.4 Isobars and Isotopes
of the atom was densely concentrated in
extremely small region. This very small The composition of any atom can be
portion of the atom was called nucleus represented by using the normal element
by Rutherford. symbol (X) with super-script on the left hand
(ii) The nucleus is surrounded by electrons side as the atomic mass number (A) and
that move around the nucleus with a very subscript (Z ) on the left hand side as the atomic
high speed in circular paths called orbits. number (i.e., AZ X).
Thus, Rutherford’s model of atom Isobars are the atoms with same mass
resembles the solar system in which the number but different atomic number for
14 14
nucleus plays the role of sun and the example, 6 C and 7 N. On the other hand, atoms
electrons that of revolving planets. with identical atomic number but different
(iii) Electrons and the nucleus are held atomic mass number are known as Isotopes.
together by electrostatic forces of In other words (according to equation 2.4), it
attraction. is evident that difference between the isotopes
is due to the presence of different number of
2.2.3 Atomic Number and Mass Number neutrons present in the nucleus. For example,
The presence of positive charge on the considering of hydrogen atom again, 99.985%
nucleus is due to the protons in the nucleus. of hydrogen atoms contain only one proton.
As established earlier, the charge on the 1
This isotope is called protium (1 H). Rest of the
proton is equal but opposite to that of percentage of hydrogen atom contains two other
electron. The number of protons present in
isotopes, the one containing 1 proton and 1
the nucleus is equal to atomic number (Z ). 2
neutron is called deuterium (1 D, 0.015%)
For example, the number of protons in the
and the other one possessing 1 proton and 2
hydrogen nucleus is 1, in sodium atom it is 3
11, therefore their atomic numbers are 1 and neutrons is called tritium ( 1 T ). The latter
11 respectively. In order to keep the electrical isotope is found in trace amounts on the earth.
neutrality, the number of electrons in an Other examples of commonly occuring
atom is equal to the number of protons isotopes are: carbon atoms containing 6, 7 and
(atomic number, Z ). For example, number of 8 neutrons besides 6 protons ( 12 13 14
6 C, 6 C, 6 C
);
electrons in hydrogen atom and sodium atom chlorine atoms containing 18 and 20 neutrons
are 1 and 11 respectively. besides 17 protons ( 17 35 37
Cl, 17 Cl ).
Atomic number (Z) = number of protons in Lastly an important point to mention
the nucleus of an atom regarding isotopes is that chemical properties
= number of electrons of atoms are controlled by the number of
in a nuetral atom (2.3) electrons, which are determined by the
number of protons in the nucleus. Number of
While the positive charge of the nucleus
is due to protons, the mass of the nucleus, neutrons present in the nucleus have very little
due to protons and neutrons. As discussed effect on the chemical properties of an element.
earlier protons and neutrons present in the Therefore, all the isotopes of a given element
nucleus are collectively known as nucleons. show same chemical behaviour.
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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 35 Br
. shows that the planets describe well-defined
Solution orbits around the sun. The gravitational force
In this case, 80
35 Br
, Z = 35, A = 80, species between the planets is given by the expression
is neutral
 m1m 2 
Number of protons = number of electrons  G. 2  where m1 and m2 are the masses, r
= Z = 35 r
Number of neutrons = 80 – 35 = 45, is the distance of separation of the masses and
(equation 2.4) G is the gravitational constant. The theory can
also calculate precisely the planetary orbits and
Problem 2.2 these are in agreement with the experimental
The number of electrons, protons and measurements.
neutrons in a species are equal to 18, 16 The similarity between the solar system
and 16 respectively. Assign the proper and nuclear model suggests that electrons
symbol to the species. should move around the nucleus in well
Solution defined orbits. Further, the coulomb force
The atomic number is equal to (kq1q2/r2 where q1 and q2 are the charges, r is
number of protons = 16. The element is the distance of separation of the charges and
sulphur (S). k is the proportionality constant) between
electron and the nucleus is mathematically
Atomic mass number = number of
similar to the gravitational force. However,
protons + number of neutrons
when a body is moving in an orbit, it
= 16 + 16 = 32 undergoes acceleration even if it is moving with
Species is not neutral as the number of a constant speed in an orbit because of
protons is not equal to electrons. It is changing direction. So an electron in the
anion (negatively charged) with charge nuclear model describing planet like orbits is
equal to excess electrons = 18 – 16 = 2. under acceleration. According to the
32 2–
Symbol is 16 S . electromagnetic theory of Maxwell, charged
A
Note : Before using the notation Z X, find particles when accelerated should emit
electromagnetic radiation (This feature does
out whether the species is a neutral atom,
a cation or an anion. If it is a neutral atom, not exist for planets since they are uncharged).
Therefore, an electron in an orbit will emit
equation (2.3) is valid, i.e., number of
protons = number of electrons = atomic radiation, the energy carried by radiation
comes from electronic motion. The orbit will
number. If the species is an ion, determine
thus continue to shrink. Calculations show
whether the number of protons are larger
that it should take an electron only 10–8 s to
(cation, positive ion) or smaller (anion,
spiral into the nucleus. But this does not
negative ion) than the number of electrons.
happen. Thus, the Rutherford model
Number of neutrons is always given by
cannot explain the stability of an atom.
A–Z, whether the species is neutral or ion.
If the motion of an electron is described on the
basis of the classical mechanics and
2.2.5 Drawbacks of Rutherford Model
electromagnetic theory, you may ask that
As you have learnt above, Rutherford nuclear since the motion of electrons in orbits is
model of an atom is like a small scale solar leading to the instability of the atom, then
system with the nucleus playing 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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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 facts
pull the electrons toward the nucleus to form about electromagnetic radiations.
a miniature version of Thomson’s model James Maxwell (1870) was the first to give
of atom. a comprehensive explanation about the
Another serious drawback of the interaction between the charged bodies and
Rutherford model is that it says nothing about the behaviour of electrical and magnetic fields
distribution of the electrons around the on macroscopic level. He suggested that when
nucleus and the energies of these electrons. electrically charged particle moves under
accelaration, alternating electrical and
2.3 DEVELOPMENTS LEADING TO THE
magnetic fields are produced and transmitted.
BOHR’S MODEL OF ATOM
These fields are transmitted in the forms of
Historically, results observed from the studies waves called electromagnetic waves or
of interactions of radiations with matter have electromagnetic radiation.
provided immense information regarding the
Light is the form of radiation known from
structure of atoms and molecules. Neils Bohr
early days and speculation about its nature
utilised these results to improve upon the
dates back to remote ancient times. In earlier
model proposed by Rutherford. Two
days (Newton) light was supposed to be made
developments played a major role in the
of particles (corpuscules). It was only in the
formulation of Bohr’s model of atom. These
19th century when wave nature of light was
were:
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
radiation by heated objects. These are called Fig.2.6 The electric and magnetic field
thermal radiations. They tried to find out of components of an electromagnetic wave.
what the thermal radiation is made. It is now These components have the same
a well-known fact that thermal radiations wavelength, frequency, speed and
amplitude, but they vibrate in two
consist of electromagnetic waves of various
mutually perpendicular planes.
frequencies or wavelengths. It is based on a
number of modern concepts, which were
Although electromagnetic wave motion is
unknown in the mid-nineteenth century. First
complex in nature, we will consider here only
active study of thermal radiation laws occured
a few simple properties.
in the 1850’s and the theory of electromagnetic
waves and the emission of such waves by (i) The oscillating electric and magnetic fields
accelerating charged particles was developed produced by oscillating charged particles
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38 CHEMISTRY
are perpendicular to each other and both (iv) Different kinds of units are used to
are perpendicular to the direction of represent electromagnetic radiation.
propagation of the wave. Simplified
These radiations are characterised by the
picture of electromagnetic wave is shown
in Fig. 2.6. properties, namely, frequency ( ν ) and
wavelength (λ).
(ii) Unlike sound waves or waves produced
in water, electromagnetic waves do not The SI unit for frequency ( ν ) is hertz
require medium and can move in (Hz, s–1), after Heinrich Hertz. It is defined as
vacuum. the number of waves that pass a given point
(iii) It is now well established that there are in one second.
many types of electromagnetic radiations, Wavelength should have the units of length
which differ from one another in and as you know that the SI units of length is
wavelength (or frequency). These
meter (m). Since electromagnetic radiation
constitute what is called electromagnetic
consists of different kinds of waves of much
spectrum (Fig. 2.7). Different regions of
the spectrum are identified by different smaller wavelengths, smaller units are used.
names. Some examples are: radio Fig.2.7 shows various types of electro-
frequency region around 106 Hz, used for magnetic radiations which differ from one
broadcasting; microwave region around another in wavelengths and frequencies.
1010 Hz used for radar; infrared region In vaccum all types of electromagnetic
around 10 13 Hz used for heating; radiations, regardless of wavelength, travel at
ultraviolet region around 10 16 Hz a
the same speed, i.e., 3.0 × 108 m s–1 (2.997925
component of sun’s radiation. The small
× 108 m s–1, to be precise). This is called speed
portion around 10 15 Hz, is what is
ordinarily called visible light. It is only of light and is given the symbol ‘c‘. The
this part which our eyes can see (or frequency (ν ), wavelength (λ) and velocity of light
detect). Special instruments are required (c) are related by the equation (2.5).
to detect non-visible radiation. c=ν λ (2.5)
ν
(a)
(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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The other commonly used quantity

specially in spectroscopy, is the wavenumber Frequency of red light
( ). It is defined as the number of wavelengths
per unit length. Its units are reciprocal of ν= = 4.00 × 1014 Hz
wavelength unit, i.e., m–1. However commonly The range of visible spectrum is from
used unit is cm–1 (not SI unit). 4.0 × 1014 to 7.5 × 1014 Hz in terms of
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? λ=5800Å = 5800 × 10–8 cm
Solution = 5800 × 10–10 m
The wavelength, λ, is equal to c/ν, where
c is the speed of electromagnetic radiation
in vacuum and ν is the frequency.
Substituting the given values, we have
c
λ=
v
(b) Calculation of the frequency (ν )
2.3.2 Particle Nature of Electromagnetic

