Structure of Atom PDF

1
Chapter
Structure of Atom

T he universe is a concourse of atoms.
Marcus Aurelius
1.1 iNTRODUCTION
John Dalton was born in England in 1766. His
The introduction of atomic theory by John Dalton early in the family was poor, and his formal education stopped
nineteenth century marks the beginning of modern era in when he was eleven years old. He became a school
the research initiatives in the field of Chemistry. The virtue teacher. He was colour blind. His appearance and
of Dalton’s theory was not that it was new or original, for manners were awkward, he spoke with difficulty in
theories of atoms are older than the science of chemistry, public. As an experiment he was clumsy and slow.
but that it represented the first attempt to place the cor- He had few, if any outward marks of genius.
puscular concept of matter upon a quantitative basis. In 1808, Dalton published his celebrated New
The theory of the atomic constitution of matter dates back at Systems of Chemical Philosophy in a series of publica-
least 2,500 years to the scholars of ancient Greece and early tions, in which he developed his conception of atoms as
Indian philosophers who were of the view that atoms are the fundamental building blocks of all matter. It ranks
fundamental building blocks of matter. According to them, among two greatest of all monuments to human intel-
the continued subdivision of matter would ultimately yield ligence. No scientific discovery in history has had a
atoms which would not be further divisible. The word more profund affect on the development of knowledge.
‘atom’ has been derived from the Greek word ‘a-tomio’ Dalton died in 1844. His stature as one of the
which means ‘uncuttable’ or non-divisible. Thus, we greatest scientists of all time continues to grow.
might say that as far as atomic theory is concerned, Dalton
added nothing new. He simply displayed a unique ability to
crystallize and correlate the nebulous notions of the atomic Thus, to Dalton, the atoms were solid, hard, impene-
constitution prevalent during the early nineteenth century trable particles as well as separate, unalterable individuals.
into a few simple quantitative concepts. Dalton’s ideas of the structure of matter were born out of
considerable amount of subsequent experimental evidence
1.2 Atomic Theory as to the relative masses of substances entering into chemi-
cal combination. Among the experimental results and rela-
The essentials of Dalton’s atomic theory may be summa- tionship supporting this atomic theory were Gay-Lussac’s
rized in the following postulates: law of combination of gases by volume, Dalton’s law of
1. All matter is composed of very small particles called atoms. multiple proportions, Avagadro’s hypothesis that equal vol-
2. Atoms are indestructible. They cannot be subdivided, umes of gases under the same conditions contain the same
created or destroyed. number of molecules, Faraday’s laws relating to electrolysis
3. Atoms of the same element are similar to one another and Berzelius painstaking determination of atomic weights.
and equal in weight.
4. Atoms of different elements have different properties
Modern Atomic Theory
and different weights.
5. Chemical combination results from the union of atoms Dalton’s atomic theory assumed that the atoms of elements
in simple numerical proportions. were indivisible and that no particles smaller than atoms
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1.2 Structure of Atom
exist. As a result of brilliant era in experimental physics To vacuum

which began towards the end of the nineteenth century Gas at low pressure pump
extended into the 1930s paved the way for the present
modern atomic theory. These refinements established that Cathode Anode
atoms can be divisible into sub-atomic particles, i.e., elec- − +
trons, protons and neutrons—a concept very different from
that of Dalton. The major problems before the scientists at
that time were
(i) How the sub-atomic particles are arranged within the
atom and why the atoms are stable?
(ii) Why the atoms of one element differ from the atoms High voltage
of another elements in their physical and chemical
Fig 1.1 Cathode ray discharge tube
properties?
(iii) How and why the different atoms combine to form
molecules?
(iv) What is the origin and nature of the characteristics of the charge necessary to deposit one atom of a 1-valent
electromagnetic radiation absorbed or emitted by atoms? element by Stoney in 1891. In 1879, Crookes discov-
ered that when a high voltage is applied to a gas at low
pressure streams of particles, which could communicate
1.3 Sub-Atomic Particles momentum, moved from the cathode to the anode. It did
not seem to matter what gas was used and there was
We know that the atom is composed of three basic sub-atomic
strong evidence to suppose that the particles were com-
particles namely the electron, the proton and the neutron. The
mon to all elements in a very high vacuum they could not
characteristics of these particles are given in Table 1.1.
be detected. The cathode ray discharge tube is shown
It is now known that many more sub-atomic particles
in Fig 1.1.
exist, e.g., the positron, the neutrino, the meson, the hyperon
The properties of the cathode rays are given below:
etc, but in chemistry only those listed in Table 1.1 generally
need to be considered. The discovery of these particles and (i) When a solid metal object is placed in a discharge
the way in which the structure of atom was worked out are tube in their path, a sharp shadow is cast on the end
discussed in this chapter. of the discharge tube, showing that they travel in
straight lines.
(ii) They can be deflected by magnetic and electric fields,
1.3.1 Discovery of Electron the direction of deflection showing that they are neg-
The term ‘electron’ was given to the smallest particle atively charged.
that could carry a negative charge equal in magnitude to (iii) A freely moving paddle wheel, placed in their path, is
set in motion showing that they possess momentum,
Table 1.1 The three main sub-atomic particles i.e., particle nature.
(iv) They cause many substances to fluoresce, e.g., the
Particle Symbol Mass Charge familiar zinc sulphide coated television tube.
(v) They can penetrate thin sheets of metal.
Electron e 1/1837 of – 4.8 × 10−10 esu
H-atom or 9.109 × or –1.602 × 10−19 J.J. Thomson (1897) extended these experiments and
10−28 g coulombs (–1 unit) determined the velocity of these particles and their charge/
or 9.1×10−31 kg mass ratio as follows.
Proton p 1.008 amu or + 4.8 × 10−10 esu The particles from the cathode were made to pass
1.672 × 10−24 g or + 1.602 × 10−19 through a slit in the anode and then through a second slit.
or 1.672×10−27 kg coulombs (+ 1 unit) They then passed between two aluminium plates spaced
(1 unit) about 5 cm apart and eventually fell onto the end of the
Neutron n 1.0086 amu or No charge tube, producing a well-defined spot. The position of the
1.675 × 10−24 g spot was noted and the magnetic field was then switched
or 1.675 × 10−27 kg on, causing the electron beam to move in a circular arc
(1 unit) while under the influence of this field (Fig 1.2).
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Structure of Atom 1.3
Spot of light
when top plate is
+ positive
Gas at low pressure
Anode (+)
Spot of light
when plate is
not charged
Cathode
² Deflecting
plates
²
Fluorescent
screen
Fig 1.2 Thomson’s apparatus for determining e/m for the electron
Thomson proposed that the amount of deviation of the Millikan Oil Drop Method
particles from their path in the presence of electrical and
To vacuum pump
magnetic field depends on M
(i) Greater the magnitude of the charge on the particle, −
greater is the interaction with the electric and mag- v
V
B
netic fields, and thus greater is the deflection. Oil sprayer
+ A
(ii) Lighter the particle, greater the deflection Oil
(iii) The deflection of electrons from its original path globules
increase in the voltage across the electrodes, or the W1 W2
E
strength of the magnetic field. x – Rays
Light
By careful and quantitative determination of the mag- E1
netic and electric fields on the motion of the cathode rays,
Thomson was able to determine the value of charge to mass
ratio as Fig 1.3 Millikan’s apparatus for determining the value of
the electronic charge
e
= 1.758820 × 1011 C kg −1 (1.1)
me
e 1.6022 × 10 −19 C
me is the mass of the electron in kg and e is the me = = (1.2)
magnitude of the charge on the electron in Coulomb. e / me 1.758820 × 1011 C kg −1
= 9.1094 × 10−31 kg (1.3)

1.3.2 Charge on the Electron
Small droplets of oil from an atomiser are blown into a
Thomson’s experiments show electrons to be negatively still thermostated airspace between parallel plates, and the
charged particles. Evidence that electrons were discrete rate of fall of one of these droplets under gravity is observed,
particles was obtained by Millikan by his well known oil from which its weight can be calculated. The airspace is
drop experiment during the years 1910-14. By a series of now ionized with an X-ray beam, enabling the droplets to
very careful experiments Millikan was able to determine pick up charge by collision with the ionized air molecules.
the value − electronic charge, and the mass. Millikan By applying a potential of several thousand volts across the
found the charge on the electron to be −1.6 × 10−19 C. parallel metal plates, the oil droplet can either be speeded
The present-day accepted value for the charge on the elec- up or made to rise, depending upon the direction of the elec-
tron is 1.602 × 10−19 C. When this value for ‘e’ is com- tric field. Since, the speed of the droplet can be related to its
pared with the most modern value of e/m, the mass of the weight, the magnitude of the electric field, and the charge it
electron can be calculated. picks up, the value of the charge can be determined.
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1.3.3 Discovery of Proton 9

4 6 C + 0n
Be + 24 He → 12 1
If the conduction of electricity, through gases is due to

particles, which are similar to those involved during Where the superscript refers to the atomic mass and
electrolysis, it was to be expected that positive as well as the subscript refers to the atomic number (the number of
negative ones should be involved, and that they would be protons in the nucleus). Notice that a new element, carbon,
drawn to the cathode. By using a discharge tube contain- emerges from this reaction.
ing a perforated cathode, Goldstein (1886) had observed
the formation of rays (shown to the right of the cathode in 1.4 Atomic Models
Fig 1.4).
J.J. Thomson (1910) measured their charge/mass ratio The discovery that atoms contained electrons caused some
from which he was able to deduce that the particles were consternation. Left to themselves, atoms were known to be
positive ions, formed by the loss of electrons from the electrically neutral. So, the negative charge of the electrons
residual gas in the discharge tube. The proton is the small- had to be balanced by an equal amount of positive charge.
est positively charged particle equal in magnitude to that The puzzle was to work out how the two types of charges
on the electron and is formed from the hydrogen atom by were arranged. To explain this, different atomic models
the loss of an electron. were proposed. Two models proposed by J.J. Thomson and
Earnest Rutherford are discussed here though they cannot
H → H+ + e− explain about the stability of atoms.
Unlike cathode rays, the characteristics of posi-
tively charged particles depend upon the nature of the 1.4.1 Thomson Model of Atom
gas present in the cathode ray tube. These are positively
charged ions. The charge to mass ratio of these parti-
cles is found to be dependent upon the gas from which “A theory is a tool not a creed.” J.J. Thomson
these originate. Some of the positively charged particles Sir Joseph John Thomson 1856–1940
carry a multiple of the fundamental unit of electrical Thomson’s researches on discharge of electricity
charge. The behaviour of these particles in the magnetic through gases led to the discovery of the electron and
or electric field is opposite to that observed for electron isotopes.
or cathode rays.
In 1898, Sir J.J. Thomson proposed that the electrons

1.3.4 Discovery of Neutron are embedded in a ball of positive charge (Fig 1.5). This
The neutron proved to be a very elusive particles to track model of the atom was given the name plum pudding or
down and its existence, predicted by Rutherford in 1920, raisin pudding or watermelon. According to this model
was first noticed by Chadwick in 1932. Chadwick was we can assume that just like the seeds of a watermelon are
bombarding the element beryllium with α-particles and embedded within the reddish juicy material, the electrons
noticed a particle of great penetrating power which was are embedded in a ball of positive charge. It is important
unaffected by magnetic and electric fields. It was found to to note that in Thomson’s model, the mass of the atom is
have approximately the same mass as the proton (hydrogen
ion). The reaction is represented as
Perforated cathode
_
+ H e H+
+
H _ H
_e Positive+ rays
H e
H
Anode
Fig 1.5 The Thomson model of atom. The positive
– charge was imagined as being spread over the entire atom
Fig 1.4 and the electrons were put in this background
Chapter_01.indd 4 8/17/2013 3:42:13 PM

uniformly distributed over the atom. Though this model g-rays are high energy radiations like X-rays, are neutral in
could explain the overall neutrality of the atom, it could not nature and do not consist of particles. As regards penetrat-
explain the results of later experiments. ing power, a-particles have the least followed by b-rays
(100 times that of a-particles) and g-rays (1000 times that
of a-particles).
The Discovery of X-rays and Radioactivity
In 1895, Rontgen noticed when electrons strike a mate-
1.4.2 Rutherford’s Nuclear Model of Atom
rial in the cathode ray tubes, produces a penetrating radia-
tion emitted from the discharge tubes, and it appeared to
originate from the anode. The radiation had the following
properties: Ernest Rutherford 1871–1937
(i) It blackened the wrapped photographic film.
(ii) It ionized gases, so allowing them to conduct Rutherford was born in New Zealand in 1871. He
electricity. was educated at the University of New Zealand and at
(iii) It made certain substances fluoresce, e.g., zinc Cambridge University. He taught at McGill Univer-
sulphide. sity, and at the University of Manchester. In 1919,
he became director of the celebrated Cavendish lab-
Furthermore, the radiation was shown to carry no oratory at Cambridge. In 1908, he received Nobel
charge since it could not be deflected by magnetic or elec- prize for chemistry. Rutherford made many of the
tric fields. Since Rontgen did not know the nature of the basic discoveries in the field of radioactivity. With
radiation, he named them as X-rays and the name is still Bohr and others, he elaborated a theory of atomic
carried on. The true nature of X-rays was not discovered structure. In 1919, he produced the first artificial
until 1912, when it became apparent that its properties transmutation of an element (that of nitrogen into
could be explained by assuming to be wave like in char- oxygen). For many years. he was a vigorous leader
acter, i.e., similar to light but is much smaller wavelength. in laying the foundation of the greatest develop-
It is now known that X-rays are produced whenever fast- ments in atomic science, which he did not live to
moving electrons are stopped in their tracks by impinging see. He died in 1937.
on a target, the excess energy appearing mainly in the form
of X-radiation.
The year after Rontgen discovered X-rays, Henry
In 1911, Ernest (later Lord) Rutherford demonstrated
Becquerel observed that uranium salts emitted a radia-
a classic experiment for testing the Thomson’s model.
tion with properties similar to those possessed by X-rays.
Rutherford, Geiger and Harsden studied in detail the effect
The Curies followed up this work and discovered that
of bombarding a thin gold foil by high speed a-particle
the ore pitchblend was more radioactive than purified
(positively charged helium particles). A thin parallel beam
uranium oxide; this suggested that something more
of a-particles was directed onto a thin strip of gold and the
intensely radioactive than uranium was responsible for
subsequent path of the particles was determined. Since the
this increased activity and eventually the Curies suc-
a-particles were very energetic, it was thought they would
ceeded in isolating two new elements called polonium
go right through the metal foils. To their surprise they
and radium, which were responsible for this increased
observed some unexpected results which are summarized
activity.
as follows:
In 1889, Becquerel reported that the radiation from
(i) It was observed that 99 per cent of the alpha particles
the element radium could be deflected by a magnetic field
passed straight through the foil and struck the screen
and in the same year, Rutherford noticed that the radia-
at the centre.
tion from uranium was composed of at least two distinct
(ii) A few of the alpha particles deflected from their
types. Subsequently, it was shown that the radiation from
original path through varying angles.
both sources contained three distinct components and are
(iii) Hardly one out of the 20, 000 a-particles was bounced
named as a – b and g-rays. Rutherford found that a-rays
back on its path.
consist of high energy particles carrying two units of posi-
tive charge and four units of atomic mass. He concluded The results of Rutherford’s experiment is represented
that a-particles are helium nuclei as when a-particles more explicitly in Fig 1.6.
combined with two electrons yielded helium gas. b-rays Rutherford’s Explanation Rutherford pointed out
are negatively charged particles similar to electrons. The that his results are not in agreement with Thomson’s model.
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++ (i) An atom has a centre of the nucleus, in which posi-

tive charge and mass are concentrated and he called
++ this centre as the nucleus.
The quantitative results of scattering experiments
such as Rutherford’s indicate that the nucleus of an
atom has a diameter of approximately one to six Fer-
mis (1 Fermi = 10−10 m) and atoms have diameters about
100000 times as great as the size of the nucleus, i.e., of
the order 10−5 m.
(ii) The atom as a whole is largely an empty space and
the nucleus is located at the centre of the atom.
(a) (iii) The nucleus is surrounded by the electrons which are
revolving round the nucleus in closed paths like the
− − planets.
++
++ (iv) Electrons and the nucleus are held together by elec-
– trostatic forces of attraction.
Alpha particles
Rutherford, therefore, contemplated the dynamical

+ Nucleus
stability and imagined the electrons to be whirling about
the nucleus, similar to the planetary motion.
++
– –
– – Drawbacks of the Rutherford Model
++
Following objections were raised against the Rutherford’s
++ model:
(b) (i) It did not explain how the protons could be close-
packed to give a stable nucleus.
Fig 1.6 Results of Rutherford’s experiment (a) One (ii) When an electron revolves round the nucleus, it
layer of metal atoms each with nucleus (b) One atom of will radiate out energy, resulting in the loss of
the metal with nucleus energy. This loss of energy will make the electron
to move slowly and consequently, it will be mov-
He explained the above results by drawing the following ing in a spiral path and ultimately falling onto the
conclusions: nucleus. So, the atom should be unstable, but the
(i) As most of the alpha particles passed very nearly atom is stable.
straight through the foil, it means that the atom is (iii) If an electron starts losing energy continuously, the
extra ordinarily hollow with a lot of empty space observed spectrum would be continuous and have
inside. broad bands merging into one another. But most of
(ii) The only way to account for the large deflection is the atoms give line spectra. Thus, Rutherford’s model
to say that the positive charge and mass in the gold failed to explain the origin of line spectra.
foil are concentrated in very small regions. Although
most of the alpha particles can go through without
any deflection, occasionally some of them which
come closer to the region of positive charge, they
repel each other, and the repulsion may be big enough
to cause the α-particles to undergo large deviations
from its original path. + –
(iii) Due to the rigid nature of the nucleus, some Nucleus Electron
a-particles on colliding with the positive charge, turn
back on their original paths.
On the basis of above observations and conclu-
sions, Rutherford proposed the nuclear model of atom as Fig 1.7 An electron that is accelerating, radiates energy.
follows: As it loses energy, it spirals onto the nucleus
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1.5 Atomic Number Mass number (A) = Number of protons (Z) + Number
of neutrons (n)
In 1913, H.G.J. Moseley, a young English Physicist and
one of Rutherford’s brilliant students, examined the X-ray
spectra of 38 elements. When Moseley bombarded differ- 1.5.1 Isobars, Isotopes and Isotones
ent elements with cathode rays, the X-rays were generated
In modern methods, the symbols of elements are written
which had different frequencies. He suggested that the
as ZA [ X ]x , where the left hand superscript A is the mass
n
frequency of X-rays produced in this manner was related

number, left hand subscript Z is the atomic number, right
to the charge presented on the nucleus of an atom of the
hand superscript n is the number of charges and right hand
element used as anode. When he took the frequencies of a
subscript is the number of atoms.
particular line in all elements such as Ka or Kb lines, then
Different atoms having same mass number but with
the frequencies were related to each other by the equation.
different atomic numbers are called isobars, e.g., 14 6 C and
v = a (Z−b) (1.3) 14
7 N . The atoms having same atomic number but with dif-
ferent mass numbers are called isotopes. The difference
Where, v is the frequency of any particular Ka or Kb etc,
between isotopes is due to the difference in the number
line. Z is the atomic number of the element and ‘a’ and ‘b’
of neutrons present in the nucleus, e.g., 11 H, 12 D and 13 T
are constants for any particular type of line. A plot of v
are isotopes of hydrogen namely protium, deuterium and
vs Z gives a straight line showing the validity of the above
tritium respectively.
equation. This is shown in Fig 1.8.
Isotopes exhibit similar chemical properties because
However, no such relationship was obtained when the
they depend on the number of protons in the nucleus. Neu-
frequency was plotted against the atomic mass. Moseley
trons present in the nucleus show very little effect on the
further found that the nuclear charge increases by one unit
chemical properties of an element. So, all the isotopes of a
in passing from one element to the next element arranged
given element show same chemical behavior.
by Mendeleef in the order of increasing atomic weight. The
Sometimes atoms of different elements contain same
number of unit positive charges carried by the nucleus of
number of neutrons. Such atoms are called isotones. For
an atom is termed as the atomic number of the element.
example, 13 14
6 C and 7 N. Isotones differ in both atomic
Since, the atom as a whole is neutral, the atomic number
number and mass numbers but the difference in atomic
is equal to the number of positive charges present in the
number and mass number is the same.
nucleus.
Atomic number = Number of protons present in the 1.6 Developments Leading to the
nucleus Bohr Model of Atom
= Number of electrons present outside the nucleus of During the period of development of new models to
the same atom. improve Rutherford’s model of atom, two new concepts
While the positive charge of the nucleus is due to pro- played a major role. They are
tons, the mass of the nucleus is due to protons and neu- (i) Dual behaviour of electromagnetic radiation: This
trons. The total number of protons and neutrons is called means that light has both particle like and wave like
the mass number. The particles present in the nucleus are properties.
called nucleons. (ii) Atomic spectra: The experimental results regard-
ing atomic spectra of atoms can only be explained by
assuming quantized (fixed) electronic energy levels
in atoms.
Let us briefly discuss about these concepts before
studying a new model proposed by Niels Bohr known as
Bohr Model of Atom.
√υ
1.6.1 Nature of Light and Electromagnetic