Radiation: Planck’s Quantum
Theory
This is a characteristic radiowave Some of the experimental phenomenon such
wavelength. as diffraction* and interference** can be
Problem 2.4 explained by the wave nature of the
electromagnetic radiation. However, following
The wavelength range of the visible
are some of the observations which could not
spectrum extends from violet (400 nm) to
be explained with the help of even the
red (750 nm). Express these wavelengths
electromagentic theory of 19th century
in frequencies (Hz). (1nm = 10–9 m)
physics (known as classical physics):
Solution
(i) the nature of emission of radiation from
Using equation 2.5, frequency of violet
hot bodies (black -body radiation)
light
(ii) ejection of electrons from metal surface
when radiation strikes it (photoelectric
effect)
= 7.50 × 1014 Hz (iii) variation of heat capacity of solids as a
function of temperature
* 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.
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(iv) Line spectra of atoms with special of radiant energy. Furthermore, a black body
reference to hydrogen. is in thermal equilibrium with its surroundings.
These phenomena indicate that the system It radiates same amount of energy per unit area
can take energy only in discrete amounts. All as it absorbs from its surrounding in any given
possible energies cannot be taken up or time. The amount of light emitted (intensity of
radiated. radiation) from a black body and its spectral
It is noteworthy that the first concrete distribution depends only on its temperature.
explanation for the phenomenon of the black At a given temperature, intensity of radiation
body radiation mentioned above was given by emitted increases with the increase of
Max Planck in 1900. Let us first try to wavelength, reaches a maximum value at a
understand this phenomenon, which is given given wavelength and then starts decreasing
below: with further increase of wavelength, as shown
Hot objects emit electromagnetic radiations in Fig. 2.8. Also, as the temperature increases,
over a wide range of wavelengths. At high maxima of the curve shifts to short wavelength.
temperatures, an appreciable proportion of Several attempts were made to predict the
radiation is in the visible region of the intensity of radiation as a function of
spectrum. As the temperature is raised, a wavelength.
higher proportion of short wavelength (blue But the results of the above experiment
light) is generated. For example, when an iron could not be explained satisfactorily on the
rod is heated in a furnace, it first turns to dull basis of the wave theory of light. Max Planck
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 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 Fig. 2.8 Wavelength-intensity relationship
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 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 Fig. 2.8(a) Black body
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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 physicist,
i.e., atoms in the wall of black body. Their
received his Ph.D in theoretical
frequency of oscillation is changed by
interaction with oscilators of electromagnetic physics from the University of
radiation. Planck assumed that radiation Munich in 1879. In 1888, he was
could be sub-divided into discrete chunks of appointed Director of the Institute
energy. He suggested that atoms and of Theoretical Physics at the
molecules could emit or absorb energy only University of Berlin. Planck was awarded the Nobel
in discrete quantities and not in a continuous Prize in Physics in 1918 for his quantum theory.
manner. He gave the name quantum to the Planck also made significant contributions in
smallest quantity of energy that can be thermodynamics and other areas of physics.
emitted or absorbed in the form of
electromagnetic radiation. The energy (E ) of a Photoelectric Effect
quantum of radiation is proportional In 1887, H. Hertz performed a very interesting
to its frequency (ν ) and is expressed by experiment in which electrons (or electric
equation (2.6). current) were ejected when certain metals (for
E = hυ (2.6) example potassium, rubidium, caesium etc.)
The proportionality constant, ‘h’ is known were exposed to a beam of light as shown
as Planck’s constant and has the value in Fig.2.9. The phenomenon is called
6.626×10–34 J s. Photoelectric effect. The results observed in
this experiment were:
With this theory, Planck was able to explain
the distribution of intensity in the radiation (i) The electrons are ejected from the metal
from black body as a function of frequency or surface as soon as the beam of light strikes
wavelength at different temperatures. the surface, i.e., there is no time lag
between the striking of light beam and the
Quantisation has been compared to
ejection of electrons from the metal surface.
standing on a staircase. A person can stand
on any step of a staircase, but it is not possible (ii) The number of electrons ejected is
for him/her to stand in between the two steps. proportional to the intensity or brightness
The energy can take any one of the values from of light.
the following set, but cannot take on any (iii) For each metal, there is a characteristic
values between them. minimum frequency,ν0 (also known as
E = 0, hυ, 2hυ, 3hυ....nhυ..... threshold frequency) below which
photoelectric effect is not observed. At a
frequency ν >ν 0, the ejected electrons 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, number of electrons
ejected and kinetic energy associated with
Fig.2.9 Equipment for studying the photoelectric them should depend on the brightness of light.
effect. Light of a particular frequency strikes
a clean metal surface inside a vacuum
It has been observed that though the number
chamber. Electrons are ejected from the of electrons ejected does depend upon the
metal and are counted by a detector that brightness of light, the kinetic energy of the
measures their kinetic energy.
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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 electron
light [ν = (4.3 to 4.6) × 1014 Hz] of any brightness is hν0 (also called work function, W0 ; Table 2.2),
(intensity) may shine on a piece of potassium then the difference in energy
metal for hours but no photoelectrons are (hν – hν0 ) is transferred as the kinetic energy of
ejected. But, as soon as even a very weak yellow the photoelectron. Following the conservation
light (ν = 5.1–5.2 × 1014 Hz) shines on the of energy principle, the kinetic energy of the
potassium metal, the photoelectric effect is ejected electron is given by the equation 2.7.
observed. The threshold frequency (ν0) for
potassium metal is 5.0×1014 Hz. (2.7)
Einstein (1905) was able to explain the
photoelectric effect using Planck’s quantum where me is the mass of the electron and v is
theory of electromagnetic radiation as a the velocity associated with the ejected electron.
starting point. Lastly, a more intense beam of light consists
Albert Einstein, a German of larger number of photons, consequently the
born American physicist, is number of electrons ejected is also larger as
regarded by many as one of compared to that in an experiment in which a
the two great physicists the beam of weaker intensity of light is employed.
world has known (the other
is Isaac Newton). His three
Dual Behaviour of Electromagnetic
research papers (on special Radiation
relativity, Brownian motion The particle nature of light posed a dilemma
Albert Einstein
and the photoelectric effect)
(1879-1955)
for scientists. On the one hand, it could explain
which he published in 1905,
the black body radiation and photoelectric
while he was employed as a technical
assistant in a Swiss patent office in Ber ne
effect satisfactorily but on the other hand, it
have profoundly influenced the development was not consistent with the known wave
of physics. He received the Nobel Prize in behaviour of light which could account for the
Physics in 1921 for his explanation of the phenomena of interference and diffraction. The
photoelectric effect. only way to resolve the dilemma was to accept
the idea that light possesses both particle and
Shining a beam of light on to a metal wave-like properties, i.e., light has dual
surface can, therefore, be viewed as shooting behaviour. Depending on the experiment, we
a beam of particles, the photons. When a find that light behaves either as a wave or as a
photon of sufficient energy strikes an electron stream of particles. Whenever radiation
in the atom of the metal, it transfers its energy
interacts with matter, it displays particle like
instantaneously to the electron during the
properties in contrast to the wavelike
collision and the electron is ejected without
properties (interference and diffraction), which
any time lag or delay. Greater the energy
it exhibits when it propagates. This concept
possessed by the photon, greater will be
transfer of energy to the electron and greater was totally alien to the way the scientists
the kinetic energy of the ejected electron. In thought about matter and radiation and it took
other words, kinetic energy of the ejected them a long time to become convinced of its
electron is proportional to the frequency of the validity. It turns out, as you shall see later,
electromagnetic radiation. Since the striking that some microscopic particles like electrons
photon has energy equal to hν and the 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)
2020-21
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 = hν The energy of one mole of photons
–34
h = 6.626 ×10 Js = 6.626 ×10–19 J × 6.022 ×1023 mol–1
ν = 5×10 s (given)
14 –1
= 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
5 –1
Energy of one mole of photons = (3.99 –1.68) 10 J mol
5 –1
= (3.313 ×10–19 J) × (6.022 × 1023 mol–1) = 2.31 × 10 J mol
= 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 second This corresponds to the wavelength
by the bulb.
Solution hc
∴λ=
Power of the bulb = 100 watt E
= 100 J s
–1 6.626 × 10 −34 J s × 3.0 × 108 m s −1
=
Energy of one photon E = hν = hc/λ 3.84 × 10 −19 J
= 517 nm
6.626 × 10 −34 J s × 3 × 108 m s−1
= (This corresponds to green light)
400 × 10 −9 m
Problem 2.9
= 4.969 × 10 J
-19
The threshold frequency ν0 for a metal is
Number of photons emitted 14 –1
7.0 ×10 s . Calculate the kinetic energy
of an electron emitted when radiation of
100 J s−1 15 –1
= 2.012 × 1020 s −1 frequency ν =1.0 ×10 s hits the metal.
4.969 × 10 −19 J
Solution
Problem 2.8 According to Einstein’s equation
2
When electromagnetic radiation of Kinetic energy = ½ mev =h(ν – ν0 )
wavelength 300 nm falls on the surface –34 15 –1
= (6.626 ×10 J s) (1.0 × 10 s – 7.0
of sodium, electrons are emitted with a 14 –1
×10 s )
kinetic energy of 1.68 ×105 J mol–1. What –34 14 –1
= (6.626 ×10 J s) (10.0 ×10 s – 7.0
is the minimum energy needed to remove 14 –1
×10 s )
an electron from sodium? What is the –34 14 –1
maximum wavelength that will cause a = (6.626 ×10 J s) × (3.0 ×10 s )
–19
photoelectron to be emitted? = 1.988 ×10 J
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44 CHEMISTRY
2.3.3 Evidence for the quantized* spectrum. A continuum of radiation is passed

Electronic Energy Levels: Atomic through a sample which absorbs radiation of
spectra certain wavelengths. The missing wavelength
The speed of light depends upon the nature of which corresponds to the radiation absorbed
by the matter, leave dark spaces in the bright
the medium through which it passes. As a
continuous spectrum.
result, the beam of light is deviated or refracted
The study of emission or absorption
from its original path as it passes from one
spectra is referred to as spectroscopy. The
medium to another. It is observed that when a
spectrum of the visible light, as discussed
ray of white light is passed through a prism,
above, was continuous as all wavelengths (red
the wave with shorter wavelength bends more to violet) of the visible light are represented in
than the one with a longer wavelength. Since the spectra. The emission spectra of atoms in
ordinary white light consists of waves with all the gas phase, on the other hand, do not show
the wavelengths in the visible range, a ray of a continuous spread of wavelength from red
white light is spread out into a series of to violet, rather they emit light only at specific
coloured bands called spectrum. The light of wavelengths with dark spaces between them.
red colour which has longest wavelength is Such spectra are called line spectra or atomic
deviated the least while the violet light, which spectra because the emitted radiation is
has shortest wavelength is deviated the most. identified by the appearance of bright lines in
The spectrum of white light, that we can see, the spectra (Fig. 2.10 page 45).
ranges from violet at 7.50 × 1014 Hz to red at Line emission spectra are of great
4×10 14 Hz. Such a spectrum is called interest in the study of electronic structure.
continuous spectrum. Continuous because Each element has a unique line emission
violet merges into blue, blue into green and so spectrum. The characteristic lines in atomic
on. A similar spectrum is produced when a spectra can be used in chemical analysis to
rainbow forms in the sky. Remember that identify unknown atoms in the same way as
visible 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 matter, spectrum of the atoms of a known element with
atoms and molecules may absorb energy and the lines from an unknown sample quickly
reach to a higher energy state. With higher establishes the identity of the latter, German
energy, these are in an unstable state. For chemist, Robert Bunsen (1811-1899) was one
returning to their normal (more stable, lower of the first investigators to use line spectra to
energy states) energy state, the atoms and identify elements.
molecules emit radiations in various regions Elements like rubidium (Rb), caesium (Cs)
of the electromagnetic spectrum. thallium (Tl), indium (In), gallium (Ga) and
scandium (Sc) were discovered when their
Emission and Absorption Spectra minerals were analysed by spectroscopic
The spectrum of radiation emitted by a methods. The element helium (He) was
substance that has absorbed energy is called discovered in the sun by spectroscopic method.
an emission spectrum. Atoms, molecules or Line Spectrum of Hydrogen
ions that have absorbed radiation are said to
be “excited”. To produce an emission When an electric discharge is passed through
spectrum, energy is supplied to a sample by gaseous hydrogen, the H2 molecules dissociate
heating it or irradiating it and the wavelength and the energetically excited hydrogen atoms
(or frequency) of the radiation emitted, as the produced emit electromagnetic radiation of
sample gives up the absorbed energy, is discrete frequencies. The hydrogen spectrum
recorded. consists of several series of lines named after
An absorption spectrum is like the their discoverers. Balmer showed in 1885 on
photographic negative of an emission the basis of experimental observations that if
* The restriction of any property to discrete values is called quantization.
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(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 five
hydrogen spectrum obey the following formula: series of lines that correspond to n1 = 1, 2, 3,
4, 5 are known as Lyman, Balmer, Paschen,
(2.8) Bracket and Pfund series, respectively,
Table 2.3 shows these series of transitions in
where n is an integer equal to or greater than the hydrogen spectrum. Fig 2.11 (page, 46)
3 (i.e., n = 3,4,5,....) shows the Lyman, Balmer and Paschen series
The series of lines described by this formula of transitions for hydrogen atom.
are called the Balmer series. The Balmer series Of all the elements, hydrogen atom has the
of lines are the only lines in the hydrogen simplest line spectrum. Line spectrum becomes
spectrum which appear in the visible region
Table 2.3 The Spectral Lines for Atomic
of the electromagnetic spectrum. The Swedish Hydrogen
spectroscopist, Johannes Rydberg, noted 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......
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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 does not take
place in a continuous manner.
Angular Momentum
Just as linear momentum is the product
of mass (m) and linear velocity (v), angular
momentum is the product of moment of
Fig. 2.11 T ransitions of the electron in the inertia (I) and angular velocity (ω). For an
hydrogen atom (The diagram shows electron of mass me, moving in a circular
the Lyman, Balmer and Paschen series path of radius r around the nucleus,
of transitions)
angular momentum = I × ω
more and more complex for heavier atom. There
Since I = mer2, and ω = v/r where v is the
are, however, certain features which are
linear velocity,
common to all line spectra, i.e., (i) line spectrum
of element is unique and (ii) there is regularity ∴angular momentum = mer2 × v/r = mevr
in the line spectrum of each element. The
questions which arise are: What are the iii) The frequency of radiation absorbed or
reasons for these similarities? Is it something emitted when transition occurs between
to do with the electronic structure of atoms? two stationary states that differ in energy
These are the questions need to be answered. by ∆E, is given by:
We shall find later that the answers to these ∆E E 2 − E1
questions provide the key in understanding ν= = (2.10)
h h
electronic structure of these elements.
Where E1 and E2 are the energies of the
2.4 BOHR’S MODEL FOR HYDROGEN lower and higher allowed energy states
ATOM respectively. This expression is commonly
Neils Bohr (1913) was the first to explain known as Bohr’s frequency rule.
quantitatively the general features of the iv) The angular momentum of an electron is
structure of hydrogen atom and its spectrum. quantised. In a given stationary state it
He used Planck’s concept of quantisation of can be expressed as in equation (2.11)
energy. Though the theory is not the modern h
quantum mechanics, it can still be used to m e v r = n. n = 1,2,3..... (2.11)
2π
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Where me is the mass of electron, v is the