Z Radiation
Fig 1.8 Variation of x–rays frequency with atomic A radiation is a mode of transference of energy of differ-
number ent forms. Light, X-rays and g-radiations are examples of
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(mm), nanometer (nm), picometer (pm) etc. These

units are related to SI unit (m) as
1 Å = 10−10 m; 1 m = 10−6 m, 1 mm = 10−9 m,
1 nm = 10−9 m; 1 pm = 10−12 m
2. Frequency (n): The number of waves passing through
a given point in a unit time is known as its frequency.
It is denoted by the Greek letter n (nu). The frequency
is inversely proportional to the wavelength. Its unit in
cycles per second (cps) of Hertz (Hz); 1 cps = 1 Hz.
A cycle is said to be completed when a wave consisting
crest and trough passes through a point.
Fig 1.9 Diffraction of the waves while passing through
3. Velocity (c): The distance travelled by the wave in one
a slit
second is called the velocity of wave. It is equal to prod-
uct of wavelength and frequency of the wave. Thus,
λ
Displacement
c = vl
c
or v = (1.4)
λ
λ 4. Amplitude: It is the height of crest or depth of wave’s

Distance trough and is generally expressed by the letter ‘a’.
The amplitude of the wave determines the intensity or
Fig 1.10 Propagation of wave brightness of radiation.
5. Wave number ( v ): It is equal to the reciprocal of
wavelength. In other words, it is defined as the number
the radiant energy. The earliest view of light, due to New-
of wavelengths per centimeter. It is denoted by v and
ton, regarded light as made up of particles (commonly
is expressed in cm−1. Thus,
termed as corpuscles of light). The particle nature of light
explained some of the experimental facts such as reflec- 1
v= (1.5)
tion and refraction of light. However, it failed to explain the λ
phenomenon of interference and diffraction. The corpuscu- c c
But v = or λ =
lar theory was therefore, discarded and Huygens proposed λ v
a wave-like character of light. With the help of wave theory λ
of light, Huygens explained the phenomena of interference v= (1.6)
c
and diffraction.
We know that when a stone is thrown into water
Electromagnetic Radiation
of a quiet pond, on the surface of water waves are
produced. The waves originate from the centre of the Maxwell in 1873 proposed that light and other forms of
disturbance and propagate in the form of up and down radiant energy propagate through space in the form of
movements. The point of maximum upward displace- waves. These waves have electric and magnetic fields
ment is called the crest and the point of maximum associated with them and are, therefore, called electro-
downward displacement is called trough. Thus, waves magnetic radiations and electromagnetic waves.
may be considered as disturbance which originate from The important characteristics of electromagnetic
some vibrating source and travel outwards as a continu- radiations are
ous sequence of alternating crests and troughs as shown (i) These consist of electric and magnetic fields that
in Fig 1.10. oscillate in the directions perpendicular to the direc-
tion in which the wave is travelling as shown in
Fig 1.11. The two field components have the same
Characteristics of the Wave Motion
wavelength and frequency.
1. Wavelength (l): It is the distance between two near- (ii) All electromagnetic waves travel with the same
est crests or troughs. It is denoted by the Greek letter speed. In vacuum, the speed of all types of electro-
Lambda l and is expressed in Angstrom units (Å). It is magnetic radiation is 3. 00 × 108 ms−1. This speed is
also expressed as micron meter (m), milli micron meter called the velocity of light.
Chapter_01.indd 8 8/17/2013 3:42:17 PM

(iii) These electromagnetic radiations do not require any electromagnetic radiations, such as X-rays, ultraviolet rays,
medium for propagation. For example, light reaches infra-red rays, microwaves and radiowaves.
us from the sun through empty space. The arrangement of different types of electromagnetic
radiations in the order of increasing wavelengths (or decreas-
Electromagnetic Spectrum ing frequencies) is known as electromagnetic spectrum.
Different regions of electromagnetic spectrum are
The different electromagnetic radiations have different
identified by different names. The complete electromag-
wavelengths. The visible light in the presence of which
netic spectrum is shown in Fig 1.12.
our eyes can see, contains radiations having wavelength
The various types of electromagnetic radiations have
between 3800 Å to 7600 Å. The different colours in the
different energies and are being used for different purposes
visible light corresponds to radiations of different wave-
as listed in Table 1.2.
lengths. In addition to visible light there are many other
Z Table 1.2 Some applications of electromagnetic waves

Y
Electric field Name Frequency Wavelength Uses

g-rays 20
10 – 10 21
10 −12
Cancer treatment
X-rays 1017 – 1019 10−10 Medical
“pictures”,
material testing
Magnetic Ultraviolet 1015 – 1016 10−7 Germicidal lamps
field X
Visible 1013 – 1014 10−6 Illumination
Direction of
propagation of Infrared 1012 – 1013 10−4 Heating
em wave Microwave 109 – 1011 10−2 Cooking, radar
Radio 105 – 108 102 Signal
Fig 1.11 Electric and magnetic fields associated with an
frequency transmission
electromagnetic wave
Increasing wavelength
Decreasing freqency
24
1022 10
20
1018 10
16 14 12 10 8
106
4
10 10 10 10 10 10 102 100 v(Hz)
Cosmic
rays γ−rays X-rays UV IR Microwave FM AM Long radio waves
Radio waves
10–16 10–14 10–12 10–10 10–8 10–6 10–4 10–2 100 102 104 106 108 λ(Hz)
V I B G Y O R
I
N
D
VIOLET I BLUE GREEN YELLOW ORANGE RED
G
O
λ( ° ) 4000 4300 4500 4900 7500 °
∀ ∀
5500 5900 6500
Fig 1.12 Complete electromagnetic spectrum
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Solved Problem 1 1.6.2 Quantum Theory of Radiation

Calculate and compare the energies of two radiations, one When an object is heated, its colour gradually changes.
with a wavelength of 8000 Å and the other with 4000 Å. For example, a black coal becomes red, orange, blue and
Solution: finally ‘white hot’ with increasing temperature. This shows
According to Planck’s equation, that red radiation is most intense at a particular tempera-
c ture, blue radiation is most intense at another temperature
E = hv = h and so on. It indicates that the intensities of radiations of
λ different wavelengths emitted by a hot body depend upon
h = 6.60 × 10−34 J s; c = 3 × 1010 ms−1 the temperature. The curves representing the distribution
Also l1 = 8000 Å = 8000 × 10−10 m of radiation from a black body at different temperatures are
and l2 = 4000 Å = 4000 × 10−10 m shown in Fig 1.13.
6.62 × 10 −34 J s × 3 × 1010 m s −1 A black body is one which will absorb completely
E1 = the incident radiation of wavelength. The ideal black body
8000 × 10 −10 m
does not reflect any energy, but it does radiate energy.
= 2.475 × 10−19 J Although no actual body is perfectly black, it is possible
6.62 × 10 −34 J s × 3 × 1010 m s −1 to postulate a condition where radiation is completely
and E2 = enclosed in a space surrounded by thick walls at a con-
4000 × 10 −10 m stant temperature. Thus, we may imagine a cavity inside a
= 4.95 × 10−19 J solid body containing a small hole in one wall whereby the
E1 2.475 × 10 −19 J investigator may study the enclosed radiation without alter-
= ing its character. When a beam of light is passed through
E2 4.95 × 10 −19 J the hole, it would be absorbed by the inner walls of the
E1 1 enclosure and their temperature increases. As soon as the
or = beam was removed, since the enclosed kept at a constant
E2 2 temperature the excess energy emerges through the hole
or 2E1 = E2 in the form light. This gives a distinctive spectrum, usually
referred to as the black body spectrum. If the energy emit-
ted is plotted against its frequency or wavelength where
Solved Problem 2 n = c / l, the curve shows a maximum, as indicated in
Fig 1.13. The graph shows that the energy emitted is
A radio station is broadcasting a programme at 100 MHz
frequency. If the distance between the radio station and
the receiver set is 300 Km, how long would it take the sig-
2000°
nal to reach the receiver set from the radio station? Also
calculate wavelength and wave number of these radio
waves.
Solution:
All electromagnetic waves travel in vacuum or in air
with the same speed of 3 × 10−8 m s−1
Energy
Distance 300 × 1000 m 1750°

Time taken = = = 1 × 10 −3 s
Velocity 3 × 108 m s −1
1500°
Calculate of wavelength (l),
c = vl
1250°
c 3 × 108 m s −1
l= = = 3m 1000°
v 100 × 106 s −1
0 1 2 3 4 5 × 10–4 cm
Calculation of wave number (v ) Wavelength
1 1 Fig 1.13 Energy distribution for black body radiation at
v = = = 0.33 m −1
λ 3m different absolute temperatures
Chapter_01.indd 10 8/17/2013 3:42:19 PM

greatest at the middle wavelengths in the spectrum and

least at the highest and lowest frequencies. If curves are
plotted for a series of temperatures, as given in Fig 1.13.
It is found that the maximum moves towards shorter wave-
lengths as the temperature rises.
Max Planck 1858–1947

Quantized energy Continuous change of energy
A German physicist. He received his Ph.D. in theo- (a) (b)
retical physics from the University of Munich in
1879. Max Planck was well known for the Quan- Fig 1.14
tum Theory which won the Nobel Prize for physics
in 1918. He also made significant contributions to
thermodynamics and other areas of physics.
Electron
KE
The shapes of the curves could not be explained on Metal hυ 1
mv2 = hυ - hυ0
the basis of wave theory of radiation. Max Planck in 1900 2
resolved this discrepancy by postulating the assumption
that the black body radiates energy — not continuously x = Work
but discontinuously in the form of energy packets called function = hυ0
quanta. The general quantum theory of electromagnetic
radiations can be stated as Radiation
(i) When atoms or molecules absorb or emit the radiant
energy, they do so in separate units of waves. These
waves are called quanta or photons.
(ii) The energy of a quantum or photon is given by – e– +
e– e–
E = hv (1.7)
Evacuated tube
where, v is the frequency of the emitted radiation and
h is the Planck’s constant.
(iii) An atom or molecule emits or absorbs either one G
quantum of energy (hv) or any whole number
Fig 1.15 (a) Einstein’s explanation of photoelectric
multiples of this unit.
effect, and (b) Experimental device for photoelectric
This theory provided the basis for explaining the photo- effect
electric effect, atomic spectra and also helped in understand-
and the ball can have any value of energy correspond-
ing the modern concepts of atomic and molecular structure.
ing to any point on the ramp. Energy in this case in not
quantized.
Quantization of Energy
The restriction of any property to discrete values is called 1.6.3 Photoelectric Effect
quantization. A quantity cannot vary continuously to have When a beam of light falls on a clean metal plate in vac-
any arbitrary values but can change only discontinuously uum, the plate emits electrons. This effect was discovered
to have some specific values. For example, a ball moves by Hertz in 1887, and is known as the photoelectric effect.
down a staircase (Fig 1.14a) then the energy of the ball The metal surface emits electrons by the action of light,
changes discontinuously and it can have only certain def- that can be demonstrated using negatively charged gold
inite values of energy corresponding to the energies of leaf electroscope (Fig 1.15). As the light from carbon arc
various steps. Energy of the ball in this case is quantized. falls on the metal plate, the diversion of leaves is reduced
On the other hand, if the ball moves down a ramp (Fig slowly. This shows that electrons come out of all metal
1.14b), then the energy of the ball changes continuously plates.
Chapter_01.indd 11 8/17/2013 3:42:20 PM

The studies have revealed the following facts: Metal Li Na K Mg Cu Ni

(i) Photoelectric effect is instantaneous, i.e., as soon as
the light rays fall on the metal surface, electrons are W (eV) 2.42 2.3 2.25 3.7 4.8 4.3
ejected.
(ii) Only light of a certain characteristic frequency is Solved Problem 3
required for expulsion of electrons from a particular
metal surface. Calculate the energy in one photon of yellow light of wave-
(iii) The number of electrons emitted are directly propor- length 589 nm.
tional to the intensity of the light. Solution:
(iv) The gas surrounding the metal plate has no effect on The energy E, of one photon
photoelectric transmission. hc
E = hν = w
(v) Kinetic energy of photoelectron depends upon the λ
nature of metal.
(vi) For the same metal kinetic energy of photoelectrons Substituting the values
varies directly with the frequency of light. (6.626 × 10 −34 Js) (3.00 × 108 m s −1 )
E= = 3.375 × 10 −19 J
If the frequency is decreased below a certain value 5890 × 10 −10 m
(Threshold frequency), no electrons are ejected at all.
The classical wave theory of light was completely Solved Problem 4
inadequate to interpret all these facts. Einstein applied the When a radiation of wavelength 200 nm falls on a metal
quantum theory of radiation to explain this phenomenon. surface, the work function of the metal being 5 eV, the elec-
An electron in a metal is found by a certain amount of tron is ejected. What is the velocity of the electron?
energy. The light of any frequency is not able to cause the Solution:
emission of electrons from the metal surface. There is cer- Work function 5 eV = 5 × 1.602 × 10−19 J = 8.01 × 10−19
tain minimum frequency called the threshold frequency J (\1eV = 1.602 × 10−19 J)
which can just cause the ejection of electrons. Suppose the Work function = hv0
threshold frequency of the light required to eject electrons
Work function 8.01 × 10 −19 J
from the metal is v0. When photon of light of this frequency v0 = = = 1.21 × 10 −15 S−1
strikes the metal surface, it imparts its entire energy (hv0) h 6.626 × 10 −34 J
to the electron. This enables the electrons to break away
c 3.0 × 108 m s −1
from the atom by overcoming the attractive influence of the v= =
nucleus. Thus, each photon can eject one electron. If the λ 200 × 10 −9 m
frequency of the light is less than n0, the electrons are not 1 2
= 1.5 × 1015 s −1 mv = h ( v − v0 )
ejected. If the frequency of the light (say v) is more than 2
v0, more energy is supplied to the electron. The remaining
2h 2 × 6.626 × 10 −34
energy, which will be the energy hv imparted by incident V2 = ( v − v0 ) = (1.5 − 1.21) × 1015
photon and the energy used up, i.e., hv0, would be given as m 9.11 × 10 −31 kg
kinetic energy to the emitted electron. Hence, V = 0.649 × 106 m s −1
1
hv = hv0 + mv 2 (1.8)
2 Solved Problem 5
1
where mv2 is the kinetic energy of the emitted A photon of wavelength 253.7 nm strikes a copper plate,
2 the work function of the metal being 4.65 eV. Calculate
electron and hv0 is called the work function. the energy of photon and kinetic energy of the emitted
photoelectron.
1 2 Solution:
or mv = h(v − v0) (1.9)
2 (i) Energy of the photon
This equation is known as Einstein’s photoelectric c 3 × 108 m s −1
equation. If the frequency of light is less than the thresh- v= = = 11.824 × 1014 s −1
λ 253.7 × 10 −9 m
old frequency, there will be no ejection of electrons. Values
of photoelectric work functions of some metals are given E = hv = ( 6.626 × 10 −34 Js )(11.824 × 1014 s −1 )
below. = 7.83 × 10−19 J
Chapter_01.indd 12 8/17/2013 3:42:21 PM

Since, 1 eV = 1.602 × 10−19 J

7.83 × 10 −19 J These research papers were published in 1905 while
\E = = 4.887 eV he was working as a technical assistant in a Swiss
1.602 × 10 −19 J
patent office in Berne. He received the Nobel Prize
(ii) Kinetic energy of the photon for Physics in 1921 for his explanation of the photo-
Work function = 4.65 eV electric effect. His work has influenced the develop-
KE = hv − Work function ment of physics in significant manner.
= 4.887 eV − 4.65 eV = 0.237 eV “To him who is discoverer in the field (or sci-
ence), the products of his imagination appear so nec-
1.6.4 Compton Effect essary and natural that he regards them, and would
like to have them regarded by others, not as creations
According to classical electromagnetic wave theory, mon- of thought but as given realities”— Albert Einstein
ochromatic light falling upon matter should be scattered
without change in frequency. But when X-rays are impinged
on matter of low atomic weight, X-rays of slightly longer
wavelength than those of impinging beam were produced. Also according to Einstein’s mass energy equation E
In other words when a photon collides with an electron, it = mc2 where m is the mass of photon. From the above two
may leave with a lower frequency, and the electron thereby equations, we get
acquires a greater velocity. In the collision the energy of the hv = mc2 (1.10)
photon is reduced and the energy of the electron is increased.
This is called Compton effect and can be explained as a hv
m= (1.11)
result of the impact between two bodies, the photon and the c2
electron and it is of course additional proof of the corpus- h c
m= 2 ⋅ (1.12)
cular nature of light. This impact is elastic, and both kinetic c λ
energy and momentum are conserved. After the encounter h
each body has a different energy and a different momentum m= (1.13)
cλ
from the values it had before the contact, but the sum of the
energies and the sum of the momenta are unchanged. Thus, the mass of the photon can be calculated.
1.6.5 Dual Nature of Electromagnetic 1.6.6 Atomic Spectra

Radiations The velocity of light depends upon the nature of the medium
through which it passes. Because of this reason while a beam
As described, photoelectric effect and Compton effect could be
of light passing from one medium to another, deviates or
explained considering that electromagnetic radiations consist-
refracts from its original path, the radiations with shorter
ing of small packets of energy called quanta or quantum (or
wavelength deviate more than the one with a longer wave-
single photon). These packets of energy can be treated as parti-
length. If a ray of sunlight or any white light is allowed to
cles, on the other hand, radiations exhibit phenomena of inter-
pass through a prism, it splits up into a continuous band of
ference and diffraction which indicate that they possess wave
seven colours from red to violet as observed in a rainbow.
nature. So, it may be concluded that electromagnetic radiation
This phenomenon is known as dispersion and the pattern
possesses the dual nature, i.e., particle nature as well as wave
of colours is called spectrum. The red colour light radiation
nature. Einstein (1905) even calculated the mass of the photon
having longest wavelength will be deviated least while the
associated with a radiation of frequency v as given below:
radiation of violet colour having shortest wavelength will be
The energy E of the photon is given as E = hv
deviated more. The spectrum of white light that we can see
ranges from violet at 7.50 × 1014 Hz to red at 4 × 1014 Hz.
Albert Einstein 1879–1955 In this spectrum one colour merges into another colour
adjacent to it viz violet merges into blue, blue into green
Born in Germany but later shifted to America. He and so on. When electromagnetic radiation interacts with
was regarded as one of the two great physicists the matter, atoms and molecules may absorb energy and reach
world has known, the other being Isaac Newton. He to a higher energy state. While coming to the ground state
is well known for his three research papers on special (more stable lower energy state) the atoms and molecules
relativity, Brownian motion and photoelectric effect. emit radiations in various regions of the electromagnetic
spectrum.
Chapter_01.indd 13 8/17/2013 3:42:21 PM

1.6.7 Types of Spectra extended throughout the spectrum and are gener-
ally obtained from the light sources like mercury,
Spectra are of two types: Emission spectra and Absorption
sodium, neon discharge tube, etc.
spectra
(c) Band spectrum: This type of spectrum arises
(i) Emission spectra: When energy is supplied to a when the emitter in the molecular state is excited.
sample by heating or irradiating it, the atoms or mol- Each molecule emits bands which are character-
ecules or ions present in the sample absorb energy istics of the molecule concerned and that is why
and the atoms, molecules or ions having higher we call this as molecular spectrum also. The
energy are said to be excited. While coming to the sources of band spectrum are (i) carbon with a
ground (normal) state the excited species emit the metallic salt in its core, (ii) vacuum tube, etc.
absorbed energy. The spectrum of such emitted radia- In the emission spectra, bright lines on black back-
tion is called the emission spectrum. Emission spec- ground will appear.
tra are further classified according to its appearance It may be noted that the dark lines in absorption spec-
as continuous, line and band spectra. tra appear exactly at the same place where the coloured
(a) Continuous spectrum: When the source lines appear in the emission spectra.
emitting light is an incandescent solid, liquid or
(ii) Absorption spectra: It is produced when the light
gas at a high pressure, the spectrum so obtained
from a source emitting a continuous spectrum is
is continuous. In other words, this type of spec-
first passed through an absorbing substance and then
trum is obtained whenever matter in the bulk is
recorded after passing through a prism in a spectro-
heated. For example, hot iron and hot charcoal
scope. In that spectrum, it will be found that certain
gives the continuous spectra.
colours are missing which leave dark lines or bands
(b) Line spectrum: Line spectrum is obtained when
at their places. This type of spectrum is called the
the light emitting substance is in the atomic state.
absorption spectrum. Similar to emission spectra,
Hence, it is also called as the atomic spectrum.
absorption spectra are also of three types:
Line spectrum consists of discrete wavelengths
(a) Continuous absorption spectrum: This type
of spectrum arises when the absorbing material
absorbs a continuous range of wavelengths. An
Film interesting example is the one in which red glass
absorbs all colours except red and hence, a con-
Excited
tinuous absorption spectrum will be obtained.
sample
(b) Line absorption spectrum: In this type, sharp
dark lines will be observed when the absorbing
Prism
substance is a vapour or a gas. The spectrum
Increasing wavelength
obtained from sun gives Fraunhofer absorption
lines corresponding to vapours of different ele-
ments which are supposed to be present on the
Emission spectrum surface of the sun.
(c) Band absorption spectrum: When the absorp-
Fig 1.16 tion spectrum is in the form of dark bands, this is
known as band absorption spectrum An inter-
esting example is that of an aqueous solution
Emission spectrum of Barium of KMnO4 giving five absorption bands in the
green region.
The pattern of lines in the spectrum of an element is
characteristics of that element and is different from those
Absorption spectrum of Barium of all other elements. In other words, each element gives a
unique spectrum irrespective of even the form in which it
is present. For example, we always get two important lines
589 nm and 589.6 nm in the spectrum of sodium whatever
may be its source. It is for this reason that the line spectra
Fig 1.17 Illustrating emission and absorption spectra are also regarded as the fingerprints of atoms.
Chapter_01.indd 14 8/17/2013 3:42:23 PM

Since atoms of different elements give characteris- Hydrogen Spectrum

tic sets of lines of definite frequencies, emission spectra
As explained above, each element emits its own charac-
can be used in chemical analysis to identify and estimate
teristic line spectrum which is different from that of any
the elements present in a sample. The elements rubidium,
other element. Since, hydrogen contains only one electron,
caesium, thallium, gallium and scandium were discov-
its spectrum is the simplest to analyze.
ered when their minerals were analyzed by spectroscopic
To get the spectrum of hydrogen, the gas is enclosed in
methods. The element helium was discovered in the Sun by
a discharge tube under low pressure and electric discharge
spectroscopic method.
is passed through it. The hydrogen molecules dissociate
into atoms and get excited by absorbing the energy: On
Absorbing the principle that what goes up must come down, sooner or
Film later the atoms must loose their energy and fall back to the
sample
ground state, by loosing the energy as light. The light that
is given out can be measured in a spectrometer and the pat-
Source of tern recorded on a photographic paper. The pattern is called
white light hydrogen spectrum.
The hydrogen spectrum obtained consists of a series
Prism of lines in the visible, ultraviolet and infrared regions.
Increasing wavelength These have been grouped into five series in Fig 1.19
which are named after their discoverers. These are given
in Table 1.3 with the year when discovered. The Balmer
series happened to be the first series of lines in the hydro-
Absorption spectrum gen spectrum. This was because the lines were in the
visible part of the spectrum and therefore the easiest to
Orange
Yellow
Indigo
observe.
Green
Violet
Blue
Red
Balmer (1885) discovered a relationship between the

Visible spectrum wave number and the position of the line in the series.
The relation is
1  1 1 
= v = RH  2 − 2  (1.14)
λ 2 m 
Prism where, RH is the Rydberg constant and is equal to
Slit 109677 cm−1.
v is the wave number and m is an integer having values
Source of 3, 4, 5, 6, etc. Ritz (1908) gave a generalization known
white light as Ritz Combination principle which was nicely applica-
ble to hydrogen spectrum. According to this principle, the
wave number in any line in a series can be represented as a
Continuous emission spectrum of white light/sun
difference of two square terms, one of which is consistent
Fig 1.18 Emission and absorption spectra and the other varies throughout the series. Thus,
Paschen
Balmer
Lyman
Series
Series
Series
Series
Pfund
Violet Blue Blue-green Red

δ γ β α
Brackett Series α/cm–1 3500 4000 4500 5000 5500 6000 6500 7000
Wavelength in angstroms
0 20,000 40,000 60,000 80,000 100,000
(a) (b)
Fig 1.19 Hydrogen spectrum (a) Relative location of the Lyman, Balmer, Paschen, Brackett and Pfund series of hydrogen
spectrum (b) The Balmer-series spectrum of hydrogen
Chapter_01.indd 15 8/17/2013 3:42:24 PM

Table 1.3 Solution:
Region of 1 1 1  −1 15 −1
v= = RH 12 − 4 2  cm = 109677 × 16 cm
Series spectrum Value of n Values of m λ
Lyman (1914) Ultraviolet 1 2, 3, 4, ... = 102822 cm −1
Balmer (1885) Visible 2 3, 4, 5, ...
Paschen (1908) Infrared 3 4, 5, 6, ...
Brackett (1922) Infrared 4 5, 6, 7, ... 1.7 Bohr’s Model of the Atom
Pfund (1924) Infrared 5 6, 7, 8, ...
Neils Bohr 1885–1962
1 1  Born in Denmark in 1885. He received Ph.D. from

v = RH  2 − 2  (1.15)
n m  the University of Copenhagen in 1911. He spent a
where, RH is Rydberg constant. year with J.J. Thomson and Ernest Rutherford in
All the lines appearing in the hydrogen spectrum are England. In 1913, he returned to Copenhagen and in
governed by the above equation. For, 1920 he was named as Director of the Institute of
Theoretical Physics.
1 1  Bohr’s theory of atomic structure, which was
Lyman series v = RH  2 − 2  ; m = 2,3, 4 (1.16)
1 m  presented in 1913, laid a broad foundation for the
great atomic progress of recent years.
1 1 
Paschen series v = RH  2 − 2  ; m = 4,5,6 (1.17) Second only in importance to his celebrated
 3 m  theory are the facts that it was in Bohr’s laboratory
1 1  that the implications of nuclear fission were first
Brackett series v = RH  2 − 2  ; m = 5,6, 7 (1.18) predicted and that he obtained an understanding
4 m 
of nuclear stability that contributed greatly to the
1 1  spectacular development of atomic energy.
Pfund series v = RH  2 − 2  ; m = 6, 7,8 (1.19)
5 m  After the First World War, Bohr worked for
peaceful uses of atomic energy. He received the first
Solved Problem 6 Atoms for Peace award in 1957. Bohr was awarded
An electronic transition from M shell (m = 3) to K shell the Nobel Prize for Physics in 1922.
(n = 1) takes place in a hydrogen atom. Find the wave “...... The very word ‘experiment’ refers to a
number and the wavelength of radiation emitted (R = situation where we can tell others what we have done
1,09,677 cm−1). and what we have learned” — Neils Bohr.
Solution: “Our experiments are questions that we put to
Nature.” — Neils Bohr.
1 1 1 
v= = RH  2 − 2  , n = 1 and m = 3
λ n m 
In order to explain the line spectra of hydrogen and the
1 1  8 overcome to objections leveled against Rutherford’s model
= 1, 09,677  2 − 2  = 109677 ×
 1 3  9 of the atom, Neils Bohr (1913) proposed his quantum
mechanical structure of the atom. He made use of quan-
v = 97, 491 cm −1 tum theory, according to which energy is lost or gained not
gradually, but in bundles or quanta. The concept of nucleus
Wavelength, explained by Rutherford was retained in Bohr’s model.
1 1 Through this model does not meet the modern quantum
λ= = = 1.026 × 10 −5 cm = 1026 A mechanics, it is still in use to rationalize many points in the
v 97491
atomic structure and spectra. The important postulates of
the Bohr Theory are:
Solved Problem 7
1. Electrons move in certain fixed orbits associated with
In hydrogen atom, an electron jumps from fourth orbit a definite amount of energy. The energy of an electron
to first orbit. Find the wave number, wavelength and the moving in an orbit remains constant as long as it stays
energy associated with the emitted radiation. in the same orbit called stationary state or orbit.
Chapter_01.indd 16 8/17/2013 3:42:25 PM

Hence, a certain fixed amount of energy is associated Based on the above postulates, Bohr calculated the
with each electron in a particular orbit. Thus, stationary radii of the various orbits and the energies associated
orbits are also known as energy levels or energy shells. with the electrons present in those orbits. The frequen-
Bohr gave number 1, 2, 3, 4 etc, (starting from the nucleus cies of the spectral lines determined experimentally by
to these energy levels). The various energy levels are Lyman, Balmer and others are in excellent agreement
designated as K, L, M, N etc, and are termed as principal with those calculated by Bohr’s theoretical equations.
quantum numbers.
2. Energy is emitted or absorbed only when an electron
1.7.1 Bohr’s Theory of the Hydrogen Atom
jumps from one orbit to another, i.e., form one energy
level (or principal quantum number) to another. Bohr pictured the hydrogen atom as a system consisting
Since each level is associated with a definite amount of a single electron with a charge designed as e, rotating
of energy, the farther the energy level from the nucleus, the in a circular orbit of radius r about the nucleus of charge
greater is the energy associated with it. Ze with a velocity v.
3. Permissible orbits are those for which the angular
momentum is an integral multiple of (h/2p). Centrifugal
The electrons move in such orbits without any loss of forces
energy. Thus, angular momentum v mv2
_ r
nh e
me vr = (1.20) r
2π Force of
Ze + x attraction
where, n is an integer 1, 2, 3 ....... me is mass of elec-
Nucleus
tron and r is the radius of orbit. The n values corresponds
to the principal quantum number.
4. When an electron gets sufficient energy from outside,
an electron from an inner orbit of lower energy Tangential velocity of the revolving electron
state E1 moves to an outer orbit of higher energy
state E2. Calculation of velocity V: The angular momentum of
The excited state lasts for about 10−8 s. The difference the electron is defined as the product of the velocity of the
of energy E2 −E1 is thus radiated out. During the emission electron in its orbit, its mass, and the radius of its orbit. The
or absorption of radiant energy to Planck’s, Einstein equa- product is symbolized as mvr. According to Bohr’s postu-
tion E = hv is obeyed. Thus the frequency of emitted radia- lates, the angular momentum are whole multiples of h / 2p.
tion is given by Therefore, according to this quantum restriction,
angular momentum may be restricted as
hv = DE = E2 − E1 (1.21)
nh
mvr =
2π
n=6 \ The velocity of the electron in an orbit,
n=5
n=4 nh
n=3 v= (1.22)
2πmr
n=2
n=1 Radius of an Orbit
K L M NO P According to Coulomb’s law, the electrostatic force of attraction

Fe between the charges may be evaluated mathematically as
Ze 2
Fe = 2 (1.23)
r
By definition, the magnitude of the centrifugal force
Fc for an electron of mass m, with a velocity in its orbit of
V and with an orbit radius r is given as
Fig 1.20 Bohr’s orbit-like representation of various mv 2
Fc = (1.24)
energy levels r
Chapter_01.indd 17 8/17/2013 3:42:26 PM

In order that the electron’s orbit may remain stable, it 2π2 me 4 Z 2

is necessary to assume that the two forces, electrostatic and En = − × 2 (1.33)
h2 n
centrifugal, are equal and opposed to each other. From this
assumption may be deduced the following mathematical where, En is the total energy of the electron in the orbit
relationship designated by the quantum number n.
mv 2 Ze 2
= 2 (1.25)
r r Solved Problem 8
Calculate the (i) radius of first orbit (ii) velocity of electron in
and upon solving for
the first orbit, and (iii) energy of first orbit of hydrogen atom.
Ze 2 Solution:
v= (1.26) n2 h2
mr (i) Radius of an orbit is given by r = 2
4 π mZe 2
Equations (1.26) and (1.22) may be equated since they
Since, n = 1 and Z for hydrogen = 1
are equal to each other
h2
Ze 2 nh r=
= (1.27) 4 π2 me 2
mr 2πmr
( 6.626 × 10 ergs )
−27 2
and upon solving for r, we obtain r=

4 × π2 × ( 9.109 × 10 −28 g )( 4.803 × 10 −10 esu )
2
2 2
nh
r= 2 (1.28)
4 π mZe 2 = 0.529 × 10−8 cm = 0.529 Å
Consequently, the radius r0 of the smallest orbit (first (ii) Velocity of electron in the first orbit of hydrogen
orbit) for the hydrogen atom is
nh
h2 V=
r0 = 2 2 (1.29) 2πmr
4 π me
1 × 6.626 × 10 −27 ergs
V=
2 × π × ( 9.109 × 10 −28 g )( 0.529 × 10 −8 cm )
Energy of the Electron
1 2 = 2.188 × 108 cm−1
By definition the kinetic energy of body is equal to mv .
2 (iii) Energy of electron
The total energy E of the electron is the sum of its kinetic
and potential energies. If the potential energy of an electron 2π2 me 4 Z 2
En = × 2
is taken as zero when it is at an infinite distance from the h2 n
nucleus, the value at a distance r is given by −Ze2 / r. This
Since, n = 1, and Z = 1
value may be obtained by integrating Eq. (1.24) between
Energy of electron in the first orbit
the limits of r and infinity. The negative sign indicates that
work must be performed on the electron to transfer it to 2π2 me 4
E=
infinity. Therefore, the total energy of the electron is h2
2π2 ( 9.109 × 10 −28 g )( 4.803 × 10 −10 esu )
4
mv 2 Ze 2 E=
E= − (1.30)
( 6.626 × 10 ergs )
−27 2
2 r
From Eq (1.25) we may obtain = 2.179 × 10−11 erg / atom
mv 2 Ze 2 The energy of an electron is usually expressed in Kcal

= (1.31) or KJ mol−1 or electron volt (eV)
2 2r
One erg/molecule = 1.44 × 1013 Kcal / mol
and upon combining Eqs (1.30) and (1.31) the follow- = 6.22 × 1013 KJ / mol
ing expression may be derived \ E1 = (−2.179 × 10−11) × (1.44 × 1013)
Ze 2 = −313.77 Kcal / mol = −1312.19 KJ / mol
E=− (1.32) Now 1eV = 1.602 × 10−12 ergs
2r
Now if we substitute the value r from Eq. (1.28) into 2.179 × 10 −11 erg
\ E1 = = −13.6 eV /atom
(1.32) the total energy of the electron may be stated as 1.602 × 10 −12
Chapter_01.indd 18 8/17/2013 3:42:28 PM

1.7.2 Origin of Spectral Lines and the If the term wave number is used for frequency
Hydrogen Spectrum v
v=
c
As described by Bohr, energy is radiated when an electron
moves from one orbit of a quantum number of n2 to an 2π2 Z 2 e 4 m  1 1 
v=  2 − 2 (1.36)
orbit of quantum number n1, where n1 is the inner orbit. h3 c  n1 n2 
Energy is absorbed if the electron moves in opposite direc-
tion, i.e., from inner orbit to outer orbit. The energy DE All the terms in the fraction 2p2Z2 e4 m/h3c are
which is emitted may be represented as a difference in constant. For hydrogen atom Z is 1. If we evaluate the
energy of the two electronic states and can be indicated by fraction from the constant terms, the following value is
the equation obtained:
∆E = E2 − E1 = hv (1.34) 2π2 12 e 4 m
= 109, 700 cm −1 = R (1.37)
h3 c
where, E2 is the energy of orbit n2 and E1 is the energy of
inner orbit n1. where, R is the Rydberg constant. Moreover, when
Spectral lines are produced by the radiation of pho- we substitute R in Eq. 1.36
tons, and the position of the lines on the spectral scale is  1 1 
determined by the frequency, or frequencies, of the pho- v = R 2 − 2  (1.38)
 n1 n2 
tons emitted. Transitions to the innermost level n1 from
orbits n2, n3, n4 etc, gives rise to the first, second, third etc, Equation 1.38 is identical with the general equa-
lines of the Lyman series in the UV region. Transitions tion for the wave number of any spectral line within
from the outer most energy levels gives rise to spectral any of the spectral series of the hydrogen atom as given
lines of higher frequencies. Transition of electron to n2 in Eq. (1.15).
level from outer level gives Balmer series of lines in the
visible region. Similar transitions from higher orbits to
the third orbit (n = 3) produces Paschen series in the infra- 1.7.3 Limitations of the Bohr’s Model
red region. Other series of lines have been discovered for Bohr’s atomic model was a very good improvement
similar shifts in the far infrared region. A sketch indicat- over Rutherford’s nuclear model and enabled in calcu-
ing the transitions which produces these spectral lines is lation of radii and energies of the permissible orbits in
given in Fig 1.21. the hydrogen atom. The calculated values were in good
From the Eq. (1.34) the difference between the agreement with the experimental values. Bohr’s theory
energies of an electron in the two orbits n2 and n1 may be could also explain the hydrogen spectra successfully
indicated as and also the spectra of hydrogen like atoms (He +, Li 2+,
2π2 Z 2 e 4 m  1 1  Be3+, etc). The theory was, therefore, largely accepted
∆E = En2 − En1 = hv =  2 − 2  (1.35)
h  n1 n2  and Bohr was awarded Nobel prize in recognition of
Pfund series
8
7
Paschen 6
series
Principal quantum number n
5
4 Brackett series Radiation
Brackett of long
(not to scale)
3 wavelength
Balmer series
series Paschen series Radiation
1 3 with intermediate
2 wavelength
2
3 Balmer series
4 Radiation with short
Pfund wavelength
5 series
6 1
Lyman series
Lyman
series
Fig 1.21 Origin of emission spectrum of hydrogen atom
Chapter_01.indd 19 8/17/2013 3:42:29 PM