velocity and r is the radius of the orbit in which Niels Bohr
(1885–1962)
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 Ph.D.
integral multiple of h/2π. That means angular from the University of
momentum is quantised. Radiation is emitted Copenhagen in 1911. He
or obsorbed only when transition of electron then spent a year with J.J.
takes place from one quantised value of angular Thomson and Er nest Rutherford in England.
momentum to another. Therefore, Maxwell’s In 1913, he returned to Copenhagen where
electromagnetic theory does not apply here that he remained for the rest of his life. In 1920
is why only certain fixed orbits are allowed. he was named Director of the Institute of
The details regarding the derivation of theoretical Physics. After first World War,
energies of the stationary states used by Bohr, Bohr worked energetically for peaceful uses
are quite complicated and will be discussed in of atomic energy. He received the first Atoms
higher classes. However, according to Bohr’s for Peace award in 1957. Bohr was awarded
theory for hydrogen atom: the Nobel Prize in Physics in 1922.
a) The stationary states for electron are Fig. 2.11 depicts the energies of different
numbered n = 1,2,3.......... These integral stationary states or energy levels of hydrogen
numbers (Section 2.6.2) are known as atom. This representation is called an energy
Principal quantum numbers. level diagram.
b) The radii of the stationary states are
When the electron is free from the influence
expressed as: of nucleus, the energy is taken as zero. The
rn = n2 a0 (2.12) electron in this situation is associated with the
where a0 = 52.9 pm. Thus the radius of stationary state of Principal Quantum number
the first stationary state, called the Bohr = n = ∞ and is called as ionized hydrogen atom.
orbit, is 52.9 pm. Normally the electron When the electron is attracted by the nucleus
in the hydrogen atom is found in this orbit and is present in orbit n, the energy is emitted
(that is n=1). As n increases the value of r
will increase. In other words the electron What does the negative electronic
will be present away from the nucleus. energy (En) for hydrogen atom mean?
c) The most important property associated The energy of the electron in a hydrogen
with the electron, is the energy of its atom has a negative sign for all possible
stationary state. It is given by the orbits (eq. 2.13). What does this negative
expression. sign convey? This negative sign means that
the energy of the electron in the atom is
 1 lower than the energy of a free electron at
En = − R H  2  n = 1,2,3.... (2.13)
n  rest. A free electron at rest is an electron
that is infinitely far away from the nucleus
where RH is called Rydberg constant and its
and is assigned the energy value of zero.
value is 2.18×10–18 J. The energy of the lowest
Mathematically, this corresponds to
state, also called as the ground state, is setting n equal to infinity in the equation
1 (2.13) so that E∞=0. As the electron gets
E1 = –2.18×10–18 ( ) = –2.18×10–18 J. The closer to the nucleus (as n decreases), En
12
becomes larger in absolute value and more
energy of the stationary state for n = 2, will and more negative. The most negative
1 energy value is given by n=1 which
be : E2 = –2.18×10–18J ( )= –0.545×10–18 J. corresponds to the most stable orbit. We
22 call this the ground state.
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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 =  − 2H  −  − 2H  (where n and n
(2.13) and depicts its stability relative to the  nf   ni  i f
reference state of zero energy and n = ∞. stand for initial orbit and final orbits)
d) Bohr’s theory can also be applied to the
ions containing only one electron, similar  1 1 −18  1 1
∆E = R H  2 − 2  = 2.18 × 10 J  2 − 2 
to that present in hydrogen atom. For  n i nf   ni nf 
example, He+ Li2+, Be3+ and so on. The
energies of the stationary states associated (2,17)
with these kinds of ions (also known as The frequency (ν ) associated with the
hydrogen like species) are given by the absorption and emission of the photon can be
expression. evaluated by using equation (2.18)
 Z2 ∆ E RH  1 1
E n = − 2.18 × 10 −18  2  J (2.14) ν= =  2
− 2
n  h h  ni nf 
and radii by the expression
2.18 × 10 −18 J  1 1
2
52.9 (n ) = −34  2
− 2 (2.18)
rn = pm (2.15) 6.626 × 10 J s  n i n f 
Z
where Z is the atomic number and has values  1 1
= 3.29 × 1015  2 − 2  Hz (2.19)
2,3 for the helium and lithium atoms  ni n f 
respectively. From the above equations, it is
and in terms of wavenumbers ( )
evident that the value of energy becomes more
negative and that of radius becomes smaller ν RH  1 − 1 
ν= = (2.20)
with increase of Z . This means that electron c hc  n i2 n f2 
will be tightly bound to the nucleus.
e) It is also possible to calculate the velocities 3.29 × 1015 s−1  1 1
of electrons moving in these orbits. = 8 −s  2
− 2
3 × 10 m s  n i n f 
Although the precise equation is not given
here, qualitatively the magnitude of
velocity of electron increases with increase  1 1
= 1.09677 × 107  2 − 2  m −1 (2.21)
of positive charge on the nucleus and  ni nf 
decreases with increase of principal
quantum number. In case of absorption spectrum, nf > ni and
the term in the parenthesis is positive and energy
2.4.1 Explanation of Line Spectrum of is absorbed. On the other hand in case of
Hydrogen emission spectrum ni > nf , ∆ E is negative and
Line spectrum observed in case of hydrogen energy is released.
atom, as mentioned in section 2.3.3, can be The expression (2.17) is similar to that used
explained quantitatively using Bohr’s model. by Rydberg (2.9) derived empirically using the
According to assumption 2, radiation (energy) experimental data available at that time. Further,
is absorbed if the electron moves from the orbit each spectral line, whether in absorption or
of smaller Principal quantum number to the emission spectrum, can be associated to the
orbit of higher Principal quantum number, particular transition in hydrogen atom. In case
whereas the radiation (energy) is emitted if the of large number of hydrogen atoms, different
electron moves from higher orbit to lower orbit. possible transitions can be observed and thus
The energy gap between the two orbits is given leading to large number of spectral lines. The
by equation (2.16) brightness or intensity of spectral lines depends
upon the number of photons of same wavelength
∆E = Ef – Ei (2.16)
or frequency absorbed or emitted.
Combining equations (2.13) and (2.16)
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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+, Li2+, Be3+,
Solution and so on). However, Bohr’s model was too
Since ni = 5 and nf = 2, this transition gives simple to account for the following points.
rise to a spectral line in the visible region i) It fails to account for the finer details
of the Balmer series. From equation (2.17) (doublet, that is two closely spaced lines)
1 1 of the hydrogen atom spectrum observed
∆E = 2.18 × 10 −18 J  2 − 2  by using sophisticated spectroscopic
5 2 
−19
techniques. This model is also unable to
= − 4.58 × 10 J explain the spectrum of atoms other than
It is an emission energy hydrogen, for example, helium atom which
possesses only two electrons. Further,
The frequency of the photon (taking
Bohr’s theory was also unable to explain
energy in terms of magnitude) is given by
the splitting of spectral lines in the presence
∆E of magnetic field (Zeeman effect) or an
ν= electric field (Stark effect).
h
ii) It could not explain the ability of atoms to
form molecules by chemical bonds.
In other words, taking into account the
= 6.91×1014 Hz points mentioned above, one needs 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 this In view of the shortcoming of the Bohr’s model,
orbit? attempts were made to develop a more suitable
and general model for atoms. Two important
Solution
developments which contributed significantly
(2.18 × 10 −18 J )Z 2 in the formulation of such a model were :
En = − atom–1
n2 1. Dual behaviour of matter,
For He , n = 1, Z = 2
+ 2. Heisenberg uncertainty principle.
−18 2
(2.18 × 10 J)(2 ) 2.5.1 Dual Behaviour of Matter
E1 = − = −8.72 × 10 −18 J
12 The French physicist, de Broglie, in 1924
The radius of the orbit is given by equation proposed that matter, like radiation, should
(2.15) also exhibit dual behaviour i.e., both particle
and wavelike properties. This means that just
(0.0529 nm )n 2
rn = as the photon has momentum as well as
Z wavelength, electrons should also have
Since n = 1, and Z = 2 momentum as well as wavelength, de Broglie,
from this analogy, gave the following relation
(0.0529 nm )12
rn = = 0.02645 nm between wavelength (λ) and momentum (p) of
2 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 (2.22)
physicist, studied history as an
h (6.626 × 10 −34 Js)
undergraduate in the early λ= =
mv (0.1 kg )(10 m s −1 )
1910’s. His interest turned to
science as a result of his = 6.626 × 10–34 m (J = kg m2 s–2)
assignment to radio Problem 2.13
communications in World War I.
The mass of an electron is 9.1×10–31 kg. If
He received his Dr. Sc. from the University of
its K.E. is 3.0×10 –25 J, calculate its
Paris in 1924. He was professor of theoretical
wavelength.
physics at the University of Paris from 1932 untill
his retirement in 1962. He was awarded the
Solution
Nobel Prize in Physics in 1929. Since K. E. = ½ mv2
1/ 2 1/ 2
h h  2K.E.  2 × 3.0 × 10−25 kg m 2 s −2 
v = =
λ= = (2.22)  m   9.1 × 10 −31 kg 
mv p
where m is the mass of the particle, v its = 812 m s–1
velocity and p its momentum. de Broglie’s
prediction was confirmed experimentally h 6.626 × 10−34 Js
λ= =
when it was found that an electron beam m v (9.1 × 10 −31 kg )(812 m s−1 )
undergoes diffraction, a phenomenon = 8967 × 10–10 m = 896.7 nm
characteristic of waves. This fact has been put
to use in making an electron microscope, Problem 2.14
which is based on the wavelike behaviour of Calculate the mass of a photon with
electrons just as an ordinary microscope wavelength 3.6 Å.
utilises the wave nature of light. An electron Solution
microscope is a powerful tool in modern λ = 3.6 Å = 3.6 × 10–10 m
scientific research because it achieves a Velocity of photon = velocity of light
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
ordinary objects are so short (because of their = 6.135 × 10–29 kg
large masses) that their wave properties cannot
be detected. The wavelengths associated with 2.5.2 Heisenberg’s Uncertainty Principle
electrons and other subatomic particles (with Werner Heisenberg a German physicist in
very small mass) can however be detected
1927, stated uncertainty principle which is the
experimentally. Results obtained from the
consequence of dual behaviour of matter and
following problems prove these points
qualitatively. radiation. It states that it is impossible to
determine simultaneously, the exact
Problem 2.12 position and exact momentum (or velocity)
What will be the wavelength of a ball of of an electron.
mass 0.1 kg moving with a velocity of 10 Mathematically, it can be given as in
m s–1 ? equation (2.23).
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(2.23)  h
momentum photons of such light  p = 
λ
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 about the
velocity of the electron after the collision.
where ∆x is the uncertainty in position and ∆px
(or ∆vx ) is the uncertainty in momentum (or Significance of Uncertainty Principle
velocity) of the particle. If the position of the One of the important implications of the
electron is known with high degree of accuracy Heisenberg Uncertainty Principle is that it
(∆x is small), then the velocity of the electron rules out existence of definite paths or
will be uncertain [∆(vx) is large]. On the other trajectories of electrons and other similar
hand, if the velocity of the electron is known particles. The trajectory of an object is
precisely (∆(vx ) is small), then the position of determined by its location and velocity at
the electron will be uncertain various moments. If we know where a body is
(∆x will be large). Thus, if we carry out some at a particular instant and if we also know its
physical measurements on the electron’s velocity and the forces acting on it at that
position or velocity, the outcome will always instant, we can tell where the body would be
depict a fuzzy or blur picture. sometime later. We, therefore, conclude that the
position of an object and its velocity fix its
The uncertainty principle can be best
trajectory. Since for a sub-atomic object such
understood with the help of an example. as an electron, it is not possible simultaneously
Suppose you are asked to measure the to determine the position and velocity at any
thickness of a sheet of paper with an given instant to an arbitrary degree of
unmarked metrestick. Obviously, the results precision, it is not possible to talk of the
obtained would be extremely inaccurate and trajectory of an electron.
meaningless, In order to obtain any accuracy, The effect of Heisenberg Uncertainty
you should use an instrument graduated in Principle is significant only for motion of
units smaller than the thickness of a sheet of microscopic objects and is negligible for
the paper. Analogously, in order to determine that of macroscopic objects. This can be
the position of an electron, we must use a seen from the following examples.
meterstick calibrated in units of smaller than If uncertainty principle is applied to an
the dimensions of electron (keep in mind that object of mass, say about a milligram (10–6 kg),
an electron is considered as a point charge and then
is therefore, dimensionless). To observe an
electron, we 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 an = 0.579×107 m s–1 (1J = 1 kg m2 s–2)
electron on the other hand. ∆v.∆x obtained is = 5.79×106 m s–1
much larger and such uncertainties are of real
consequence. For example, for an electron Problem 2.16
whose mass is 9.11×10–31 kg., according to A golf ball has a mass of 40g, and a speed
Heisenberg uncertainty principle of 45 m/s. If the speed can be measured
within accuracy of 2%, calculate the
uncertainty in the position.
Solution
The uncertainty in the speed is 2%, i.e.,
Using the equation (2.22)