this work. However, Bohr’s model could not explain the

following points: Louis de Broglie 1892–1987
(i) Bohr’s model could not explain the spectra of atoms
containing more than one electron. Also, it could He was a French physicist. Studied history but while
not explain hydrogen spectrum obtained using high working on radio communications during the First
resolution spectroscopes. Each spectral line, on high World War as an assignment, he developed interest
resolution was found to consist of two closely spaced in science. He received his Dr Sc. from the Univer-
lines. sity of Paris in 1924. He was professor of theoretical
(ii) It was observed that in the presence of a magnetic physics in the University of Paris from 1932 to 1962.
field each spectral line gets splitted up into closely He was awarded Nobel Prize for physics in 1929.
spaced lines. This phenomenon, known as Zeeman
effect, could not be explained by the Bohr’s model.
Similarly, the splitting of spectral line under the By making use of the Einstein’s (E = mc2) and Planck’s
effect of applied electric field, known as Stark effect, quantum theory, (E = hv) de Broglie deduced a fundamen-
could not be explained by the Bohr’s model. tal relation called the de Broglie equation:
(iii) It could not explain the spectra of atom of elements h
λ= (1.39)
other than hydrogen. mv
(iv) Bohr’s model could not explain the ability of atoms This equation gives the relationship between the
to form molecules and the geometry and shapes of wavelength of the moving particle and its mass. In the
molecule. Eq. (1.39), l is the wavelength of the wave associated with
an electron of mass ‘m’ moving with velocity v.
Eq. (1.39) can be written as
h
1. 8 Waves and Particles mv = (1.40)
λ
Because of the limitations of Bohr’s atomic model sev- 1
eral scientists tried to develop a more subtle and gen- mv ∝ (1.41)
λ
eral model for atoms. During that period two important 1
proposals were contributed significantly for the mod- p∝ (1.42)
ern quantum mechanical model of the atom. They are λ
(i) Dual nature, i.e., wave as well as particle nature of In the E.q. (1.42) ‘p’ represents the momentum mv of
matter. particle; and l corresponds to the wave character of matter
(ii) Heisenberg’s uncertainty principle. and p its particle character. Thus, the momentum (p) of a
moving particle is inversely proportional to the wavelength
of the waves, associated with it.
The revolutionary postulate of de Broglie received
1.8.1 Dual Nature of Matter direct experimental verification in 1927 by Davisson and
According to Maxwell’s concept, light, radiation con- Germer, G.P. Thomson and later by Stern. They showed
sists of waves while Planck’s quantum theory considers that heavier particles (H2, He etc.) showed diffraction pat-
photons as particles. Thus, light, which consists of elec- terns when reflected from the surface of crystals. Particu-
tromagnetic radiation, is both a wave and particle. Based larly Davisson and Germer found that electron beam was
on this analogy in 1924, the Frenchman, Prince Louis de diffracted when striken on a single crystal of nickel, which
Broglie published an exceedingly complicated account proves the wave like character of electrons.
of the wave-particle duality. de Broglie stated that any
form of matter such as electron, proton, atom or mol-
de Broglie’s Relationship Concept and
ecules, etc, has a dual character. The waves predicted by
Bohr’s Theory
de Broglie are known as matter waves. These waves are
quite different from electromagnetic waves in following Application of de Broglie’s relationship to a moving elec-
two respects: tron around a nucleus puts some restrictions on the size of
(i) Matter waves cannot radiate through empty space the orbits. It means that electron is not a mass particle mov-
like the electromagnetic waves. ing in a circular path but instead a standing wave train (non-
(ii) Speed of matter waves is different from that of energy, radiating motion) extending around the nucleus in
electromagnetic waves. the circular path as shown in Fig 1.22 (a) and 1.22 (b).
Chapter_01.indd 20 8/17/2013 3:42:29 PM

de Broglie’s equation is true for material particles of all

sizes and dimensions. However, in the case of small micro
objects like electrons, the wave character is of significance
only. In the case of large macro-objects the wave charac-
ter is negligible and cannot be measured properly. Thus, de
Broglie equation is more useful for small particles.
Meaning of y and its Significance
(a) (b) y is the wave function or the amplitude of the wave. The
value of amplitude increases and reaches the maximum
Fig 1.22 Diagrammatic representation of electron orbits which is indicated by peak in the curve. This is shown by
one of which is (a) in phase; and the other (b) out of phase the upward arrow in the figure. The value of the amplitude
decreases after reaching the maximum value. This is shown
by the downward arrow.
For the wave to remain continually in phase, the cir- Above the X-axis the amplitude is shown as +ve,
cumference of the orbit should be an integral multiple of along the X-axis it is zero and below the X-axis it is nega-
wavelength l, tive. The intensity of light is proportional to the square of
2pr = nl (1.43) amplitude (or A2). Therefore, A2 can be taken as a measure
of the intensity of light since light is considered to consist
where, r is the radius of the orbit, and n is a whole
of photons (corpuscular theory), the density of photons is
number.
considered to be proportional to A2. Thus, as far as light
From Eq. (1.40) we know
waves are concerned A2 indicates the density of photons in
h space or the intensity of light.
λ= (1.44)
mv This concept can be extended even to the y functions
Substituting the value of l in Eq. (1.43), we get moving in the atom since electron moving with high speed
is associated with a wave characteristics. Therefore, y2 in
nh
2πr = the case of electron wave denotes the probability of finding
mv an electron in the space around the nucleus or the electron
nh density around the nucleus. If y2 is maximum, the prob-
or mvr = (1.45)
2π ability of finding an electron is also maximum.
which is the same as Bohr’s postulate for angular moment
Solved Problem 9
of electron. From the E.q. (1.45) it can be known that elec-
trons can move only is such orbits for which the angular An electron with mass of 9.1 × 10−31 kg is moving with a
momentum must be an integral multiple of h/2π. If the velocity of 103 m/s. Calculate its kinetic energy and wave-
circumference is bigger or smaller than the value as given length (Planck’s constant h = 6.6 × 10−34 kg m2 s−1).
by in Fig 1.22 b, the electron wave will be out of phase. Solution:
Thus, de Broglie relation provides a theoretical basis for Kinetic energy KE
1 1
= mv 2 = × ( 9.1× 10 −31 kg )(103 m s −1 )
the Bohr’s postulate for angular momentum. In Fig 1.22 (a) 2
the wave is in phase continually. 2 2

= 4.55 × 10−7 J
h 6.6 × 10 −34 kg m 2 s −1
In the summer of 1927 physicists from all over the Wavelength l = =
mv 9.1× 10 −31 kg × 103 ms −1
world arrived in Brussels at the Solvay Congress. At
= 7.25 × 10−7 m
this congress de Broglie’s concept on the relationship
between waves and particles was totally rejected. For
many years to come, a complete different representa- +
tion of this relationship led the way. It was Heisen- X
berg and Schrodinger who supported and strongly –
represented the concept of de Broglie at another
congress and got it accepted.
Fig 1.23
Chapter_01.indd 21 8/17/2013 3:42:31 PM

Solved Problem 10 “If an electron is exhibiting the dual nature, i.e., wave
and particle, is it possible to know the exact location of the
A moving electron has 2.8 × 10−25 J of kinetic energy.
electron in space at some given instant?”
Calculate its wavelength (mass of electron = 9.1 × 10−31 kg).
The answer to the above question was given by
Solution:
1 Heisenberg in 1927 who stated that
Kinetic energy = mv 2
2 “For a subatomic object like electron, it is impossible
2 × Kinetic energy to simultaneously determine its position and velocity at any
V =2
given instant to an arbitary degree of precision.”
m
Heisenberg gave mathematical relationship for the
2 × 2.8 × 10 −25 2 −2
= m s uncertainty principle by relating the uncertainty in position
9.1 × 10 −31 (Dx) with uncertainty in momentum (Dp) as
2 × 2.8 × 10 −25 2 −2 h
= m s ∆ p×∆x ≥ (1.46)
9.1 × 10 −31 4π

= 61538.61 m2 s2 The ≥ in the Eq. (1.46) means that the product of Dx and
\ v = 784.46 m s−1 Dp can be either greater than or equal to but would be never
By de Broglie’s equation, we have smaller than h / 4p. But h / 4p is constant. Therefore, it follows
h 6.6 × 10 −34 kgm 2 s −2 s from Eq. (1.46) that smaller the uncertainty in locating the
λ= = × exact position (Dx), greater will be the uncertainty in locating
mv 9.1× 10 −31 × 784.46 kgm s −1
the exact momentum (Dp) of the particle and vice versa.
= 9.2455 × 10−7 m As Dp is equal to mDv the Eq. (1.46) is equivalent to
saying that position and velocity cannot be simultaneously
determined to an arbitrary precision.
1.8.2 Heisenberg’s Uncertainty Principle However, in our daily life, these principles have no
significance. This is because we come across only large
Werner Heisenberg (1901–1976) objects. The position and velocity of these objects can be
determined accurately because in these cases the changes
He received his Ph.D. in physics from the Univer- that occur due to the impact of light are negligible. The
sity of Munich in 1923. Later he worked with Max microscopic objects suffer a change in position or velocity
Born at Gottingen and with Niels Bohr at Copen- as a result of the impact of light. For example, to observe
hagen. He spent about 14 years (1927–1941) as an electron, we have to illuminate it with light or elec-
professor of physics at the University of Leipzig. tromagnetic radiation. The light must have a wavelength
He led the German team working for atomic bomb smaller than the wavelength of electron. When the photon
during the Second World War. Once the war ended of such light strikes the electron, the energy of the electron
he became the director of Max Planck Institute for changes. In this process, no doubt, we shall be able to cal-
physics in Gottingen. He was awarded Nobel Prize culate the position of the electron, but we would know very
for physics 1932. little about the velocity of the electron after the collision.
The exact sciences also start from the assump-
tion that in the end, it will always be possible to 1.8.3 Significance of Uncertainty Principle
understand nature, even in every new field of experi- The most important consequence of the Heisenberg
ence but we make no priori assumptions about the uncertainty principle is that it rules out existence of defi-
meaning of the word understand. nite paths or trajectories of electrons and other similar
W. Heisenberg particles. The trajectory of an object is determined by
its location and velocity at various moments. At any par-
According to classical mechanics, a moving electron ticular instant if we know the position of a body and also
is considered to be a particle. Therefore, its position and its velocity and the forces acting on it at that instant we
momentum could be determined with a desired accuracy. can predict at what position it will present at a particular
On the other hand de Broglie also considered a moving time. This indicates that the position of an object, and its
electron to be wave-like. Therefore, it becomes impossible velocity completely determine its trajectory. Because, it
to locate the exact position of the electron on the wave is not possible simultaneously to determine the position
because it is extending throughout a region of space. So, and velocity of an electron at any given instant precisely
the following fundamental question arises: it is not possible to talk of the trajectory of an electron.
Chapter_01.indd 22 8/17/2013 3:42:31 PM

The effect of Heisenberg’s uncertainty principle is Bohr model. In calculating electron orbits precisely, Bohr
significant only for motion of microscopic objects and is was violating this fundamental requirement and hence his
negligible for that of macroscopic objects. This can be seen theory was only partially successful. So, a model which
from these illustrated examples. can account the wave-particle duality of matter and be
consistent with Heisenberg uncertainty principle was in
Solved Problem 11 quest. This came with the advent of quantum machanics.
Calculate the uncertainty (Dv) in the velocity of a cricket
Concept of Probability
ball of mass 1 kg, if certainty (Dx) in its position is of the
order of 1 Å. The consequences of the uncertainty principle are far reaching
Solution: and probability takes the place of exactness in velocity (which
In the above example. is related to kinetic energy) of an electron. The Bohr concept
h of the atom, which regards the electrons as rotating in defi-
∆V =
4π∆x m nite orbits around the nucleus, must be abandoned and should
be replaced by a theory which considers probability of find-
But h = 6.6 × 10−34 kg m2 s−2 s;
ing the electrons in a particular region of space. This means
Dx = 1Å = 10−10 m and
that, it is possible to state the probabilities of the electron to
m = 1 kg
be various distances with respect to the nucleus. In the same
6.6 × 10 −34 kg m 2 s −1 s way, probable values of velocity can also be given. It should
∆V = −10
×
4 × π × 10 × 1 m kg be clearly understood, however, that a knowledge of probabil-
7 × 6.6 × 10 −34 ity for an electron ‘moves’ from one location to another.
= m s −1
4 × 22 × 10 −10
1.8.4 Quantum Mechanical Model of Atom
= 5.25 × 10−25 m s−1
Classical mechanics based on Newton’s laws of motion suc-
Solved Problem 12 cessfully describes the motion of all macroscopic objects since
the uncertainties in position and velocity are small enough
A microscope using suitable photons is employed to locate
to be neglected. However, it fails in the case of microscopic
an electron in an atom within a distance of 0.1 Å. What is
objects like electrons, atoms, molecules etc. So, while consid-
the uncertainty involved in the measurement of its velocity?
ering the motion of microscopic objects, the concept of dual
Solution:
h behaviour of matter and the uncertainty principle are taken
∆v = into account. The branch of science that takes into account
4 π∆x m
this dual behaviour of matter is called quantum mechanics.
But h = 6.626 × 10 −34 kg m 2 s −2 s; As far as the other dynamical variables of an electron
are concerned, we can show that the uncertainty principle
Dx = 0.1Å = 1 × 10−11 m and
leads to the following result.
m = 9.11 × 10−31 kg
The total energy of an electron in an atom or mol-
6.626 × 10 −34 kg m2 s −2 s ecule has a well-defined (sharp) value. The probability
\ ∆v = ×
4 × π × 10 −11 × 9.11× 10 −31 m kg distribution as well as the sharp values can be calculated
= 0.579 × 107 m s−1 from a function designated as y (x) and called the wave
function or the psi function. y (x) is obtained by solv-
= 5.79 × 106 m s−1
ing the Schrodinger equation which is the fundamental
Why Bohr’s Model was a Failure? equation in quantum mechanics in the same manner that
Newton’s equation is fundamental in classical mechanics.
Bohr considered the electron as a charged particle mov-
ing in well defined circular orbits around the nucleus. So, Important Features of the Quantum Mechanical
the position and the velocity of the electron can be known Model of Atom
exactly at the same time. Uncertainty principle shows that
it is impossible to measure these variables simultaneously Quantum mechanical model of the atom is the outcome
because the wave character of electron was not consid- of the application of Schrodinger wave equation to atoms.
ered in the Bohr model. Calculation of the trajectory of Its important features are
an electron in an atom or molecule is, therefore, a futile • Quantization of the energy of electron in atoms, i.e.,
exercise. We can now appreciate the major fault of the it can have certain discrete values.
Chapter_01.indd 23 8/17/2013 3:42:32 PM

• The allowed solutions of Schrödinger wave equation Austrian physicist Erwin Schrödinger who invented a
tell about the existence of quantized electronic method of showing how the properties of waves could be
energy levels for electrons in atoms having wave like used to explain the behaviour of electrons in atoms. Schro-
properties. dinger published his ideas in January 1926. This date repre-
• As per Heisenberg’s uncertainty principle, both the sents one of the milestones in the history of Chemistry. His
position and velocity of an electron cannot be deter- work formed the basis of all our present ideas on how atoms
mined simultaneously and exactly. So, the path of the bond together. The heart of his method was his prediction
electron can never be determined accurately. Because of the equation that governed the behaviour of electrons,
of this reason the concept of probability was introduced and the method of solving it. Schrodinger’s equation is
for finding the electron at different points in an atom.
∂ 2 ψ ∂ 2 ψ ∂ 2 ψ 8π2 m
• The wave function for an electron in an atom is the + + + 2 ( E −U ) = 0 (1.43)
atomic orbital. Whenever we say about electron by ∂x 2 ∂y 2 ∂z 2 h
a wave function it occupies that orbital. Because where, m = Mass of electron
several wave functions are possible for an electron, E = Total energy of the electron (kinetic energy +
there also as many atomic orbitals. These one elec- potential energy)
tron orbital wave functions or orbital form the basis U = Potential energy
for electronic structure of atoms. Every orbital pos- h = Planck’s constant
sess certain energy and can accommodate only two y = Wave function
electrons. In atoms having several electrons, the elec- This equation applies to stationary waves as it does not
trons are filled in the order of increasing energy. In have the time dependence part of the wave function.
the multielectron atoms each electron has an orbital Schrödinger won the Nobel prize for physics in
wave function characteristic of the orbital it occupies. 1933. The solution of this equation are very complex
All the information about the electron in an atom is and you will learn them for different systems in higher
stored in its orbital wave function y and quantum classes.
mechanics makes it possible to extract this informa- For a system (such as an atomic or a molecule whose
tion out of y. energy does not change with time), the Schrödinger equa-
The probability of finding the electron at a point tion is written as Ĥ y = Ey, where Ĥ is a mathematical
within an atom is proportional to y2 at that point. operator called Hamiltonian. Schrödinger gave a recipe
Though y is sometimes negative, y2 is always posi- of constructing this operator from the expression for the
tive and is known as the probability density. The total energy of the system. The total energy of the system
values of y2 predicts the different points in a region takes into account the kinetic energies of all the sub-atomic
within an atom at which the electron will be most particles (electrons, nuclei) attractive potential between
probably found. the electrons and nuclei and repulsive potential among the
electrons and nuclei individually. Solutions of this equation
1.8.5 Schrödinger Wave Equation gives E and y.
1.8.6 The Meaning of Wave Function

Erwin Schrödinger 1887–1966
The wave function could only be used to provide informa-
Erwin Schrödinger was born in Austria. He received tion about the probability of finding the electron in a given
his Ph.D. in theoretical physics from the University region of space around the nucleus. Max Born, a German
of Vienna in 1910. At the request of Max Planck, physicist proposed that we must give up ideas of the elec-
Schrödinger became his successor at the University tron orbiting the nucleus at a precise distance. In this respect
of Berlin in 1927. Because of his opposition to Hitler Bohr was wrong in thinking that the electron in the ground
and Nazi policies, he left Berlin and returned to state of the hydrogen atom was always to be found at a dis-
Austria and in 1936, when Austria was occupied by tance a0 form the nucleus. Rather, it was only most probably
Germany, he was forcibly removed from his profes- to be found at this distance. The electron had a smaller prob-
sorship. Then he moved to Dublin, Ireland. He shared ability of being found at a variety of other distances as well.
the 1933 Nobel Prize for physics with P.A.M. Dirac. It is important to realise that we should not try to talk
about finding the electron at a given point. The reason for
During 1920 there was a great deal of interest in wave- this is that there is an infinite number of points around the
particle duality and de Broglie’s matter waves. It was the nucleus. So, the probability of finding the electron at any
Chapter_01.indd 24 8/17/2013 3:42:32 PM