It, therefore, means that if one tries to 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 m 2 s −1
≈ 104 ms −1
10 −8 m = 1.46×10 –33 m
This is nearly ~ 1018 times smaller than
which is so large that the classical picture of
the diameter of a typical atomic nucleus.
electrons moving in Bohr’s orbits (fixed) cannot
As mentioned earlier for large particles, the
hold good. It, therefore, means that the uncertainty principle sets no meaningful
precise statements of the position and limit to the precision of measurements.
momentum of electrons have to be
replaced by the statements of probability,
that the electron has at a given position Reasons for the Failure of the Bohr Model
and momentum. This is what happens in One can now understand the reasons for the
the quantum mechanical model of atom. failure of the Bohr model. In Bohr model, an
electron is regarded as a charged particle
Problem 2.15 moving in well defined circular orbits about
the nucleus. The wave character of the electron
A microscope using suitable photons is
is not considered in Bohr model. Further, an
employed to locate an electron in an atom
orbit is a clearly defined path and this path
within a distance of 0.1 Å. What is the
can completely be defined only if both the
uncertainty involved in the measurement
position and the velocity of the electron are
of its velocity?
known exactly at the same time. This is not
Solution possible according to the Heisenberg
h h uncertainty principle. Bohr model of the
∆x ∆p = or ∆x m ∆v = hydrogen atom, therefore, not only ignores
4π 4π dual behaviour of matter but also contradicts
Heisenberg uncertainty principle. In view of
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properties. It specifies the laws of motion that