1.9 Quantum Numbers

The mathematical solution of three dimensional Schrödinger
a0
wave equation gives three values of E for acceptable values
of y. These values are related to one another through whole
numbers. These values are termed as Quantum numbers
and represented with n, l, m — called principal, azimuthal
Fig 1.24 Electron density and magnetic quantum numbers, respectively. These
three quantum numbers together with the fourth called spin
one of these points is infinitely small, i.e., zero. Then to quantum number describe fully the location and energy of
predict the position of electron, we can imagine taking out an electron. Thus, quantum numbers are the numbers which
a series of photographs of an atom to give us an instan- determine the energy of electron, the angular momentum,
taneous picture of the whereabouts of the electron. If we shape of the electron orbital, the orientation of the orbital
combine all pictures we would end up with a picture as and spin of the electron. Thus, each quantum number is
shown in Fig 1.24. The separate dots have overlapped to associated with a particular characteristic of the electron.
give regions in which the density of dots is very high and These quantum numbers are discussed below briefly.
regions where the density of dots is much lower. In the high 1. Principal Quantum Number (n): The number allot-
density regions, we say that there is a high probability den- ted to Bohr’s original stationary states, visualized as
sity. The maximum in the density comes at exactly the same circular orbits is called the principal quantum number.
distance a0, as Bohr predicted in his work. The circulated The innermost orbit, i.e., that nearest to the nucleus
symmetry of the probability density is clear. However, we has a principal quantum number 1, the second orbit has
should remember that atoms exist in three dimensions, so a quantum number of 2, and so on. So, the principal
really the diagram should be shown as a sphere. quantum number denoted by n have value 1, 2, 3, 4,
It is easier to draw circles rather than spheres, so usually ..... Alternatively, letters are used to characterize the
we draw the density diagram as a circle. Also, it is common orbits, K, L, M, N, ... for 1, 2, 3, 4, .... The choice of
practice not to include the shading and to agree that when a letters originates from Mosely’s work on the X-ray
circle is drawn, it provides a boundary surface within which, spectra of the elements. He called group of lines in the
say, there is a 95 per cent probability of finding the electron. spectra the K, L, M, N, ... groups.
When Schrödinger equation is solved for hydrogen The number of electrons in an atom which can have the
atom, the solution gives the possible energy levels the elec- same principal quantum number is limited and is given by 2n2
tron can occupy and the corresponding wave function(s) y where n is the principal quantum number concerned. Thus,
of the electron associated with each energy level.
Accepted solutions to the wave functions are called Principal quantum number (n) 1 2 3 4
Eigen wave functions. The probability of finding an elec- Letter designation K L M N
tron at a point in space whose coordinates are x, y and Maximum number of electrons 2 8 18 32
z is given by |y (x, y, z)|2dv. This three dimensional region
obtained where the probability to find the electron is about This is the most important quantum number as it
95 per cent, is called an orbital. determines to a large extent the energy of an electron. It
also determines the average distance of an electron from
Because atomic behavor is so unlike ordinary experi- the nucleus. As the value of n increases, the electron gets
ence, it is very difficult to get used to and it appears farther away from the nucleus and its energy increases. The
peculiar and mysterious to everyone, both to the nov- higher the value of n, the higher is the electronic energy.
ice and to the experienced scientist. Even the experts For hydrogen and hydrogen like species, the energy and
do not understand it the way they would like to, and it size of the orbital are determined by the principal quantum
is perfectly reasonable that they should not, because number alone.
all of direct human experience and of human intution The principle quantum number also identifies the
applies to large objects. We know how large objects number of allowed orbitals within a shell. With the increase
will act, but things on a small scale just do not act in the value of ‘n’ the number of allowed orbitals increases
that way. So, we have to learn about them in a sort of and are given by n2. All the orbitals of a given value of ‘n’
abstract or imaginative fashion and not by connec- constitute a single shell of atom.
tion with our direct experience. Feynman Lectures on 2. Azimuthal Quantum Number (l): It is also known
Physics Vol. l Chapter 37. as orbital angular momentum or subsidiary quantum
number. It defines the three dimensional shape of the
Chapter_01.indd 25 8/17/2013 3:42:33 PM

sub-shell. For each value of the principal quantum These different orientations are called orbitals. The
number there are several closely associated orbitals, number of orbitals in a particular sub-shell within a
so that the principal quantum number represents a principal energy level is given by the number of values
group or shell of orbits. In any one shell, having the allowed to ml which in turn depends upon on the value
same principal quantum number the various subsidi- of l. The possible values of ml range from + l through 0
ary orbits are denoted as s, p, d, f, ... sub-shells. The to − l, thus making a total of (2l + 1) values. Thus, in a
letters originates from the sharp, principal, diffuse and subshell, the number of orbitals is equal to (2l + 1).
fundamental series of the lines in spectra. For l = 0 (i.e., s-subshell) ml can have only one value
The number of sub-shells or sub-levels in a principal ml = 0. It means that s-subshell has only one orbital.
shell is equal to the value of n. The values of subshells For l = 1 (i.e., p-subshell) ml can have three values +1,
is represented with l. l can have values ranging from 0 and −1. This implies that p-subshell has three
0 to n − 1, i.e., for a given value of n the possible value of orbitals.
l can be 0, 1, 2......(n−l). For example when n = 1 value of For l = 2 (i.e., d-subshell) ml can have five values +2,
l is only 0. For n = 2 the possible value of l can be 0 and +1, 0, and −2. It means that d-subshell has five
1. For n = 3 the possible values are 0, 1 and 2. Sub-shells orbitals.
corresponding to different values are as follows: For l = 3 (i.e., f-subshell) ml can have seven values
+3, +2, +1, 0, −1, −2 and −3. It means that
value for l 0 1 2 3 4 5…….. f-subshell has seven orbitals.
Notation for s p d f g h ... The number of orbitals in various types of subshells
subshell are as given below.
The permissible values for ‘l’ for a given principal quan- Sub-shell s p d f g
tum number and the corresponding sub-shell notation are Value of l 0 1 2 3 4
as follows. No. of orbitals (2l + 1) 1 3 5 7 9
l values 1 2 3 4 5 6 7
The relationship between the principal quantum
0 1s 2s 3s 4s 5s 6s 7s
number (n), angular momentum quantum number (l ) and
1 2p 3p 4p 5p 6p 7p
magnetic quantum number (ml) is summed up in Table 1.4.
2 3d 4d 5d
4. Spin Quantum Number (ms): This quantum number
3 4f 5f
which is denoted by ms does not follow from the wave
mechanical treatment. Electron spin was first postu-
3. Magnetic Quantum Number (ml): This quantum lated in 1925 by Uhlenbeck and Goudsmit to account
number which is denoted by ml refers to the different ori- for the splitting of many single spectral lines into
entations of the electron cloud in a particular subshell. double lines when examined under a spectroscope of
Table 1.4 Relationship amongst the value of n, l and ml
Number of orbitals
Principal
Energy quantum Possible values Designation In a given In a given
level number (n) of (l) of sub-shell Possible values of ml sub-shell energy level
K 1 0 1s 0 1 1
L 2 0 2s 0 1
1 2p +1, 0, –1 3 4
M 3 0 3s 0 1
1 3p +1, 0, –1 3 9
2 3d +2, +1, 0, –1, –2 5
N 4 0 4s 0 1
1 4p +1, 0, –1 3 16
2 4d +2, +1, 0, –1, –2 5
3 4f +3, +2, +1, 0, –1, –2, –3 7
Chapter_01.indd 26 8/17/2013 3:42:33 PM

high resolving power. The electron in its motion about which expresses the amplitude of vibration of a plucked
the nucleus also rotates or spins about its own axis. In string.
other words, an electron has, besides charge and mass, As it is the square of amplitude of the vibrating string
an intrinsic spin angular quantum number. which measures the intensity of the wave involved, so |y|2
Spin angular momentum of the electron: A vector measures the probability of an electron existing at a point,
quantity, can have two orientations relative to a chosen meaning therefore, that the chance of finding an electron at
axis. The spin quantum number can have only two values that point is zero. A high value of |y|2 at a point means that
1 1 1 there is a high chance of finding an electron at the point.
which are + and − . The + value indicates the
2 2 2 The value of the wave function y, for an elec-
clockwise spin, generally represented by an arrow upwards, tron in an atom is dependent, in general, both on the
i.e., ↑ and the other indicates anti-clockwise spin, generally radial distance, r, of the electron from the nucleus of
represented by an arrow downwards, i.e., ↓. The electrons the atom and on its angular direction away from the
1 1 nucleus.
that have different ms values (one + and the other − )
2 2 The nucleus, itself, however, cannot provide any sense
are said to have opposite spins. An orbital cannot hold of direction until a set of arbitrary chosen axes are super-
more than two electrons and these two electrons should imposed. If cartesian axes are chosen as in Fig 1.25 (a) then
have opposite spins. a point in space, P, around the nucleus, N, can be defined
in terms of x−, y− and z-coordinates. Such axes do not,
however, have any absolute directional significance until
Orbit and Orbital an external magnetic field is applied. The axes then have
a definite direction in relation to the direction of the mag-
Orbit and orbitals are different terms. Bohr proposed netic field. Alternatively, polar coordinates in Fig 1.25 (b)
an orbit as a circular path around the nucleus in can be used.
which the electrons moves. As per Heisenberg’s The mathematical relationship between y and r and the
uncertainty principle the precise description is not angular direction can be established accurately for a single
possible. So, its physical existence cannot be demon- electron in a hydrogen like atom. For more complicated
strated experimentally. atoms containing more than one electron, the correspond-
An orbital is a three-dimensional region calcu- ing relationships can only be established approximately
lated from the allowed solutions of the Schrödinger’s because of the difficulty involved in solving the mathemat-
equation. It is quantum mechanical concept and ical equations.
refers to one electron wave function y in an atom. It The differences between s−, p− and d-orbitals depend
is characterised by three quantum numbers (n, l and on the ways in which y and / or y2 vary with r and with the
ml) and its value depends upon the coordinates of the angular direction, as explained in the following sections.
electron. y has no physical meaning but its square The probability of finding an electron in a given
|y|2 at any point in an atom gives the value of prob- volume of space is represented by radial probabil-
ability density at that point. Probability density (|y|2) ity distribution curves. These curves indicate how the
is the probability per unit volume and the electron in probability of finding an electron varies with the radial
that volume. |y|2 varies from one region to another distance from the nucleus without any reference to its
region in the space but its value can be assumed to
be constant within a small volume. The total prob-
ability of finding the electron in a given volume can Z Z
be calculated by the sum of all products of |y|2 and φ
the corresponding volume elements. It is thus pos- P
sible to get the probable distribution of an electron θ P
N r
in an orbital. N
1.10 Shapes of Orbitals (a) (b)

The nature of the Schrödinger equation is such that the wave Fig 1.25 The position of a point P relative to point
function y may be regarded as an amplitude function. This N can be expressed in terms of (a) Cartesian coordinates
corresponds, on a three-dimensional scale, to the function x, y, z or (b) Polar coordinates r, θ and f.
Chapter_01.indd 27 8/17/2013 3:42:34 PM

R1.0 R2.0 R3.0

1s 2s 3s
r r r
Fig 1.26 Plots of y n, l versus r for electron belonging to different orbitals
direction from the nucleus. The radial wave function is

generally written as yn, l. Let us now plot the function yn, l r
against r for electrons belonging to different orbitals and
try to correlate them with the probability density around O r + dr
a point at a distance r from the nucleus. The plots are as
shown in Fig 1.26.
From these plots, it is clear that y n, l cannot be related Fig 1.27 Division of space around the nucleus into small
with probability density around any point at a distance r spherical shells of very small thickness
from the nucleus because
(i) y n, l is maximum at r = 0. If y n, l represents probabil-
ity density the electron will have maximum probabil- The volume of such a shell viz, dV, will be given by
ity of occurring at the nucleus. This cannot be true dV = (4/3) p (r + dr)3 − (4/3) pr3 (1.44)
as the actual probability of finding an electron at the
nucleus is zero. 4
=   π [r 3 + dr 3 + 3r 2 dr + 3rd 2 − r 3 ] (1.45)
(ii) y n, l has both positive as well as negative values (if 3
probability curves for 2s and 3s electrons). How- Neglecting very small terms dr2 and dr3, we get
ever, probability density cannot have a negative
value. dV = 4pr2 dr (1.46)
Objection No. (ii) can be removed by considering |yn, l|2 The probability of finding electron within the small
to be related to probability density instead of y n, l. Now radial shell of thickness dr around the nucleus, called
even if y n, l is negative at some space its square has to be radial probability will therefore be given by
positive. The plots of y n, l versus r for electrons belonging r dV = yn, l × dV (1.47)
to different orbitals are as shown in Fig 1.28.
= 4pr2 dr |y2n, l | (1.48)
The curves do not exhibit negative value for the
radial wave functions at any distance. But even |y n, l|2 can- The radial probability distribution between r = 0 to
not be related with probability density because |yn, l|2 is r = r will be given by the summation of all the probability
maximum at r = 0. This means that the probability of distributions for concentric radial shells from r = 0 to
finding electron is maximum on the nucleus which again r = r, i.e., by
cannot be true (as already explained). Thus, neither y r =r
n, l nor y n, l can be directly related with probability of

2 ∫r =0
4 πr 2 dr ψ 2n,l (1.49)
finding electron at a point which is at a distance r from In other words, the radial probability distribu-
the nucleus. tion of electron may be obtained by plotting the function
Let us consider the space around the nucleus (taken at 4pr2 |y2 n, l| against r, its distance from the nucleus. Such
the centre) to be divided into a large number of thin con- graphs are radial probability distribution curves.
centric spherical shells of thickness dr. Consider one of The radial probability distribution curves for 2s, 3s, 3p
these shells with the inner radius r (Fig 1.27). and 3d electrons are shown in Fig 1.29.
Chapter_01.indd 28 8/17/2013 3:42:36 PM

ψ21,0 1s 2s 3s
ψ22,0 ψ23,0
r r r
Fig 1.28 Plots of y2
n, l. versus r for electrons belonging to different orbitals
3p 3s
4πr2 R23,2
4πr2 R22,0
r r
3d
2s
4πr2 R23,1
4πr2 R23,1
r r
Fig 1.29 Radial probability distribution curves for 2s, 3s, 3p and 3d electrons.
It may be noted that for 1s orbital, the probability den- These probability density variations can be visualized
sity is maximum at the nucleus and it decreases sharply in terms of charge cloud diagrams (Fig 1.30). In these
as we move away from it. On the other hand, for 2s orbital diagrams, the density of the dots in the region represents
the probability density first decreases sharply to zero and electron probability density in that region.
again starts increasing. After reaching a small maxima
it decreases again and approaches zero as the value of
1.10.1 Boundary Surface Diagrams
r increases further. The region where this probability den-
sity function reduces to zero is called nodal surfaces or s-orbitals: The shapes of the orbitals in which constant
nodes. In general it has been found that ns-orbital has (n−1) probability density for different orbitals can be represent-
nodes, that is, number of nodes increases with increase of ed with boundary surface diagram. The value of prob-
principal quantum number n. In other words, number of ability density |y|2 is constant in this boundary surface
nodes for 2s orbital is one, two for 3s and so on. drawn in space. In principle, many such boundary surfaces
Chapter_01.indd 29 8/17/2013 3:42:37 PM

Z Z Z
Y Y Y
–X X –X X –X X
–Y –Y –Y
Radial node Radial node
–Z 1s orbital –Z 2s orbital –Z 3s orbital
Fig 1.30 The shapes of various s-orbitals
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 or-
bital which encloses a region or volume in which the prob- 1s
ability of finding the electron is very high, say 90 per cent,
but cannot be 100 per cent because always there will be
some value, however small it may be, at any finite distance
4πr 2 R21,0
from the nucleus. Boundary surface diagram for an ‘s’ or-
bital is actually a sphere centred on the nucleus. In two
dimensions, this sphere looks like a circle. The probability
of finding the electron at any given distance is equal in all
directions. It is also observed that the size of the s-orbital
increases in n, that is, 4s > 3s > 2s > 1s and the electron r
0.529Å
is located further away from the nucleus as the principal
quantum number increases.
p-orbitals: The probability density diagrams for p orbit-
als are very different to those of s-orbitals. If you look
back at quantum numbers you will find that we said that
the magnetic quantum number can tell us the number of 2p
orbitals of a given type. The result is that for s-orbitals the
4πr 2 R22,1
magnetic quantum number, ml, has only one value. This

means that there is only one variety of s-orbitals that is
the variety we have already met; the spherically symmet-
ric ones. For p-orbitals there are three possible values of m
(+1, 0, −1) — the three types of p-orbitals are called px, py
and pz. The boundary surface diagrams are known as ra-
dial probability distribution curves or radial charge den-
sity curves or simply as radial distribution curves. Such r
curves truly depict the variation of probability density Fig 1.31 Radial probability distribution curves for 1s and
of electronic charge with respect to r (distance of charge 2p electrons
from the nucleus.)
Radial probability at a distance r is the probability of
The radial probability function 4pr2| ψ n, l | written for
2
finding electron at all points in space which are at a distance
r from the nucleus and the radial probability distribution is the the sake of simplicity as 4pr |yn, l| is evidently the product
2 2
graph of these probabilities as a function of r. of two factors. While the probability factor y2 decreases
The radial probability distribution curves for 1s and 2p as r increases. This gives rise to curves of the type shown
electrons are as shown in Fig 1.31. in Fig 1.31. At r = 0, though the factor |y|2 is maximum,
Chapter_01.indd 30 8/17/2013 3:42:39 PM

z z z Z Z Z
Nodal plane
Y Y Y
+
-
y +
+ y y − + +X − + X − + X
- -X -X -X
x px orbital x py orbital x pz orbital -Y 2Px -Y 3px -Y 4px
z z z -Z -Z -Z
Fig 1.33 The exact shapes of 2px, 3px and 4px orbitals
y y y
+
+ showing the radial nodes
+ x x x
-
symmetric structure about the z-axis having a ring-like
2px 2py 2pz collar in XY plane. The dumbell shaped part of the curve
Fig 1.32 The shapes and boundary surface diagrams for has a positive geometric sign (because whatever be the
2px, 2py and 2pz orbitals sign of z positive or negative, its square is always posi-
tive), ring the collar in the XY plane has a negative geo-
metric sign.
(Fig 1.28) the factor 4pr2 is zero. Similarly, when r is very The orbital d xy has a double dumbell shape. The quan-
large, the factor 4pr2 is no doubt very large but the prob- tity XY will be positive when both x and y are positive or
ability factor |y|2 is negligible so that the radial probability when both are negative. However, XY will be negative
is exceedingly small as shown in Fig 1.32. when either of x or y is negative. Thus, the sign of the curve
Here, unlike s-orbitals, the boundary surface diagrams is positive in first and third quadrants while it is negative in
are not spherical. Instead each p-orbital consists of two sec- second and fourth quadrants. The shape of d xz , d yz orbirals
tions called lobes that are one either side of the plane that can be explained in a similar manner.
passes through the nucleus. The probability density func- The orbital d x2 − y2 is also double dumbell shaped but its
tion is zero on the plane where the two lobes touch each lobes lie on X and Y axes. The signs of the lobes on X-axis
other. This plane is called nodal plane. The nodal plane for will always be positive (∵whatever be the sign of X, X 2 will
px orbital is YZ-plane, for py orbital, the nodal plane is XZ always be positive) whereas the sign of the lobes on Y axis
plane, and for pz orbital nodal plane is XY plane. It should will always be negative (∵ whatever be the sign of Y, − Y 2 will
be understood, however, that there is no simple relation always be negative). The exact shapes of d orbitals are
between the values of ml (−1, 0 and +1) and the x, y and z obtained by taking into consideration the total wave func-
directions. The size, shape and energy of the three orbitals tion. Accordingly 3d x2 − y2 orbital would be similar in shape to
are identical. 4 d x2 − y2 orbital or 5d x2 − y2 orbital except for the fact that
Like s-orbitals, p-orbitals increase in size and energy 1. A 5d orbital would have two, a 4d orbital have one and
with increase in the principal quantum number and hence a 3d orbital have no radial node.
the order of the energy and size of various p-orbitals is 2. A 5d orbital would occupy more space than a 4d orbital
4p > 3p > 2p. Further, like s-orbitals, the probability density and a 4d orbital would occupy more space than a 3d
functions for p-orbital also pass through value zero, besides orbital as shown in Fig 1.35.
at zero and infinite distance, as the distance increases. The
number of nodes are given by n − 2, that is, number of Every d-orbital also has two nodal planes passing
radial nodes is 1 for 3p-orbital, two for 4p-orbital three and through the origin and bisecting the XY plane containing
so on. The shapes of 2px, 3px and 4px orbits with radial Z axis. These are called angular nodes and are given by l.
nodes are shown in Fig 1.33.
d-orbitals: The orbitals having l value as 2 are known as d- For any orbital
orbitals. The minimum value of principal quantum number (i) The number of angular nodes (nodal planes)
must be 3 to have l value 2 as the value of l cannot be is equal to l value.
greater than n − 1. There are five d-orbitals corresponding (ii) The number of radial nodes (nodal surfaces or
to ml values (−2, −1, 0, +1 and +2) for l = 2. Their boundary nodes) is equal to (n−l−1).
surface diagrams are shown in Fig 1.34. (iii) The total number of radial nodes and angular nodes
The five d-orbitals are designed as d xy , d yz , d xz , d x2 − y2 for any orbital is equal to (n − l − 1) + l = n − 1.
and d z 2 The orbital d z 2 has a dumbell shaped curve
Chapter_01.indd 31 8/17/2013 3:42:41 PM

z z z z z
+ +
+
− + + −
− − − y − −
+ −
+ – − + + +
x y x y x y x y
dxz x
dxy dyz dx2−y2 orbital dz2
z z z
z z
− + y + y + y
y − y
− + x x x + − x − x
+ − − + −
+ − + −
+
3dxy 3dyz 3dxz 3dx2−y2 3dz2
Fig 1.34 Shapes and boundary surface diagrams for 3dxy ,3dyz ,3dxz , 3dx2 – y2 and 3dz2 orbitals. The nodal planes for dx2 – y2
are shown. Similarly there will be two nodal planes for each dxy ,dyz and dxz orbitals
Y Y Y 1.10.2 Energies of Orbitals