Erwin Schrödinger, an
these objects obey. When quantum mechanics
Austrian physicist
is applied to macroscopic objects (for which
received his Ph.D. in
wave like properties are insignificant) the
theoretical physics from
results are the same as those from the classical
the University of Vienna mechanics.
in 1910. In 1927
Quantum mechanics was developed
Schrödinger succeeded
independently in 1926 by Werner Heisenberg
Max Planck at the
and Erwin Schrödinger. Here, however, we
University of Berlin at shall be discussing the quantum mechanics
Planck’s request. In 1933, Erwin Schrödinger which is based on the ideas of wave motion.
(1887-1961)
Schrödinger left Berlin The fundamental equation of quantum
because of his opposition to Hitler and Nazi mechanics was developed by Schrödinger and
policies and returned to Austria in 1936. After it won him the Nobel Prize in Physics in 1933.
the invasion of Austria by Ger many, This equation which incorporates wave-
Schrödinger was forcibly removed from his particle duality of matter as proposed by de
professorship. He then moved to Dublin, Ireland Broglie is quite complex and knowledge of
where he remained for seventeen years. higher mathematics is needed to solve it. You
Schrödinger shared the Nobel Prize for Physics will learn its solutions for different systems in
with P.A.M. Dirac in 1933. higher classes.
these inherent weaknesses in the Bohr model, For a system (such as an atom or a
there was no point in extending Bohr model molecule whose energy does not change with
to other atoms. In fact an insight into the time) the Schrödinger equation is written as
structure of the atom was needed which could where is a mathematical operator
called Hamiltonian. Schrödinger gave a recipe
account for wave-particle duality of matter and
of constructing this operator from the
be consistent with Heisenberg uncertainty
expression for the total energy of the system.
principle. This came with the advent of
The total energy of the system takes into
quantum mechanics.
account the kinetic energies of all the sub-
2.6 QUANTUM MECHANICAL MODEL OF atomic particles (electrons, nuclei), attractive
ATOM potential between the electrons and nuclei and
Classical mechanics, based on Newton’s laws repulsive potential among the electrons and
of motion, successfully describes the motion nuclei individually. Solution of this equation
of all macroscopic objects such as a falling gives E and ψ.
stone, orbiting planets etc., which have Hydrogen Atom and the Schrödinger
essentially a particle-like behaviour as shown Equation
in the previous section. However it fails when When Schrödinger equation is solved for
applied to microscopic objects like electrons, hydrogen atom, the solution gives the possible
atoms, molecules etc. This is mainly because energy levels the electron can occupy and the
of the fact that classical mechanics ignores the corresponding wave function(s) (ψ) of the
concept of dual behaviour of matter especially electron associated with each energy level.
for sub-atomic particles and the uncertainty These quantized energy states and
principle. The branch of science that takes into corresponding wave functions which are
account this dual behaviour of matter is called characterized by a set of three quantum
quantum mechanics. numbers (principal quantum number n,
Quantum mechanics is a theoretical azimuthal quantum number l and
science that deals with the study of the motions magnetic quantum number m l ) arise as a
of the microscopic objects that have both natural consequence in the solution of the
observable wave like and particle like Schrödinger equation. When an electron is 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 all energy levels is a direct result of the wave
information about the electron. The wave like properties of electrons and are
function is a mathematical function whose allowed solutions of Schrödinger wave
value depends upon the coordinates of the equation.
electron in the atom and does not carry any 3. Both the exact position and exact velocity
physical meaning. Such wave functions of of an electron in an atom cannot be
hydrogen or hydrogen like species with one determined simultaneously (Heisenberg
uncertainty principle). The path of an
electron are called atomic orbitals. Such wave
electron in an atom therefore, can never
functions pertaining to one-electron species be determined or known accurately.
are called one-electron systems. The That is why, as you shall see later on,
probability of finding an electron at a point one talks of only probability of finding
within an atom is proportional to the |ψ|2 at the electron at different points in
that point. The quantum mechanical results an atom.
of the hydrogen atom successfully predict all 4. An atomic orbital is the wave function
aspects of the hydrogen atom spectrum ψ for an electron in an atom.
including some phenomena that could not be Whenever an electron is described by a
explained by the Bohr model. wave function, we say that the electron
occupies that orbital. Since many such
Application of Schrödinger equation to
wave functions are possible for an
multi-electron atoms presents a difficulty: the electron, there are many atomic orbitals
Schrödinger equation cannot be solved exactly in an atom. These “one electron orbital
for a multi-electron atom. This difficulty can wave functions” or orbitals form the
be overcome by using approximate methods. basis of the electronic structure of atoms.
Such calculations with the aid of modern In each orbital, the electron has a
computers show that orbitals in atoms other definite energy. An orbital cannot
than hydrogen do not differ in any radical way contain more than two electrons. In a
from the hydrogen orbitals discussed above. multi-electron atom, the electrons are
filled in various orbitals in the order of
The principal difference lies in the consequence
increasing energy. For each electron of
of increased nuclear charge. Because of this a multi-electron atom, there shall,
all the orbitals are somewhat contracted. therefore, be an orbital wave function
Further, as you shall see later (in subsections characteristic of the orbital it occupies.
2.6.3 and 2.6.4), unlike orbitals of hydrogen All the information about the electron
or hydrogen like species, whose energies in an atom is stored in its orbital wave
depend only on the quantum number n, the function ψ and quantum mechanics
energies of the orbitals in multi-electron atoms makes it possible to extract this
depend on quantum numbers n and l. information out of ψ.
5. The probability of finding an electron at
Important Features of the Quantum a point within an atom is proportional
Mechanical Model of Atom to the square of the orbital wave function
2 2
Quantum mechanical model of atom is the i.e., |ψ| at that point. |ψ| is known
picture of the structure of the atom, which as probability density and is always
2
emerges from the application of the positive. From the value of |ψ | at
Schrödinger equation to atoms. The different points within an atom, it is
following are the important features of the possible to predict the region around
quantum-mechanical model of atom: the nucleus where electron will most
probably be found.
1. The energy of electrons in atoms is
quantized (i.e., can only have certain
specific values), for example when 2.6.1 Orbitals and Quantum Numbers
electrons are bound to the nucleus in A large number of orbitals are possible in an
atoms. atom. Qualitatively these orbitals can be
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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 = 0.
there is more chance of finding the electron near There are two sub-shells (l = 0, 1) in the second
the nucleus. Similarly shape and orientation shell (n = 2), three (l = 0, 1, 2) in third shell (n =
mean that there is more probability of finding 3) and so on. Each sub-shell is assigned an
the electron along certain directions than azimuthal quantum number (l). Sub-shells
along others. Atomic orbitals are precisely corresponding to different values of l are
distinguished by what are known as quantum represented by the following symbols.
numbers. Each orbital is designated by three Value for l : 0 1 2 3 4 5 ............
quantum numbers labelled as n, l and m l. notation for s p d f g h ............
The principal quantum number ‘n’ is sub-shell
a positive integer with value of n = 1,2,3....... Table 2.4 shows the permissible values of
The principal quantum number determines the ‘l ’ for a given principal quantum number and
size and to large extent the energy of the the corresponding sub-shell notation.
orbital. For hydrogen atom and hydrogen like Table 2.4 Subshell Notations
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.
Azimuthal quantum number. ‘l’ is also
known as orbital angular momentum or
Magnetic orbital quantum number. ‘ml’
subsidiary quantum number. It defines the
gives information about the spatial
three-dimensional shape of the orbital. For a
orientation of the orbital with respect to
given value of n, l can have n values ranging
standard set of co-ordinate axis. For any
from 0 to n – 1, that is, for a given value of n,
sub-shell (defined by ‘l’ value) 2l+1 values
the possible value of l are : l = 0, 1, 2, ..........
of ml are possible and these values are given
(n–1)
by :
For example, when n = 1, value of l is only
0. For n = 2, the possible value of l can be 0 ml = – l, – (l –1), – (l – 2)... 0,1... (l – 2), (l –1), l
and 1. For n = 3, the possible l values are 0, 1 Thus for l = 0, the only permitted value of
and 2. ml = 0, [2(0)+1 = 1, one s orbital]. For l = 1, ml
Each shell consists of one or more sub- can be –1, 0 and +1 [2(1)+1 = 3, three p
shells or sub-levels. The number of sub-shells orbitals]. For l = 2, ml = –2, –1, 0, +1 and +2,
in a principal shell is equal to the value of n. [2(2)+1 = 5, five d orbitals]. It should be noted
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56 CHEMISTRY
that the values of ml are derived from l and that electron has, besides charge and mass,
the value of l are derived from n. intrinsic spin angular quantum number. Spin
Each orbital in an atom, therefore, is angular momentum of the electron — a vector
defined by a set of values for n, l and ml. An quantity, can have two orientations relative to
orbital described by the quantum numbers the chosen axis. These two orientations are
n = 2, l = 1, ml = 0 is an orbital in the p sub-shell distinguished by the spin quantum numbers
of the second shell. The following chart gives ms which can take the values of +½ or –½.
the relation between the subshell and the These are called the two spin states of the
number of orbitals associated with it. electron and are normally represented by two
arrows, ↑ (spin up) and ↓ (spin down). Two
Value of l 0 1 2 3 4 5 electrons that have different ms values (one +½
Subshell notation s p d f g h and the other –½) are said to have opposite
spins. An orbital cannot hold more than two
number of orbitals 1 3 5 7 9 11
electrons and these two electrons should have
Electron spin ‘s’ : The three quantum opposite spins.
numbers labelling an atomic orbital can be To sum up, the four quantum numbers
used equally well to define its energy, shape provide the following information :
and orientation. But all these quantum i) n defines the shell, determines the size of
numbers are not enough to explain the line the orbital and also to a large extent the
spectra observed in the case of multi-electron energy of the orbital.
atoms, that is, some of the lines actually occur
in doublets (two lines closely spaced), triplets ii) There are n subshells in the nth shell. l
(three lines, closely spaced) etc. This suggests identifies the subshell and determines the
the presence of a few more energy levels than shape of the orbital (see section 2.6.2).
predicted by the three quantum numbers. There are (2l+1) orbitals of each type in a
subshell, that is, one s orbital (l = 0), three
In 1925, George Uhlenbeck and Samuel
p orbitals (l = 1) and five d orbitals (l = 2)
Goudsmit proposed the presence of the fourth
per subshell. To some extent l also
quantum number known as the electron
determines the energy of the orbital in a
spin quantum number (ms ). An electron
multi-electron atom.
spins around its own axis, much in a similar
way as earth spins around its own axis while iii) ml designates the orientation of the orbital.
revolving around the sun. In other words, an For a given value of l, ml has (2l+1) values,
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 ψ in an atom. It is characterized by three quantum numbers (n, l and
ml) and its value depends upon the coordinates of the electron. ψ has, by itself, no physical
2 2
meaning. It is the square of the wave function i.e., |ψ| which has a physical meaning. |ψ|
at any point in an atom gives the value of probability density at that point. Probability density
2 2
(|ψ| ) is the probability per unit volume and the product of |ψ| and a small volume (called a
volume element) yields the probability of finding the electron in that volume (the reason for
2
specifying a small volume element is that |ψ| 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 | ψ| 2 and the corresponding volume elements. It is thus possible to get the probable
distribution of an electron in an orbital.
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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 orbital
(n = 3, l = 0 and ml = 0); there are three 3p
orbitals (n = 3, l = 1 and ml = –1, 0, +1);
there are five 3d orbitals (n = 3, l = 2 and Fig. 2.12 The plots of (a) the orbital wave
ml = –2, –1, 0, +1+, +2). function ψ (r ); (b) the variation of
probability density ψ (r) as a function
2
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
2
(i.e.,ψ ) at a point gives the probability density
Problem 2.18
of the electron at that point. The variation of
Using s, p, d, f notations, describe the ψ 2 as a function of r for 1s and 2s orbitals is
orbital with the following quantum given in Fig. 2.12(b). Here again, you may note
numbers that the curves for 1s and 2s orbitals are
(a) n = 2, l = 1, (b) n = 4, l = 0, (c) n = 5, different.
l = 3, (d) n = 3, l = 2 It may be noted that for 1s orbital the
Solution probability density is maximum at the nucleus
n l orbital and it decreases sharply as we move away from
it. On the other hand, for 2s orbital the
a) 2 1 2p
probability density first decreases sharply to
b) 4 0 4s zero and again starts increasing. After reaching
c) 5 3 5f a small maxima it decreases again and
d) 3 2 3d approaches zero as the value of r increases
further. The region where this probability
2.6.2 Shapes of Atomic Orbitals density function reduces to zero is called
The orbital wave function or ψ for an electron nodal surfaces or simply nodes. In general,
in an atom has no physical meaning. It is it has been found that ns-orbital has (n – 1)
simply a mathematical function of the nodes, that is, number of nodes increases with
coordinates of the electron. However, for increase of principal quantum number n. In
different orbitals the plots of corresponding other words, number of nodes for 2s orbital is
wave functions as a function of r (the distance one, two for 3s and so on.
from the nucleus) are different. Fig. 2.12(a), These probability density variation can be
gives such plots for 1s (n = 1, l = 0) and 2s (n = visualised in terms of charge cloud diagrams
2, l = 0) orbitals. [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
2
density |ψ| 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 or volume in which the Fig. 2.13 (a) Probability density plots of 1s and
probability of finding the electron is very high, 2s atomic orbitals. The density of the
say, 90%. The boundary surface diagram for dots represents the probability
1s and 2s orbitals are given in Fig. 2.13(b). density of finding the electron in that
One may ask a question : Why do we not draw region. (b) Boundary surface diagram
a boundary surface diagram, which bounds a for 1s and 2s orbitals.
region in which the probability of finding the
electron is, 100 %? The answer to this question
2
is that the probability density |ψ| 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 probability
of finding the electron at a given distance is equal
in all the directions. It is also observed that the
size of the s orbital increases with increase in n, Fig. 2.14 Boundary surface diagrams of the
that is, 4s > 3s > 2s > 1s and the electron is three 2p orbitals.
located further away from the nucleus as the diagrams are not spherical. Instead each
principal quantum number increases. p orbital consists of two sections called lobes
Boundary surface diagrams for three 2p that are on either side of the plane that passes
orbitals (l = 1) are shown in Fig. 2.14. In these through the nucleus. The probability density
diagrams, the nucleus is at the origin. Here, function is zero on the plane where the two
unlike s-orbitals, the boundary surface lobes touch each other. The size, shape and
2
* If probability density |ψ| is constant on a given surface, |ψ| is also constant over the surface. The boundary
2
surface for |ψ| and |ψ| are identical.
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energy of the three orbitals are identical. They there are, therefore, three p orbitals whose axes
differ however, in the way the lobes are are mutually perpendicular. Like s orbitals, p
oriented. Since the lobes may be considered orbitals increase in size and energy with
to lie along the x, y or z axis, they are given the increase in the principal quantum number and
designations 2px, 2py, and 2pz. It should be hence the order of the energy and size of
understood, however, that there is no simple various p orbitals is 4p > 3p > 2p. Further, like
relation between the values of ml (–1, 0 and s orbitals, the probability density functions for
+1) and the x, y and z directions. For our p-orbital also pass through value zero, besides
purpose, it is sufficient to remember that, at zero and infinite distance, as the distance
because there are three possible values of m l, from 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
number (n) has to be 3. as the value of l cannot
be greater than n–1. There are five ml values (–
2, –1, 0, +1 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.
2.6.3 Energies of Orbitals
The energy of an electron in a hydrogen atom
Fig. 2.15 Boundary surface diagrams of the five
is determined solely by the principal quantum
3d orbitals.
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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 < (2.23) quantum number (shell), but also on its
and is depicted in Fig. 2.16. Although the azimuthal quantum number (subshell). That
is, for a given principal quantum number, s,
shapes of 2s and 2p orbitals are different, an
p, d, f ... all have different energies. Within a
electron has the same energy when it is in the
given principal quantum number, the energy
2s orbital as when it is present in 2p orbital.
of orbitals increases in the order s<p<d<f. For
The orbitals having the same energy are called
higher energy levels, these differences are
degenerate. The 1s orbital in a hydrogen
sufficiently pronounced and straggering of
atom, as said earlier, corresponds to the most
orbital energy may result, e.g., 4s<3d and
stable condition and is called the ground state 6s<5d ; 4f<6p. The main reason for having
and an electron residing in this orbital is most different energies of the subshells is the mutual
strongly held by the nucleus. An electron in repulsion among the electrons in multi-
the 2s, 2p or higher orbitals in a hydrogen atom electron atoms. The only electrical interaction
is in excited state. present in hydrogen atom is the 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 the
nucleus by the inner shell electrons. This is
known as the shielding of the outer shell
Fig. 2.16 Energy level diagrams for the few electrons from the nucleus by the inner
electronic shells of (a) hydrogen atom shell electrons, and the net positive charge
and (b) multi-electronic atoms. Note that experienced by the outer electrons is known
orbitals for the same value of principal
as effective nuclear charge (Zeff e). Despite
quantum number, have the same
energies even for different azimuthal the shielding of the outer electrons from the
quantum number for hydrogen atom. nucleus by the inner shell electrons, the
In case of multi-electron atoms, orbitals attractive force experienced by the outer shell
with same principal quantum number electrons increases with increase of nuclear
possess different energies for different charge. In other words, the energy of
azimuthal quantum numbers. interaction between, the nucleus and electron
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(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. In other words, for a given shell
(principal quantum number), the Z eff
experienced by the electron decreases with
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 levels same subshell decrease with increase in
within the same shell (or same principal the atomic number (Zeff). For example, energy
quantum number), that is, energy of electron of 2s orbital of hydrogen atom is greater than
in an orbital, as mentioned earlier, depends that of 2s orbital of lithium and that of lithium
upon the values of n and l. Mathematically, is greater than that of sodium and so on, that
the dependence of energies of the orbitals on n is, E2s(H) > E2s(Li) > E2s(Na) > E2s(K).
and l are quite complicated but one simple rule 2.6.4 Filling of Orbitals in Atom
is that, the lower the value of (n + l) for an
orbital, the lower is its energy. If two The filling of electrons into the orbitals of
orbitals have the same value of (n + l), the different atoms takes place according to the
orbital with lower value of n will have the aufbau principle which is based on the Pauli’s
lower energy. The Table 2.5 illustrates the (n exclusion principle, the Hund’s rule of
+ l ) rule and Fig. 2.16 depicts the energy levels maximum multiplicity and the relative
of multi-electrons atoms. It may be noted that energies of the orbitals.
different subshells of a particular shell have Aufbau Principle
different energies in case of multi–electrons The word ‘aufbau’ in German means ‘building
atoms. However, in hydrogen atom, these have 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 from
atoms, the orbitals are filled in order of right top to bottom left. With respect to
their increasing energies. In other words, placement of outermost valence electrons, it is
electrons first occupy the lowest energy orbital remarkably accurate for all atoms. For
available to them and enter into higher energy example, valence electron in potassium must
orbitals only after the lower energy orbitals are choose between 3d and 4s orbitals and as
filled. As you have learnt above, energy of a predicted by this sequence, it is found in 4s
given orbital depends upon effective nuclear orbital. The above order should be assumed
charge and different type of orbitals are affected to be a rough guide to the filling of energy
to different extent. Thus, there is no single levels. In many cases, the orbitals are similar
ordering of energies of orbitals which will be in energy and small changes in atomic
universally correct for all atoms. structure may bring about a change in the
However, following order of energies of the order of filling. Even then, the above series is a
orbitals is extremely useful: useful guide to the building of the electronic
structure of an atom provided that it is
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f,
remembered that exceptions may occur.
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 that the two electrons can
have the same value of three quantum numbers
n, l and ml, but must have the opposite spin
quantum number. The 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 into
the orbitals belonging to the same subshell
Fig.2.17 Order of filling of orbitals (that is, orbitals of equal energy, called
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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 two
same subshell (p, d or f) does not take place electrons differ from each other with opposite
until each orbital belonging to that spin, as can be seen from the orbital diagram.
subshell has got one electron each i.e., it
is singly occupied.
Since there are three p, five d and seven f The third electron of lithium (Li) is not
orbitals, therefore, the pairing of electrons will allowed in the 1s orbital because of Pauli
start in the p, d and f orbitals with the entry of exclusion principle. It, therefore, takes the next
4th, 6th and 8th electron, respectively. It has available choice, namely the 2s orbital. The
been observed that half filled and fully filled electronic configuration of Li is 1s22s1. The 2s
degenerate set of orbitals acquire extra stability orbital can accommodate one more electron.
due to their symmetry (see Section, 2.6.7). The configuration of beryllium (Be) atom is,
2.6.5 Electronic Configuration of Atoms therefore, 1s2 2s2 (see Table 2.6, page 66 for
the electronic configurations of elements).
The distribution of electrons into orbitals of an
atom is called its electronic configuration. In the next six elements—boron
If one keeps in mind the basic rules which (B, 1s22s22p1), carbon (C, 1s22s22p2), nitrogen
govern the filling of different atomic orbitals, (N, 1s22s22p3), oxygen (O, 1s22s22p4), fluorine
the electronic configurations of different atoms (F, 1s22s22p5) and neon (Ne, 1s22s22p6), the 2p
can be written very easily. orbitals get progressively filled. This process
is completed with the neon atom. The orbital
The electronic configuration of different
picture of these elements can be represented
atoms can be represented in two ways. For
as follows :
example :
(i) s a p bd c ...... notation
(ii) Orbital diagram
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
negative spin. The advantage of second notation The electronic configuration of the elements
over the first is that it represents all the four sodium (Na, 1s 2 2s 2 2p 6 3s 1 ) to argon
quantum numbers. (Ar,1s22s22p63s23p6), follow exactly the same
The hydrogen atom has only one electron pattern as the elements from lithium to neon
which goes in the orbital with the lowest with the difference that the 3s and 3p orbitals
energy, namely 1s. The electronic are getting filled now. This process can be
configuration of the hydrogen atom is 1s1 simplified if we represent the total number of
meaning that it has one electron in the 1s electrons in the first two shells by the name of
orbital. The second electron in helium (He) can element neon (Ne). The 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). The orbitals takes place. The elements after
electrons in the completely filled shells are uranium (U) are all short-lived and all of them
known as core electrons and the electrons that are produced artificially. The electronic
are added to the electronic shell with the configurations of the known elements (as
highest principal quantum number are called determined by spectroscopic methods) are
valence electrons. For example, the electrons tabulated in Table 2.6 (page 66).
in Ne are the core electrons and the electrons One may ask what is the utility of knowing
from Na to Ar are the valence electrons. In the electron configuration? The modern
potassium (K) and calcium (Ca), the 4s orbital, approach to the chemistry, infact, depends
being lower in energy than the 3d orbitals, is almost entirely on electronic distribution to
occupied by one and two electrons respectively. understand and explain chemical behaviour.
A new pattern is followed beginning with For example, questions like why two or more
scandium (Sc). The 3d orbital, being lower in atoms combine to form molecules, why some
energy than the 4p orbital, is filled first. elements are metals while others are non-
Consequently, in the next ten elements, metals, why elements like helium and argon
scandium (Sc), titanium (Ti), vanadium (V), are not reactive but elements like the halogens
chromium (Cr), manganese (Mn), iron (Fe), are reactive, find simple explanation from the
cobalt (Co), nickel (Ni), copper (Cu) and zinc electronic configuration. These questions have
(Zn), the five 3d orbitals are progressively no answer in the Daltonian model of atom. A
occupied. We may be puzzled by the fact that detailed understanding of the electronic
chromium and copper have five and ten structure of atom is, therefore, very essential
electrons in 3d orbitals rather than four and for getting an insight into the various aspects
nine as their position would have indicated with of modern chemical knowledge.
two-electrons in the 4s orbital. The reason is
that fully filled orbitals and half-filled orbitals 2.6.6 Stability of Completely Filled and
have extra stability (that is, lower energy). Thus Half Filled Subshells
p3, p6, d5, d10,f 7, f14 etc. configurations, which The ground state electronic configuration of the
are either half-filled or fully filled, are more atom of an element always corresponds to the
stable. Chromium and copper therefore adopt state of the lowest total electronic energy. The
the d 5 and d 10 configuration (Section electronic configurations of most of the atoms
2.6.7)[caution: exceptions do exist] follow the basic rules given in Section 2.6.5.
With the saturation of the 3d orbitals, the However, in certain elements such as Cu, or
filling of the 4p orbital starts at gallium (Ga) Cr, where the two subshells (4s and 3d) differ
and is complete at krypton (Kr). In the next slightly in their energies, an electron shifts from
eighteen elements from rubidium (Rb) to xenon a subshell of lower energy (4s) to a subshell of
(Xe), the pattern of filling the 5s, 4d and 5p higher energy (3d), provided such a shift
orbitals are similar to that of 4s, 3d and 4p results in all orbitals of the subshell of higher
orbitals as discussed above. Then comes the energy getting either completely filled or half
turn of the 6s orbital. In caesium (Cs) and the filled. The valence electronic configurations of
barium (Ba), this orbital contains one and two Cr and Cu, therefore, are 3d5 4s1 and 3d10 4s1
electrons, respectively. Then from lanthanum respectively and not 3d4 4s2 and 3d9 4s2. It has
(La) to mercury (Hg), the filling up of electrons been found that there is extra stability
takes place in 4f and 5d orbitals. After this, associated with these electronic configurations.
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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 coulombic repulsion
energy, and (iii) larger exchange energy.
Details about the exchange energy will be Fig. 2.18 Possible exchange for a d5
dealt with in higher classes. configuration
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66 CHEMISTRY
Table 2.6 Electronic Configurations of the Elements
* Elements with exceptional electronic configurations
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** 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) (ψ) (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
+ 2+
(such as He , Li 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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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 (i) Calculate the total number of electrons present in one mole of methane.
(ii) Find (a) the total number and (b) the total mass of neutrons in 7 mg of 14C.
–27
(Assume that mass of a neutron = 1.675 × 10 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH3 at
STP.
Will the answer change if the temperature and pressure are changed ?
2.3 How many neutrons and protons are there in the following nuclei ?
13 16 24 56 88
6 C, 8 O, 12 Mg, 26 Fe, 38 Sr
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.
(iii) Z = 4 , A = 9.
2.5 Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate
the frequency (ν) and wavenumber ( ν ) of the yellow light.
2.6 Find energy of each of the photons which
15
(i) correspond to light of frequency 3×10 Hz.
(ii) have wavelength of 0.50 Å.
2.7 Calculate the wavelength, frequency and wavenumber of a light wave whose period
is 2.0 × 10–10 s.
2.8 What is the number of photons of light with a wavelength of 4000 pm that provide
1J of energy?
–7
2.9 A photon of wavelength 4 × 10 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
–19
(1 eV= 1.6020 × 10 J).
2.10 Electromagnetic radiation of wavelength 242 nm is just sufficient to ionise the
sodium atom. Calculate the ionisation energy of sodium in kJ mol–1.
2.11 A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57µm.
Calculate the rate of emission of quanta per second.
2.12 Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 6800 Å. Calculate threshold frequency (ν0 ) and work function
(W0 ) of the metal.
2.13 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
2.14 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).
2.15 What is the maximum number of emission lines when the excited electron of a
H atom in n = 6 drops to the ground state?
2.16 (i) The energy associated with the first orbit in the hydrogen atom is
–18 –1
–2.18 × 10 J atom . What is the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
2.17 Calculate the wavenumber for the longest wavelength transition in the Balmer
series of atomic hydrogen.
2.18 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
–11
electron energy is –2.18 × 10 ergs.
–18 2
2.19 The electron energy in hydrogen atom is given by En = (–2.18 × 10 )/n J. Calculate
the 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?
2.20 Calculate the wavelength of an electron moving with a velocity of 2.05 × 107 m s–1.
–31 –25
2.21 The mass of an electron is 9.1 × 10 kg. If its K.E. is 3.0 × 10 J, calculate its
wavelength.
2.22 Which of the following are isoelectronic species i.e., those having the same number
of electrons?
+ + 2+ 2+ 2–
Na , K , Mg , Ca , S , Ar.
2.23 (i) Write the electronic configurations of the following ions: (a) H – (b) Na+ (c) O2–
–
(d) F
(ii) What are the atomic numbers of elements whose outermost electrons are
1 3 5
represented by (a) 3s (b) 2p and (c) 3p ?
(iii) Which atoms are indicated by the following configurations ?
1 2 3 2 1
(a) [He] 2s (b) [Ne] 3s 3p (c) [Ar] 4s 3d .
2.24 What is the lowest value of n that allows g orbitals to exist?
2.25 An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for
this electron.
2.26 An atom of an element contains 29 electrons and 35 neutrons. Deduce (i) the
number of protons and (ii) the electronic configuration of the element.
2.27 Give the number of electrons in the species
2.28 (i) An atomic orbital has n = 3. What are the possible values of l and ml ?
(ii) List the quantum numbers (ml and l ) of electrons for 3d orbital.
(iii) Which of the following orbitals are possible?
1p, 2s, 2p and 3f
2.29 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.
2.30 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
2.31 How many electrons in an atom may have the following quantum numbers?
(a) n = 4, ms = – ½ (b) n = 3, l = 0
2.32 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.
2.33 What transition in the hydrogen spectrum would have the same wavelength as the
+
Balmer transition n = 4 to n = 2 of He spectrum ?
2.34 Calculate the energy required for the process
+ 2+ –
He (g) g He (g) + e
–18 –1
The ionization energy for the H atom in the ground state is 2.18 × 10 J atom
2.35 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.
2.36 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.
2.37 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.
–16
2.38 A certain particle carries 2.5 × 10 C of static electric charge. Calculate the number
of electrons present in it.
2.39 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.
2.40 In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum
etc. have been used to be bombarded by the α-particles. If the thin foil of light
atoms like aluminium etc. is used, what difference would be observed from the
above results ?
79 79 35 35
2.41 Symbols 35 Br and Br can be written, whereas symbols 79 Br
and Br are not
acceptable. Answer briefly.
2.42 An element with mass number 81 contains 31.7% more neutrons as compared to
protons. Assign the atomic symbol.
2.43 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.
2.44 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.
2.45 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.
2.46 Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of
24
photons emitted is 5.6 × 10 , calculate the power of this laser.
2.47 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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72 CHEMISTRY
2.48 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.
2.49 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
15
during the pulse source is 2.5 × 10 , calculate the energy of the source.
2.50 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.
2.51 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.
2.52 Following results are observed when sodium metal is irradiated with different
wavelengths. Calculate (a) threshold wavelength and, (b) Planck’s constant.
λ (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.
2.54 If the photon of the wavelength 150 pm strikes an atom and one of tis inner bound
7 –1
electrons is ejected out with a velocity of 1.5 × 10 m s , calculate the energy with
which it is bound to the nucleus.
2.55 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.
2.56 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.
2.57 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
6
other type of material. If the velocity of the electron in this microscope is 1.6 × 10
–1
ms , calculate de Broglie wavelength associated with this electron.
2.58 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.
6 –1
2.59 If the velocity of the electron in Bohr’s first orbit is 2.19 × 10 ms , calculate the
de Broglie wavelength associated with it.
2.60 The velocity associated with a proton moving in a potential difference of 1000 V is
5 –1
4.37 × 10 ms . If the hockey ball of mass 0.1 kg is moving with this velocity,
calcualte the wavelength associated with this velocity.
2.61 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/4πm × 0.05 nm, is there any problem in defining this value.
2.62 The quantum numbers of six electrons are given below. Arrange them in order of
increasing energies. If any of these combination(s) has/have the same energy lists:
1. n = 4, l = 2, ml = –2 , ms = –1/2
2. n = 3, l = 2, ml = 1 , ms = +1/2
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3. n = 4, l = 1, ml = 0 , ms = +1/2
4. n = 3, l = 2, ml = –2 , ms = –1/2
5. n = 3, l = 1, ml = –1 , ms = +1/2
6. n = 4, l = 1, ml = 0 , ms = +1/2
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 ?
2.64 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.
2.65 The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will
experience more effective nuclear charge from the nucleus ?
2.66 Indicate the number of unpaired electrons in : (a) P, (b) Si, (c) Cr, (d) Fe and (e) Kr.
2.67 (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 ?
2020-21