Z Z − In the hydrogen atom the energy of an electron depends
− −
mainly on the principal quantum number. So, the energies
+ + X + + X + + X
−X −X −X of all the sub shells in a principal quantum number are
− − − equal. For example,
−Z −Z 5dx2−y2
3dx2−y2 4dx2−y2 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
−Y −Y −Y
Through the shapes of different sub shells are different,
Fig 1.35 The 3dx2 -y2, 4dx2 − y2 and 5dx2 − y2 orbitals in three
the energy of the electron is the same when present in any
dimensional space showing radial nodes one of the sub shells belonging to the same principal quan-
tum number. The orbitals having same energy are called
z degenerate orbitals. In hydrogen atom when electron is
z z 3 nodal of planes
of f-orbital present in 1s orbital, the hydrogen atom is considered in
+ – + most stable condition and it is called the ground state.
+ –
x This is because the electron is nearer to the nucleus. But
+ + + when electron is present in 2s, 2p or higher orbitals in the
x – x x y
dz2 hydrogen atom, it is said to be in the excited state.
fz3 (fx3 and fy3 are fz (x2–y2) fxyzorbital In multielectron atoms, unlike the hydrogen atom,
similar) fx (y2–z2) and the energy of an electron depends both on its principal
fy(z2–x2) are similar quantum number (shell), and the azimuthal quantum
number (sub shell). This means that different sub shells
Fig 1.36 Shapes of f-orbitals viz., s, p, d, f, ... in a principal quantum number will
have different energies, because of the mutual repulsion
f-orbitals: The orbitals having l value as 3 are known between the electrons. In hydrogen atom there is only
as f-orbitals. The minimum value of principal quantum attractive force between nucleus and electron but no
number must be 4 to have l value 3 as the value of l can- repulsive forces. The stability of an electron in a multi-
not be greater than n − 1. There are seven f-orbitals corre- electron atom is because the total attractive interactions
sponding to ml values (−3, −2, −1, 0, +1, +2, +3) for l = 3. are more than the repulsive interactions experienced by
Their boundary surface diagrams are shown in Fig 1.36. every electron with other electrons. The attractive force
Chapter_01.indd 32 8/17/2013 3:42:44 PM

sub-shells belonging to same principal quantum number have

7
different energies. However, in hydrogen atom, these have
6
the same energy. In multielectron atoms, the dependence of
energies of the sub shells on ‘n’ and ‘l’ are quite complicated
5 but in simple way is that of combined value of n and l. Lower
7p the value n + l for a sub shell, lower is its energy. If the two
7s sub-shells have the same n + l value, the orbital having lower
4 6d n value have the lower energy. The energies of sub-shells in
Principal quantum number
5f
6p the same shell decrease with increase in the atomic number
6s (Z*). For example, the energy of 2s orbital of hydrogen atom
3 5d
5p is greater than that of 2s orbital of lithium and that of lithium
5s is greater than that of sodium and so on, i.e., E2s (H) > E2s (Li)
4f
4d > E2s (Na) > E2s (K).
2 4p
4s
1.11 Filling of Orbitals
3d
1 3p The distribution of electrons in various orbitals is known as
3s
electronic configuration. Having derived the energy level
2p sequence, it is now a simple matter to write the electronic
2s
configurations of atoms by making use of Aufbau principle,
1s Pauli’s exclusion principle and the Hund’s rule of maximum
1 25 50 75 100 multiplicity.
Atomic number
Fig 1.37 The relative energies of the atomic orbitals as a Aufbau Principle
function of atomic number
Aufbau is a German term meaning “building up”. This
principle is utilized to deduce the electronic structure of
of nucleus on the electrons increases with increase in poly-electron atoms by building them up, by filling up of
the positive charge (Ze) of nucleus. The attractive power orbitals with electrons. The Aufbau principle states that
of nucleus on the electrons will be less due to screening “in the ground state of the atoms, the orbitals are filled in
effect of inner electrons. The net positive charge expe- order of their increasing energies.” In other words, in the
rienced by the electron from the nucleus is known as ground state of atom, the orbital with a lower energy is filled
effective nuclear charge (Z*). up first before the filling of the orbital with a higher energy
The attractive and repulsive interactions depend upon commences.
the shell and shape of the orbital in which the electron is The increasing order of energy of various orbitals is
present. The spherical s orbital can shield the electrons from
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, ...
the nuclear attraction more effectively than the p-orbital with
dumbell shape. This is because of the spherical nature of the The above sequence of energy levels can be easily
s-orbital can shield nucleus from all directions equally but the remembered with the help of the graphical representation
electron in a p-orbital say px can shield the nucleus in only one shown in Fig 1.38.
direction, i.e., x-direction. Similarly, because of difference in
their shape and more diffused character the d-orbitals have
Pauli’s Exclusion Principle
less shielding power than p-orbitals. Further because of their
different shapes the electron in spherical orbital spends more The four quantum numbers define completely the position
time close to the nucleus when compared to p-orbital and the of electron in an atom. It is thus possible to identify an
p-electron spends more time in the vicinity of nucleus when electron in an atom completely by stating the values of
compared to d-electron. For this reason the effective nuclear its four quantum numbers. Wolfgang Pauli, an Austrian
charge experienced by different sub shell decreases with scientist, put forward an ingenious principle which controls
increase in the azimuthal quantum number (l). From this we the number of electrons to be filled in various orbitals, and
can easily understand that s-electron is strongly attracted by hence, it is named as the exclusion principle. It states that
the nucleus than the p-electron which in turn will be strongly no. two electrons in an atom can have the same set of
attracted than the d-electron and so on. Thus, the different four quantum numbers.
Chapter_01.indd 33 8/17/2013 3:42:45 PM

1s
2s 2p
3s 3p 3d
4s 4p 4d 4b
5s 5p 5d 5f
Energy
6s 6p 6d
7s 7p
Fig 1.38 The order in which the atomic orbitals are used in building up the electron configuration of many electron
atoms.The orbitals are used in sequence from the bottom in accordance with the Aufbau principle, Hund’s rule and Pauli’s
exclusion principle
Thus, in the same atom any two electrons may have

three quantum numbers identical but not the fourth which electron spin may be clockwise or anti-clockwise as
must be different. This means that the two electrons can shown in Fig 1.39. This results in the formation of
have the same value of three quantum numbers, n, l and two magnets. Placing of two electrons together in the
ml but must have the opposite spin quantum numbers. same orbital results in considerable repulsion due to
This restricts that only two electrons may exist in the same same negative charge. By overcoming the repulsive
orbital and these electrons must have opposite spins. Pau- forces and to keep the two electrons together in the
li’s exclusion principle helps in calculating the number of same orbital some energy is required, called pairing
electrons to be present in any sub shell. For example, the energy. If the two electrons also have the same
1s sub-shell comprises one orbital and thus the maximum spin there will be magnetic repulsion also, caus-
number of electrons present in 1s sub-shell can be two ing the requirement of more pairing energy. But, if
because of the following two possibilities. the two electrons are spinning in opposite directions
1 and forming a pair in an orbital, mutually cancel their
n = 1, l = 0, m = 0, s = + magnetic moments. Now, we can easily understand
2
that for an electron if pairing energy is less than the
1
n = 1, l = 0, m = 0, s = − energy of next higher energy level the electron will
2 be paired in the orbital. But if the pairing energy is
The p-sub-shell which is having 3 orbitals (px, py and pz)
greater than the energy of next higher energy level
can accommodate 6 electrons, the d-sub shell which having the electron goes to the next higher energy level.
5 orbitals can accommodate 10 electrons and the f-sub-shell
having 7 orbitals can accommodate 14 electrons. 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
The orbitals belonging to same sub-shell have same energy
Here a question arises? Why only two electrons and are called degenerate orbitals. Hund’s rule states that
can present in one orbital? It can be answered the electron pairing in degenerate orbitals of a given sub
as follows. We may recall from our knowledge of shell will not take place unless all the available orbitals of
elementary physics that the motion of an electric a given shell contains one electron each.
charge creates a magnetic field. In an orbital the Since there are three p, five d and seven f orbitals, pair-
ing of electrons will start in p, d and f orbitals with the entry
Chapter_01.indd 34 8/17/2013 3:42:46 PM

N N N N (sub-shell) and x represents the number of electron in that

sub shell. In sa pb dc ... notation the sub shell is depicted
with a superscript like a, b, c, ... etc, along with the princi-
pal quantum number before the respective sub shell. In the
orbital diagram notation each orbital of the sub shell is
represented by a box and the electron is represented by
an arrow (↑) for positive spin and an arrow (↓) for nega-
S S S S tive spin. The advantage of the second notation over the
(a) Both electrons with parallel spins first notation is that it represents all the four quantum
(b) Both electrons with opposite spins numbers. Based on these notations, the electronic con-
figurations of atoms of various elements of the Periodic
Fig 1.39 No two electrons in an atom can have the
Table in their ground state are as given in Table 1.5.
same set of four quantum numbers
Hydrogen has only one electron (Z = 1). This elec-
tron will enter the lowest energy orbital which is 1s. Thus,
the solitary electron of hydrogen atom, will occupy the 1s
of 4th, 6th and 8th electrons, respectively. It is also found that orbital. The electronic configuration of hydrogen atoms is,
half-filled and fully filled degenerate set of orbitals acquire therefore, represented as 1s1.
extra stability. The next element, helium, has two electrons (Z = 2).
One of these electrons occupies the 1s orbital as in the
case of the hydrogen atom. The second electron can also
1.11.1 Electronic Configuration of Atoms enter this orbital so as to fill it completely. The elec-
The filling of electrons in different orbitals in an atom are tronic configuration of helium is therefore, represented
governed by the above three rules viz., as 1s2. The two electrons occupying this orbital will have
(i) Aufbau principle, opposite spins as can be seen from the following orbital
(ii) Pauli’s exclusion principle, and diagram:
(iii) Hund’s rule of maximum multiplicity. The electronic 1S 1S
configuration of different atoms can be represented in H He
two ways:
(i) nlx or sa pb dc ...... notation The next element is lithium. It has three electrons
(ii) Orbital diagram method (Z = 3). The third electron of lithium (Li) is not allowed
In the nlx method, n represents the principle quan- into the 1s orbital because of the Pauli exclusion prin-
tum number, l represents the azimuthal quantum number ciple. If third electron enters into 1s orbital its spin will
Table 1.5 Electronic configuration of first 10 elements
1 Hydrogen 1s1 1s 2s 2p
↑
2 Helium 1s2 ↑↓
3 Lithium 2
1s 2s 1 ↑↓ ↑
4 Beryllium 1s2 2s2 ↑↓ ↑↓
5 Boron 1s 2s 2 p
2 2 1
x
↑↓ ↑↓ ↑
6 Carbon 1
1s2 2s2 2 p 2 p
x
1
y ↑↓ ↑↓ ↑ ↑
7 Nitrogen 1
1s 2s 2 p 2 p 2 p
2 2
x
1
y
1
z
↑↓ ↑↓ ↑ ↑ ↑
8 Oxygen 2
1s2 2s2 2 p 2 p 2 p
x
1
y
1
z ↑↓ ↑↓ ↑↓ ↑ ↑
9 Fluorine 2 2 2
1s 2s 2 p 2 p 2 p
x
2
y
1
z ↑↓ ↑↓ ↑↓ ↑↓ ↑
10 Neon 1s2 2s2 2 px2 2 p 2y 2 pz2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
Chapter_01.indd 35 8/17/2013 3:42:48 PM

become similar with one of the two electrons due to which electronic shell with the highest principal quantum number
the charge repulsion and magnetic repulsion will become are called the valence electrons. For example, the elec-
more. So more pairing energy will be required. This pair- trons in Ne are the core electrons and the electrons in the
ing energy will be more than the energy of the next higher highest principal quantum number from Na to Ar are the
energy level 2s. So, the electron goes into 2s. Hence, the valence electrons.
electronic configuration of Li is 1s2 2s1. The 2s orbital can The next ten elements (Z = 21 to 30) which follow cal-
accommodate one more electron. The configuration of cium are scandium (Sc), titanium (Ti), vanadium (V), chro-
beryllium (Be) atom is therefore 1s2 2s2. mium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel
The next element boron (Z = 5) has five electrons. The (Ni), copper (Cu) and zinc (Zn). In these elements, addi-
2s orbital has already been filled up. But the principal quan- tion of electrons takes place in the inner 3d orbitals, while
tum number is now 2, there are three p-orbitals still available. the outer 4s orbitals remains fully occupied. The electronic
The fifth electron, therefore, enters one of these p-orbitals. configuration of scandium (Z = 21), the first element in this
The electronic configuration of boron is 1s2 2s2 2p1. series, is 1s2 2s2 2p6 3s2 3p6 3d1 4s2 while that (Z = 30) of
The next five elements, namely carbon (Z = 6), the last element of the series is 1s2 2s2 2p6 3s2 3p6 3d10 4s2.
nitrogen (Z = 7), Oxygen (Z = 8), fluorine (Z = 9) and Thus, while filling of 3d orbitals begins with scandium, it
neon (Z = 10) of this period get their p-orbitals succes- ends up with zinc.
sively filled up. Their electronic configurations are given Anomalous configurations of chromium and copper:
in Table 1.5. It may be noted that the configurations of chromium
It may be noted that in carbon, the arrangement of (Z = 24) and copper (Z = 29) do not follow the general trend.
electrons in p-orbitals is 2 p1x , 2 p1y , and not the 2 px2. The electronic configurations of Cr and Cu are expected to
This is because to pair the electron in 2 px pairing be as follows:
energy is required but to enter into the 2 p y orbital hav-
ing energy equal (degenerate) to 2 px pairing energy is not Cr 1s2 2s2 2p6 3s2 3p6 3d4 4s2,
required. So, the electron goes into 2 p y. and Cu 1s2 2s2 2p6 3s2 3p6 3d9 4s2
Similarly in nitrogen, the arrangement is 2 p1x 2 p1y 2 p1z actually their configuration are
and not 2 px2 2 p1y. This is in accordance with Hund’s rule
of maximum multiplicity. In oxygen the last electron has Cr 1s 2 2 s 2 2 p6 3s 2 3 p6 3d 5 4 s1
two options. One to pair in one of three p-orbitals or to go and Cu 1s 2 2 s 2 2 p6 3s 2 3 p6 3d 10 4 s1
the next higher energy level 3s. Since the pairing energy
is less than the energy required to go to 3s orbital, pairing These anamolies are attributed to the fact that exactly
of electrons starts in oxygen and continues till all the three half-filled and completely filled orbitals (i.e., p3, p6, d5,
2p orbitals are filled up. d10, f 7 and f 14) are more stable because they possess the
The principal quantum 3 (M-shell) begins with sodium lower energy. The cause of this extra stability has been dis-
(Z = 11). the eleventh electron will evidently, enter, into the cussed in detail in the subsequent sections. Thus, to acquire
3s orbitals, the electronic configuration being 1s2 2s2 2p6 3s1. an increased stability, one of the electrons from 4s orbital
The next seven elements namely magnesium (Z = 12) goes into the nearby 3d orbital so that 3d orbitals become
aluminum (Z = 13), silicon (Z = 14), phosphorus (Z = 15), exactly half-filled in the case of chromium and completely
sulphur (Z = 16), chlorine (Z = 17), and argon (Z = 18) filled up in the case of copper.
follow the sequence described above. After completely filling the 3d orbitals, the filling up
Consider now the electronic configuration of the next of 4p orbitals starts at gallium (Ga) and is complete at
element which is potassium (Z = 19). The additional elec- krypton (Kr). In the next 18 elements from rubidium (Rb)
tron (i.e., nineteenth electron) instead of entering 3d orbit- to xenon (Xe) the pattern of filling the 5s, 4d and 5p orbit-
als, all of which are lying unoccupied so far, goes into the als are similar to that 4s, 3d and 4p orbitals as discussed
4s orbital. This is because 4s orbital is at lower energy level above. Then comes the turn of the 6s orbital. In caesium
than 3d orbitals. The electronic configuration of potassium (Cs) and barium (Ba), this orbital contains one and two
may be represented as 1s2 2s2 2p6 3s2 3p6 4s1. The addi- electrons respectively. After the filling up of 6s sub shell
tional electron in calcium (Z = 20) follows the same course with barium (Z = 56) the next electron in lanthanum
and goes into the same, i.e., 4s orbitals, to fill it up com- (Z = 57) goes to 5d sub shell and not the 4f sub shell. The
pletely. So, the electronic configuration of calcium is 1s2 subsequent electrons in the succeeding elements of the
2s2 2p6 3s2 3p6 4s2. lanthanide series (from Ce to Lu Z = 58 to 71) however
The electrons in the completely filled shells are known enters the 4f sub shell by following the normal sequence
as core electrons and the electrons that are added to the of energies. The filling up of 5d sub shell recommences
Chapter_01.indd 36 8/17/2013 3:42:49 PM

only after the 4f sub shell is completely filled up with Lu Similarly, after filling up of 7s sub-shell with radium
(Z = 71). (Z = 88) the next electron in actinium (Z = 89) goes to 6d
For the sake of simplicity, we do not always write the sub shell and not to 5f sub-shell. The subsequent electrons
complete electronic configuration. Instead, the configu- in the succeeding elements of the actinides (from Th to Lr
ration of the noble gas preceding the valence shell is not Z = 90 to 103), however, enter the 5f sub-shell. Thus, the
given; it is represented by its symbol in square bracket. For configurations of Ac, Th and Pa would be as follows:
example, for Na (Z = 11), we may write [Ne] 3s1, and for
Ac (Z = 89): [Rn] 6f 1 7s2
Ca (Z = 20), we may write [Ar] 4s2. Thus, the configura-
Th (Z = 90): [Rn] 5f 1 6d1 7s2
tions of La, Ce and Pr would be as follow:
Pa (Z = 91): [Rn] 5f 2 6d1 7s2
La (Z = 57): [Xe] 4f 0 5d1 6s2 The electronic configurations of the known elements
Ce (Z = 58): [Xe] 4f 1 5d1 6s2 (as determined by spectroscopic methods are given in
Pr (Z = 59): [Xe] 4f 2 5d1 6s2 Table 1.6).
Table 1.6 Electronic configuration of the elements
Element Z 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
B 5 2 2 1
C 6 2 2 2
N 7 2 2 3
O 8 2 2 4
F 9 2 2 5
Ne 10 2 2 6
Na 11 2 2 6 1
Mg 12 2 2 6 2
Al 13 2 2 6 2 1
Si 14 2 2 6 2 2
P 15 2 2 6 2 3
S 16 2 2 6 2 4
Cl 17 2 2 6 2 5
Ar 18 2 2 6 2 6
K 19 2 2 6 2 6 1
Ca 20 2 2 6 2 6 2
Sc 21 2 2 6 2 6 1 2
Ti 22 2 2 6 2 6 2 2
V 23 2 2 6 2 6 3 2
Cr * 24 2 2 6 2 6 5 1
Mn 25 2 2 6 2 6 5 2
Fe 26 2 2 6 2 6 6 2
Co 27 2 2 6 2 6 7 2
Ni 28 2 2 6 2 6 8 2
Cu* 29 2 2 6 2 6 10 1
Zn 30 2 2 6 2 6 10 2
Ga 31 2 2 6 2 6 10 2 1
Ge 32 2 2 6 2 6 10 2 1
As 33 2 2 6 2 6 10 2 3
Chapter_01.indd 37 8/17/2013 3:42:49 PM