Structure of Atom: Unit 2

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STRUCTURE OF ATOM 29

The rich diversity of chemical behaviour of different elements

After studying this unit you will be

• know about the discovery of

2.1 DISCOVERY OF SUB-ATOMIC

field is applied, the electrons deviate from their

2.1.4 Discovery of Protons and Neutrons

Table 2.1 Properties of Fundamental Particles

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

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

Different atomic models were proposed to

massive sun and the electrons being similar

The other commonly used quantity

2.3.2 Particle Nature of Electromagnetic

arrived at a satisfactory relationship by

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

W0 /eV 2.42 2.3 2.25 3.7 4.8 4.3

C:\Chemistry XI\Unit-2\Unit-2(2)-Lay-3(reprint).pmd 27.7.6, 16.10.6 (Reprint)

Problem 2.6 Solution

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

rationalize many points in the atomic structure

Where me is the mass of electron, v is the

and its energy is lowered. That is the reason  R   R 

Problem 2.10 2.4.2 Limitations of Bohr’s Model

Problem 2.11 2.5 TOWARDS QUANTUM MECHANICAL

Louis de Broglie (1892 – 1987) Solution

The value of ∆v∆x obtained is extremely

Using the equation (2.22)

properties. It specifies the laws of motion that

Orbit, orbital and its importance

the same as the number of orbitals per

of the dots in a region represents electron

Both the attractive and repulsive

Causes of Stability of Completely Filled and Half-filled Subshells

The completely filled and completely

Table 2.6 Electronic Configurations of the Elements

* Elements with exceptional electronic configurations

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