Table 1.6 (Cont.)
Se 34 2 2 6 2 6 10 2 4
Br 35 2 2 6 2 6 10 2 5
Kr 36 2 2 6 2 6 10 2 6
Rb 37 2 2 6 2 6 10 2 6 1
Sr 38 2 2 6 2 6 10 2 6 2
Y 39 2 2 6 2 6 10 2 6 1 2
Zr 40 2 2 6 2 6 10 2 6 2 2
Nb* 41 2 2 6 2 6 10 2 6 4 1
Mo* 42 2 2 6 2 6 10 2 6 5 1
Tc 43 2 2 6 2 6 10 2 6 5 2
Ru* 44 2 2 6 2 6 10 2 6 7 1
Rh* 45 2 2 6 2 6 10 2 6 8 1
Pd* 46 2 2 6 2 6 10 2 6 10
Ag* 47 2 2 6 2 6 10 2 6 10 1
Cd* 48 2 2 6 2 6 10 2 6 10 2
In 49 2 2 6 2 6 10 2 6 10 2 1
Sn 50 2 2 6 2 6 10 2 6 10 2 2
Sb 51 2 2 6 2 6 10 2 6 10 2 3
Te 52 2 2 6 2 6 10 2 6 10 2 4
l 53 2 2 6 2 6 10 2 6 10 2 5
Xe 54 2 2 6 2 6 10 2 6 10 2 6
Cs 55 2 2 6 2 6 10 2 6 10 2 6 1
Ba 56 2 2 6 2 6 10 2 6 10 2 6 2
La * 57 2 2 6 2 6 10 2 6 10 2 6 1 2
Ce* 58 2 2 6 2 6 10 2 6 10 2 2 6 2
Pr 59 2 2 6 2 6 10 2 6 10 3 2 6 2
Nd 60 2 2 6 2 6 10 2 6 10 4 2 6 2
Pm 61 2 2 6 2 6 10 2 6 10 5 2 6 2
Sm 62 2 2 6 2 6 10 2 6 10 6 2 6 2
Eu 63 2 2 6 2 6 10 2 6 10 7 2 6 2
Gd* 64 2 2 6 2 6 10 2 6 10 7 2 6 1 2
Tb 65 2 2 6 2 6 10 2 6 10 9 2 6 2
Dy 66 2 2 6 2 6 10 2 6 10 10 2 6 2
Ho 67 2 2 6 2 6 10 2 6 10 11 2 6 2
Er 68 2 2 6 2 6 10 2 6 10 12 2 6 2
Tm 69 2 2 6 2 6 10 2 6 10 13 2 6 2
Yb 70 2 2 6 2 6 10 2 6 10 14 2 6 2
Lu 71 2 2 6 2 6 10 2 6 10 14 2 6 1 2
Hf 72 2 2 6 2 6 10 2 6 10 14 2 6 2 2
Ta 73 2 2 6 2 6 10 2 6 10 14 2 6 3 2
W 74 2 2 6 2 6 10 2 6 10 14 2 6 4 2
Re 75 2 2 6 2 6 10 2 6 10 14 2 6 5 2
Os 76 2 2 6 2 6 10 2 6 10 14 2 6 6 2
Ir 77 2 2 6 2 6 10 2 6 10 14 2 6 7 2
Pt * 78 2 2 6 2 6 10 2 6 10 14 2 6 9 2
Au 79 2 2 6 2 6 10 2 6 10 14 2 6 10 2
Hg 80 2 2 6 2 6 10 2 6 10 14 2 6 10 2
Tl 81 2 2 6 2 6 10 2 6 10 14 2 6 10 2 1
Chapter_01.indd 38 8/17/2013 3:42:49 PM

Pb 82 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2
Bl 83 2 2 6 2 6 10 2 6 10 14 2 6 10 2 3
Po 84 2 2 6 2 6 10 2 6 10 14 2 6 10 2 4
At 85 2 2 6 2 6 10 2 6 10 14 2 6 10 2 5
Rn 86 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6
Fr 87 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 1
Ra 88 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2
Ac 89 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2
Th 90 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2
Pa 91 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2 6 2
U 92 2 2 6 2 6 10 2 6 10 14 2 6 10 3 2 6 2
Np 93 2 2 6 2 6 10 2 6 10 14 2 6 10 4 2 6 2
Pu 94 2 2 6 2 6 10 2 6 10 14 2 6 10 6 2 6 2
Am 95 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 2
Cm 96 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 2
Bk 97 2 2 6 2 6 10 2 6 10 14 2 6 10 8 2 6 2
Cf 98 2 2 6 2 6 10 2 6 10 14 2 6 10 10 2 6 2
Es 99 2 2 6 2 6 10 2 6 10 14 2 6 10 11 2 6 2
Fm 100 2 2 6 2 6 10 2 6 10 14 2 6 10 12 2 6 2
Md 101 2 2 6 2 6 10 2 6 10 14 2 6 10 13 2 6 2
No 102 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 1 2
Lr 103 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 2 2
Rf 104 2 2 6 2 6 10 2 6 10 14 2 6 10 10 2 6 3 2
Db 105 2 2 6 2 6 10 2 6 10 14 2 6 10 11 2 6 4 2
Sg 106 2 2 6 2 6 10 2 6 10 14 2 6 10 12 2 6 5 2
Bh 107 2 2 6 2 6 10 2 6 10 14 2 6 10 13 2 6 6 2
Hs 108 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 7 2
Mt 109 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 8 2
Ds 110 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 9 2
Rg ** 111 2 2 6 2 6 10 2 6 10 14 2 6 10 14 2 6 10 1
* Elements with exceptional electronic configurations.

* * Elements with atomic number 112 and above have been reported but not yet fully authenticated and named.
1.11.2 Relative Stabilities of Electronic 20 different electronic arrangements as shown in Table 1.7
Configurations These different electronic arrangements would have differ-
ent energies inspite of the fact that they belong to the same
Before we discuss the relative stabilities of various elec- electronic configuration. (Some of the electronic arrange-
tronic configurations, we should clearly understand the ments may have the same energy due to similar inter elec-
difference between electronic configuration and electronic tronic repulsions). Therefore, when we talk of the stability
arrangement. For this, let us consider the nitrogen atom. of the electronic configuration, we are ipso facto concerned
Its outer electronic configuration is 2s2 2p3. From this we with the stability of the electronic arrangement of that con-
get information that three electrons are present in a set of figuration. Of all the electronic arrangements permitted by
three 2p orbitals. This configuration gives us no informa- a given configuration the most stable configuration can be
tion about the manner in which these three electrons are predicted based on the following two factors:
arranged in three 2p orbitals. 1. Symmetrical distribution of charge
It can be easily shown through permutations and 2. Hund’s rule of maximum multiplicity
combinations that there are as many as 20 different ways To explain these two factors we shall consider here
of placing these three electrons in the three 2p orbitals. the different electronic arrangements of p3 configuration as
In other words, the electronic configuration 2p3 can have shown in Table 1.7.
Chapter_01.indd 39 8/17/2013 3:42:50 PM

Table 1.7 Arrangements of three electrons in three Table 1.8 Spin multiplicity
p-orbitals
No. of
S. no. px py pz unpaired electrons S Multiplicity Name of state
1
↑
↑
↑ 0 0 1 Singlet
2 ↑ ↑ ↓
3 ↑ ↓ ↑ 1
1 2 Doublet
4 ↓ ↑ ↑ 2
5 ↓ ↓ ↓ 2 1 3 Triplet
6 ↓ ↓ ↑
7 ↓ ↑ ↓ 3
3 4 Quartet
8 ↑ ↓ ↓ 2
9 ↑↓ ↑ 4 2 5 Quintet
10 ↑↓ ↑
11 ↑↓ ↑
12 ↑ ↑↓
13 ↑ ↑↓
Configurations with even or uniform or symmetrical
14 ↑ ↑↓
distribution of charge in all directions would evidently be
15 ↑↓ ↓
associated with lower energy and hence higher stability
16 ↑↓ ↓
than the configurations with unsymmetrical distribution of
17 ↑↓ ↓
electronic charge.
18 ↓ ↑↓
To sum up: A symmetrical distribution of electronic
19 ↓ ↑↓
charge leads to a decrease in energy and hence an increase
20 ↓ ↑↓
in the stability of the system.
It can be easily seen that among 20 electronic arrange-
ments of p3 configurations of Table 1.7 1 to 8 arrange-
ments would have a uniform or symmetrical distribution of
Symmetrical Distribution of Charge
charge in space. Therefore, these configurations would be
In order to understand the effect of the symmetrical dis- more stable than all other p3 configurations.
tribution of charge in orbitals on the stability of electronic Now a question arises that among the 1 to 8 arrange-
arrangements, let us recall the shapes of various sets of ments of p3 configurations which will be more stable ? This
orbitals one by one. The s-orbital is spherical in shape can be explained based on Hund’s rule of maximum mul-
which implies that the electronic charge would be distrib- tiplicity. Then what is spin multiplicity? The spin multi-
uted uniformly in all directions whether there is one or two plicity is the value of 2S + 1 where S is the resultant spin
electrons present in the orbital. quantum number. The relation between the number of
Of the three p-orbitals, the px is symmetrical along the unpaired electrons, the resultant spin quantum number S
X-axis while the orbitals py and pz are symmetrical along and multiplicity is given in Table 1.8.
the Y- and Z-axes respectively. If one electron is present in Maximum spin multiplicity is possible only when all
px -orbital, i.e., for p1x configuration, the electronic charge the degenerate orbitals occupy with electrons of parallel
would be mainly concentrated in the X-direction only. Like- spin. In the Table 1.7 the 1 and 5 electronic arrangements
wise the electronic charge would be mainly concentrated have maximum number of unpaired electrons with paral-
in the Y-direction of p1y configuration. Similarly, in p1x p1y lel spin and thus have maximum multiplicity. So, these
configuration, the electronic charge would be mainly con- two (1 and 5) electronic arrangements are more stable
centrated in the xy plane. In a similar manner, the electronic than the other electronic arrangements. This is because
charge would be concentrated more along the X-direction in of lowering of energy in those arrangements. Then again
the configuration px2 p1y p1z and more in the plane xy in the another question arises as to why such arrangements
configuration px2 p 2y p1z. It is evident that in all the p configura- have less energy? The answer for this question can be
tions mentioned above, the charge is not evenly spread along explained involving the contribution of exchange energy
all the directions. In other words, the distribution of charge as discussed below.
is non-uniform or unsymmetrical. On the other hand, the By advanced mathematical treatment, it can be shown
distribution of charge in the configurations p1x p1y p1z and that if on exchanging the position in space of two electrons
px2 p 2y pz2 would be uniform or symmetrical in all directions. with parallel spins, there is no change in the electronic
Chapter_01.indd 40 8/17/2013 3:42:51 PM

arrangement, it would lead to decrease in energy. The

pair of electrons is called the exchange pair. The larger 1 2
the number of exchange pairs of electrons, the greater
would be the decrease of energy. The energy decrease 4 exchange by electron 1 3 exchange by electron 2
per exchange pair of electrons is termed as Columbic
exchange energy and is represented with E. it would evi-
dently, carry a negative sign. 3 4
In the electronic arrangements 1 and 5 of p3 configu-
rations in Table 1.7, three exchange pairs are possible (1, 2 exchange by electron 3 1 exchange by electron 4
2; 1, 3; and 2, 3). So the lowering of energy due to colum-
bic exchange energy will be − 3E. From 1-8 electronic Fig 1.40 Possible exchange pairs for a d5 configuration
arrangements of p3 configurations (Table 1.7) except 1and
5 there is only one exchange pair since one electron is Normal outer electronic 1s 2s 4s
with anti-clockwise spin. So, the decrease in energy due configuration of chromium ↑ ↑ ↑ ↑
to columbic exchange energy is only − E. In the remain- ↑↓
ing electronic arrangements 9 to 20 (Table 1.7) two elec- Anomalous electronic
trons are paired in one of the p orbitals which requires configuration of chromium ↑ ↑ ↑ ↑ ↑ ↑
pairing energy represented by P. Obviously, the pairing The 3d 4 4s2 configuration has only 10 exchange pairs
energy is positive. ( C2 pairs) whereas the 3d5 4s1 has 15 exchange pairs
5
Since the pairing energy has positive sign, while the (6C2 pairs) because the 3d4 4s2 has 5 electrons with paral-
Columbic exchange energy have negative sign, pairing lel spins while 3d5 4s1 arrangement has 6 electrons with
energy will destabilize the atom while exchange energy will parallel spins. Hence, in 3d5 4s1 arrangement the decrease
give stability to the atom. Thus, the overall stability of a sys- in energy is −15E while in 3d4 4s2, is −10E. Further, in 3d4
tem would be decided by the aggregate of exchange energy 4s2 configuration, there is one pair of electrons in 4s orbital
(E) and pairing energy (P). In the case of electronic arrange- which requires the pairing energy. So, the net decrease
ments 9 to 20 (Table 1.7) the net energy change will be − E + in energy of 3d4 4s2 configuration is −10E + P. Also, the
P, and is the least stable. The electronic arrangements 1 and 3d4 4s2 configuration has no symmetrical distribution of
5 (Table 1.7) are most stable because of symmetrical distri- charge. So, the 3d5 4s1 configuration for chromium is more
bution of charge and more number of columbic exchange stable than 3d4 4s2 configuration.
energies. It can thus be concluded that electronic arrangements
Similarly, the stability of anomalous electronic con- with exactly half-filled or completely filled degenerate orbitals
figuration of chromium can be explained. would be more stable than any other electronic arrangement.
Key Points
Sub-Atomic Particles • Mass of one electron is equal to 1/1837 of hydrogen

atom or 9.109 × 10−28 g or 9.1 × 10−31 kg.
• The fundamental particles of every atom are
• Mass of one mole of electrons is equal to 0.55 mg.
(i) electron (ii) proton, and (iii) neutron
• Energy of electron is not influenced by any magnetic field.
• The only element whose atoms do not contain a funda-
• Specific charge decreases with increase in velocity of
mental particle (neutron) is hydrogen.
electron due to increase in mass.
• e/m ratio is constant for the cathode ray.
Electron
Proton
• Discovered by J.J. Thomson in 1897.
• Experiment in a discharge tube: cathode rays are • Discovered by Goldstein in canal rays experiment.
formed in a discharge tube voltage (10, 000 V) and • Properties of the canal rays are characteristics of the
low pressure. gas taken in the discharge tube.
• Electron is the lightest fundamental particle. • The canal rays contain positively charged ions of gas
• Charge on electron is equal to −4.8 × 10−10 esu or present in the discharge tube.
−1.602 × 10−19 coulombs. • The smallest +ve charged particle is proton.
Chapter_01.indd 41 8/17/2013 3:42:52 PM

• The mass of proton 1.008 u or 1.672 × 10−24 g or • Atoms of different elements containing the same
1.672 × 10−27 kg. number of neutrons are called isotones.
• The charge of proton is equal to 4.8 × 10−10 esu or • Isotones differ in both atomic numbers and mass number
1.602 × 10−19 coulombs. but difference in the atomic number and mass number is
• Proton is H+ ion. the same.
Neutron Developments Leading to the Bohr’s Model

• Neutron was discovered by Chadwick. of Atom, Nature of Light
• Neutron is emitted when lighter elements like beryl- • All radiant energy propagates in the form of waves.
lium and boron are bombarded with α-particles. • The radiant energy is in the form of electromagnetic
• Neutron has no charge. waves.
• Mass of neutron is 1.00866 u or 1.675 × 10−24 g or • The radiations are associated with electric and mag-
1.675 × 10−27 kg. netic field perpendicular to one another.
• Neutron is the heaviest fundamental particle of the atom. • On the propagation of an electromagnetic radiation there
is only propagation of wave but not that of the medium.
Rutherford’s Atomic Model • Wavelength is the distance between two successive
crests or between two successive troughs of waves.
• Rutherford’s experiment proved the presence of nucleus.
(i) It is denoted by l.
• The total mass of the atom is concentrated at the centre
(ii) It is measured in Å (Angstroms) or nm (nanom-
of the spherical atom known as nucleus.
eters) 1Å = 10−8 cm or 1 nm = 10−9 m.
• The positive charge of the nucleus is counter-balanced
• Frequency is the number of waves per second passing
by the negatively charged electrons revolving round
at a given point. It is denoted by v. Units of frequency
the nucleus.
are Hertz or cycles s−1.
• Rutherford model is also known as the Planetary model.
• Velocity of light is the distance travelled by one wave
• As per the laws of electrodynamics a moving electron
in one second.
(charged particle) should continuously loose energy
• Light or all electromagnetic radiations travel in vac-
by emission of radiation. Consequently it should fall
uum or air with the same velocity.
into the nucleus.
• Velocity of light c = 3 × 108 m s−1.
• If the electron loses energy continuously, the
• Wavelength is inversely proportional to the frequency
atomic spectrum should be band spectrum but the
of the wave.
atomic spectra are line spectra.
• Velocity of light = Frequency × Wavelength or c = νλ.
• Wave number is the number of waves spread in one
Atomic Number centimeter, denoted by v.
• The number of electrons or protons in an atom is equal • Wave number v is the reciprocal of wavelength.
to its atomic number. 1 c
v = , but v = , \ v = cv
• Moseley discovered the relation between the frequen- λ λ
cies of the characteristic X-rays (v) of an element and • Units of wave number are cm−1 or m−1.
its atomic number (z).
Quantum Theory of Radiation
v = a ( z − b ) a and b are constants.
• Corpuscular theory of light was proposed by
• Sum of the number of protons and neutrons in an atom
Newton.
is called its mass number.
• According to corpuscular theory of Newton, light is
• Mass number is the corrected atomic weight to a whole
propagated in the form of small invisible particles.
number.
• Quantum Theory was proposed by Max Planck and
• Mass number A = Z + N where Z is atomic number and
was extended by Einstein.
N is the number of neutrons.
• A hot vibrating body does not emit or absorb energy
• Atoms of an element which differ in their mass but
continuously but emits or absorbs energy discontinu-
have the same atomic number are called isotopes.
ously in the form of small energy packets called quanta.
• Isotopes have same number of protons but differ in the
• The energy of radiation (E) is proportional to its
number of neutrons present in them.
frequency (n).
• Different atoms having same mass number but with
different atomic numbers are called isobars. E ∝ v (or) E = hv
Chapter_01.indd 42 8/17/2013 3:42:52 PM

h is a constant known as Planck’s constant. Its value • The spectrum formed by the emission of energy in the
is 6.6256 × 10−34 Js or kg m2 s−1 or 3.6253 × 10−27 erg form of light radiation is called an emission spectrum.
second or g cm2. • Emission spectrum consists of bright lines or bands
• A hollow sphere coated inside with platinum black and on a dark background.
having a small hole in its wall acts as a near black body. • Absorption spectrum is just opposite to emission
• Black body is a perfect absorber and perfect emitter of spectrum.
radiant energy. • The dark lines in the absorption spectrum and bright
• At a given temperature the intensity of radiation lines in the emission spectrum of a particular sub-
increases with wavelength, reaches a maximum and stance appear at the same places (same wave length).
then decreases. • The apparatus used to record the spectrum is called the
• As the temperature increases the intensity of the radia- spectrometer or spectrograph.
tion will be more towards the lower wavelengths. • Emission spectrum is due to the emission of light by
• Planck’s quantum theory explains only the black body the excited atoms or molecules.
radiations. • Absorption spectrum is due to the excitation of atoms
• Einstein extended the quantum theory to all types of or molecules by absorbing the energy.
electromagnetic radiations. • Each element has its own characteristic line spectrum
• Einstein called the energy packets of electromagnetic by which it can be identified.
radiations as photons. • Line spectra are given by atoms so known as atomic
• The emission of electrons from metal surface when spectra and band spectra are given by molecules so
exposed to radiation of suitable wavelength is known known as molecular spectra.
as photoelectric effect.
• The photoelectric effect is readily exhibited by alkali
Hydrogen Spectrum
metals like K and Cs.
• When photon strikes the metal, its energy is absorbed • Of all the spectra, hydrogen spectrum is the simplest
by the electron and emission of electrons takes place. spectrum.
• A part of the energy of the photon is used up to escape • Hydrogen spectrum consists of a groups of lines clas-
the electron from the attractive forces and the remain- sified into various series.
ing energy is used in increasing the kinetic energy of • Only Balmer series is the visible series in hydrogen
the electron. spectrum.
• Wavelength of a spectral line in hydrogen spectrum
hv = W + KE
can be calculated by using Rydberg’s equation.
hv = Energy of photon; W = Energy required to over-
1 1 1
come the attractive forces on an electron in the metal; v= = RH  2 − 2
KE = Kinetic Energy of the emitter electron. λ  n1 n2 
• A body can absorb light energy in the form of photons • R is Rydberg’s constant and its value is 109677 cm−1
and goes to the excited state E2 from the ground state E1. for hydrogen atom.
• Emission of energy will be accompanied during the • In Balmer series first line is called as Hα, second line
transition from excited state to ground state. is Hβ, third line as Hγ, fourth line as Hδ and so on.
• The wavelengths of Hα, Hβ, Hγ and Hδ are obtained by
E2 − E1 = DE = hv
substitution series in hydrogen spectrum are
Types of Spectra Name of series n1 n2 Spectral Region

Lyman series 1 2, 3, 4, 5, 6,........ Ultraviolet
• The arrangement obtained by splitting of electromag-
Balmer series 2 3, 4, 5, 6,........ Visible
netic radiation into its component wave lengths when
Paschen series 3 4, 5, 6,........ Near infrared
passed through a prism is called a spectrum.
Brackett series 4 5, 6, 7,........ Infrared
• When white light is passed through the prism, it gives a
Pfund series 5 6, 7 ...... Far infrared
continuous spectrum of seven colours (VIBGYOR).
• In a continuous spectrum each colour fades into the
next colour as in a rainbow. • The spectral lines get closer and closer as we move
• The spectrum of incandescent white light obtained by from n2 = 3 to 4 to 5 to 6 etc.
heating a solid to very high temperature is a continu- • If n2 is taken as ∝ the limiting wavelength of the lines
ous spectrum. in any series can be obtained.
Chapter_01.indd 43 8/17/2013 3:42:53 PM

• From Lyman series to Pfund series, wavelength • For hydrogen, since z = 1, the radius of orbit is equal
increases but frequency and energy decrease. to 0.529 × n2 Å. Radius of 1st orbit = 0.529 Å, radius
• Maximum difference in energy for hydrogen atom is of 2nd orbit = 2.116 Å etc.
found when n1 = 1 and n2 = 2 or higher value. 1
• RH value 109677 cm−1 is valid only for lines in the • Kinetic energy of the electron due to motion = mv 2.
2
hydrogen spectrum. e2
• For a spectral line of any one electron species like He+ • Potential energy of the electron due to position = − .
r
or Li2+, the value of R is equal to 109677 z2 cm−1 where • Total energy of the electron E = Kinetic energy +
z is the atomic number. potential energy
• Number of spectral lines when an electron is coming
to ground state or to the orbit n1 from excited state in 1 2 e2 e2 e2  e2 2
= mv − = − ∵ r = mv 
orbit n2 can be calculated as. 2 r 2r r  
n ( n + 1) e2
, where n = n2 − n1. =−
2 2r
• Bohr’s equation for calculating the energy of an orbit
Bohr’s Model of the Atom
2π2 me 4 z 2
• The basis for the Bohr’s model of atom is the Planck’s En = − × 2
h2 n
quantum theory and hydrogen spectrum.
• Electrons revolve round the nucleus in concentric cir- • The energy of an electron in an atom is negative and
cular orbits which are represented by K, L, M, N, O, inversely proportional to the square of the n value (n is
P..... or 1, 2, 3, 4, 5, 6..... etc. the number of orbit).
• Each orbit is associated with some energy. So they are • As the electron moves away from the nucleus the kinetic
known as energy levels or stationary orbits. energy decreases and potential energy increases.
• The energy of the orbit increases with increase in the • The potential energy of an electron is zero when the
distance form the nucleus. electron is at infinite distance from the nucleus.
• The energy of an electron moving in an orbit remains • As the n value of the orbit decreases, the size and
constant. energy of the orbit decreases.
• The electron can move from one orbit to another orbit • The kinetic energy of an electron (positive value) is
only when they lose or gain the energy difference of greater than the potential energy (negative value).
the orbitals. • The energy of an electron in the hydrogen atom.
• ΔE = E2 – E1 = hv 313.6
• An electron while moving from higher energy level to En = − Kcal mol−1
n2
the lower energy level emits energy in the form of light.
• The angular momentum (mvr) is quantized. It is an 1312
= − 2 KJ mol−1
h n
integral multiple of where ‘h’ is the Planck’s
2π 2.18 × 10 −11
constant. =− ergs atom−1
n2
nh 13.6
mvr = = − 2 eV atom−1
2π n
• The force of attraction between the nucleus and the
e2 • Bohr’s equation to calculate the velocity of an electron
electron = 2 . in hydrogen atom,
r
• The centrifugal force gained by the electron due the nh 2πe 2 z
Vn = = ×
mv 2 2πmr h n
revolving round the nucleus = − .
r • The velocity of electron in first orbit of hydrogen is
• Bohr’s equation to calculate the radius of an orbit is 2.188 ms−1.
• The energy emitted or absorbed when an electron
n2 h2 moves from one orbit to another orbit can be calcu-
r= 2 2
4 π 2e m lated from DE = hv = hcv .
Chapter_01.indd 44 8/17/2013 3:42:54 PM

• v can be calculated by using Rydberg’s-Ritz equation. • Depending upon the ‘l’ values the subshell in which
the electron present can be known.
1 1
v = RH  2 − 2  If l = 0, the electron belongs to s-sub-shell.
 n1 n2  If l = 1, the electron belongs to p-sub-shell.
If l = 2, the electron belongs to d-sub-shell.
2π2 me 4 If l = 3, the electron belongs to f-sub-shell.
• The RH value = = 109699 cm−1.
ch3 • The number of electrons that can be present in any
• Bohr’s theory could explain the spectra of atoms and sub-shell is equal to 2(2l + 1) or 4l + 2.
ions like He+, Li2+. Be3+ having one electron only. • The number of sub-shells present in an orbit is equal to
• Bohr’s theory correlates the velocity of light, elec- the value of principal quantum number ‘n’ value.
tronic mass, Planck’s constant and electronic charge. • Number of subs-shells in K shell (n = 1) = 1 (i.e., 1s)
• The energy of the orbit, radius of the orbit and the value • Number of sub-shells in L shell (n = 2) = 2 (i.e., 2s
of Rydberg’s constant RH calculated from Bohr’s theory and 2p)
are in good agreement with the experimental value. • Number of sub-shells in M shell (n = 3)
• Bohr’s theory could not explain the spectra of atoms = 3(i.e., 3s, 3p and 3d )
having electrons more than one. • Number of sub shells in N shell (n = 4)
• Bohr’s theory could not explain the wave nature of = 4(i.e., 4s, 4p, 4d and 4f )
electron established by de Broglie. • s-orbital is spherically symmetrical in shape.
• It could not explain Zeeman effect and Stark effect. • p-orbital is dumb-bell in shape.
• Splitting of spectral lines in a strong magnetic field is • d-orbital is double dumb-bell in shape.
called as the Zeeman effect. • f-orbital is four fold dumb-bell in shape.
• Splitting of spectral lines in strong electric field is
called the Stark effect.
• The further splitting of ordinary spectrum when taken Magnetic Quantum Number
by super-spectrometer is called the fine spectrum. • It was proposed by Lande to account for the Zeeman
effect.
Quantum Numbers • It is denoted by ml.
• It gives the orientation of the orbital.
• To explain fine spectrum each electron in an atom is • The values of ‘ml’ depends upon ‘l’ and are equal to
assigned with a set of four quantum numbers. (2l + 1) ranging from −l passing through ‘0’ to + l.
• Quantum numbers explain the orbital concept of • s-sub-shell will have only one value ‘0’. So contain
atomic model i.e., size, shape, orientation and spin of only one orbital i.e., s-orbital.
the electron. • p-sub-shell will have three orbitals having ‘ml’ value
−1, 0, +1. These are px, py and pz.
Principal Quantum Number • d-sub-shell will have five orbitals having ‘ml’ values
−2, −1, 0, +1, +2.
• It was proposed by Bohr, and is denoted by n. • f-sub-shell will have seven orbitals having ‘ml’ values
• It will have any integer value except zero. −3, −2, −1, 0, +1, +2, +3.
• It gives the size of the orbit and hence energy of orbit. • The + and – signs indicate only change in direction but
• As the value of n increases the size and energy of the the magnetic quantum number ‘ml’ as such is neither
orbit increases. positive nor negative.
• It also represents the distance of the electron from the
nucleus. Spin Quantum Number
• The number of electrons that can be present in an orbit
is equal to 2n2. • It was proposed by Uhlenbeck and Goudshmit and is
denoted by ‘s’.
• Electron moving in an orbital can spin on its own axis.
Azimuthal Quantum Number • The spin of the electron may be clockwise or
• It was proposed by Sommerfeld denoted by l. anti-clockwise.
1
• It gives the shape of an orbital. • The clockwise spin is denoted by + or ↑ and
• ‘l’ values depend upon the ‘n’ values and are equal to 2
1
‘n - l’ i.e., 0, 1, 2, 3,..... anti-clockwise spin is denoted by − or ↓.
2
Chapter_01.indd 45 8/17/2013 3:42:55 PM

• The difference between the two spin quantum numbers electron in space around the nucleus can be predicted.
is 1 which is equal to the difference between succes- • Schrodinger wave equation gives the probability of
sive quantum numbers. finding the electron in space around the nucleus.
• Modern theory of atomic structure was proposed on • Schrodinger wave equation is
the basis of quantum mechanics or wave mechanics 2 2 2 2
∂ψ ∂ψ ∂ψ 8π m
proposed independently by de Broglie, E. Schrodinger 2
+ 2
+ 2
+
2
( E −U)ψ = 0
and W. Heisenberg. ∂x ∂y ∂z h
Where y is the wave function, m is the mass of elec-
Waves and Particles tron, E is the total energy of electron, U is the potential
energy of the electron.
• Wave theory of moving particles was proposed by Schrodinger wave equation indicates the variation of
de Broglie. the y value along x, y and z axes.
• Wavelength of a moving particle can be calculated by • y is the amplitude of the wave function.
the relation λ =
h
=
h • |y|2 denotes the particle density when applied to the
mv p particles.
where l is wavelength of a moving particle h is
Planck’s constant, m is mass of the particle, v is veloc- Probability Concept
ity of particle, and p is the momentum of particle.
• The dimensions of the Planck’s constant depend upon • p-orbital has both nodal regions equal to n − 2 and
the dimensions of momentum. de Broglie derived the nodal planes equal to the value of l, i.e., = 1.
wave nature of a moving particle from Einstein’s mass • The nodal plane for px orbital is yz; for py is xz and for
energy equation (E = mc2) and Planck’s quantum the- pz is xy.
ory (E = hv). • Each d-orbital has nodal regions equal to n − 3 and
• While the electron wave is moving in an orbit if the nodal planes equal to the value of l i.e., 2.
two ends meet to give regular series of crests and • For any orbital the number of nodal regions is equal
troughs, the electron wave is said to be in phase. to n − l −1 and nodal planes equal to l.
• For the electron to be in phase it is necessary that the • The nodal regions are known as radial nodes and the
circumference of the Bohr’s orbit (= 2πr) must be nodal planes are known as angular nodes.
equal to the whole number of the wavelength (l) of
electron wave nl = 2πr. Filling of Orbitals Pauli’s Exclusion Principle
• No two electrons in the same atom can have the same
Heisenberg’s Uncertainty Principle values for all the four quantum numbers.
• It is impossible to know exactly both position and • The two electrons present in a given orbital may have
momentum of an electron or any other smaller particle the same values of n, l and ml but they must have
simultaneously and accurately. 1 1
• Mathematically the uncertainty principle can be opposite spin, i.e., either + or −
2 2
expressed as
• Pauli’s principle helps the determination of maximum
h number of electrons that can be placed in an orbital of
∆x ⋅ ∆p ≥
4π sub-shell and a main shell.
• For an electron revolving round the nucleus in an atom • Pauli’s principle is followed only while writing the
the value of n is 4. electronic configuration of atoms in their ground
state.
h
Hence, ∆x ⋅ ∆px ≥
4π
Aufbau Principle
• The electron configurations of successive elements
Schrödinger Wave Equation differ only in the last electron which is known as
• The consequence of Heisenberg uncertainty principle differentiating electron.
is that since the exact position of an electron in an atom • According to aufbau principle “the electrons tend to occupy
cannot be predicated, only probability of finding an orbitals of minimum energy” in the ground state of atom.
Chapter_01.indd 46 8/17/2013 3:42:56 PM

• The energies of different orbitals can be calculated which form 10 exchange pairs (5C2), so average
from n + l values. lowering of energies is 10E. Hence 3d5 4s1 configu-
• In case two orbitals have same n + l values, the elec- ration rather than 3d4 4s2 configuration is stable for
tron goes into the orbital whose n values is less. chromium.
• The sequence of filling different orbitals by electrons
be known form Moeller diagram. (Fig 1.38).
• The energy of 4s orbital is less than that of 3d orbital Magnetic Properties of Atoms
in elements having atomic number up to 20, but in ele- • Atoms which contain unpaired electrons exhibit
ments having atomic number above 20, the energy of paramagnetism.
3d orbital is less than 4s. • Paramagnetic substances are attracted by the external
• The energy of 4f orbital has more energy than 6s in the magnetic field.
elements having atomic number up to 57, but in the • Atoms in which all the electrons are paired exhibit
elements having atomic number around 90 the energy diamagnetism.
of 4f is less than 5s orbital. • Diamagnetic substances are repelled by the external
• Electronic configurations are written in nlx method magnetic field.
where n is the principal quantum number. l is the • The paramagnetic moments of atoms depend upon the
azimuthal quantum number and x is the number of number of unpaired electrons.
electrons present in it. • The paramagnetic moment can be calculated by using
the formula µ = n( n + 2) BM where n is the number
Hund’s Rule of unpaired electrons.
• The orbitals in a sub-shell having equal energy are
called degenerate orbitals.
• According to Hund’s rule all the available orbitals are Practice Exercise
singly filled first with electrons of parallel spin and
then only pairing of electrons starts. Multiple Choice Questions with Only
• The half-filled and completely filled degenerate orbit- One Answer
als in atoms provide the stability. Level I
• When two electrons are paired with opposite spins 1. Which statement does not form part of Bohr’s model
columbic repulsion energy is lowered. of the hydrogen atom.
• When two electrons are paired with parallel (a) energy of the electrons in the orbit is quantized.
spins they remain farther apart due to columbic (b) the electron in the orbit nearest the nucleus is in
repulsion. the lowest energy.
(c) electrons revolve in different orbits around the
Stability of Atoms nucleus.
(d) the position and velocity of the electrons in the
• On exchanging the position in space of two electrons orbit cannot be determined simultaneously.
with parallel spins, if there is no change in the elec- 2. If S1 be the specific charge (e/m) of cathode rays and
tronic arrangement it leads to decrease in energy. This S2 be that of positive rays then which is true.
pair is called the exchange pair. (a) S1 = S2 (b) S1 < S2
• The decrease in energy per exchange pair of electrons (c) S1 > S2 (d) either of these
is referred as Columbic exchange energy. 3. The mass of an electron is m, its charge e and it is
• As the number of exchange pairs increases the stabil- accelerated from rest through a potential difference V.
ity of an atom increases by the lowering of exchange The kinetic energy of the electron in joules will be
energy E for each pair. (a) V (b) eV
• For chromium with electronic configuration 3d 5 4s1 (c) MeV (d) none
has five unpaired electron in d-orbitals and one elec- 4. In the above question, the velocity acquired by the
tron in 4s orbital having parallel spin which gives electron will be
15 exchange pairs (6C2), so average lowering energy
is 15E. (a) (V / m) (b) (eV / m)
• For chromium with electronic configuration 3d4 4s2
has only four unpaired electrons in d-orbitals and (c) (2eV / m) (d) none
Chapter_01.indd 47 8/17/2013 3:42:56 PM

5. For an electron in a hydrogen atom, the wave function, 12. The angular speed of the electron in the nth orbit of
ψ is proportional to exp (r/ao), where ao is the Bohr’s Bohr hydrogen is.
radius. What is the ratio of the probability density the (a) Directly proportional to n
electron at the nucleus to the probability density at ao (b) inversely proportional to n
1 (c) inversely proportional to n2
(a) e (b) e2 (c) 2 (d) 0
e (d) inversely proportional to n3
6. Photoelectric effect is the phenomenon in which 13. The minimum energy required to excite a hydrogen
(a) photons come out of a metal when it is hit by a atom from its ground state is.
beam of electrons. (a) 3.4 eV (b) 13.6 eV
(b) photons come out of the nucleus of an atom under (c) −13.6 eV (d) 10.2 eV
the action of an electric field.
14. The binding energy of the electron in the lowest orbit
(c) electrons come out of a metal with a constant
of the hydrogen atomis 13.6 eV. The energies required
velocity which depends on the frequency and
in eV to remove an electron from three lowest orbits of
intensity of incident light wave.
the hydrogen atom are
(d) electrons come out of a metal with different
(a) 13.6, 6.8, 8.4 eV
velocities not greater than a certain value which
(b) 13.6,10.2,3,4 eV
depends only on the frequency of the incident
(c) 13.6,27.2, 40.8 eV
light wave not on its intensity.
(d) 13.6,3.4,1.5 eV
7. In photoelectric effect, the photo-current
(a) increases with increase of frequency of incident 15. The frequency of first line of Balmer series in hydro-
photon. gen atom is n0. The frequency of corresponding line
(b) decreases with increases of frequency of incident emitted by singly ionized helium atom is.
photon. (a) 2ν0 (b) 4ν0
(c) does not depend on the frequency of photon but ν0 ν
(c) (d) 0
depends only on the intensity of incident light. 2 4
(d) depends both on the frequency of the incident 16. The orbital angular momentum of an electron in
photon. 2s-orbital is.
8. Increase in the frequency of the incident radiations h
(a) (b) zero
increases the 4π
(a) rate of emission of photo electrons
h
(b) work function (c) h (d) 2
(c) kinetic energy of photo electrons 2π 2π
(d) threshold frequency 17. Which one represents an impossible arrangement.
9. A photo sensitive metal is not emitting photo elec-
n l m s
trons when irradiated. It will do so when thresh-
(a) 3 2 −2 ½
old is crossed. To cross the threshold we need to
(b) 4 0 0 ½
increase.
(a) intensity (b) frequency (c) 3 2 −3 ½
(c) wavelength (d) none (d) 5 3 0 ½
10. If E1, E2 and E3 represent respectively the kinetic ener- 18. Two electrons in the same orbital may be identified with
gies of an electron, an alpha particle and a proton each (a) n (b) l
having same de Broglie wavelength then. (c) m (d) s
(a) E1 > E3 > E2 (b) E2 > E3 > E1 19. Photoelectric emission is observed from a surface for
(c) E1 > E2 > E3 (d) E1=E2=E3 frequencies ν1 and ν2 of the incident radiation (ν1 > ν2).
11. A surface ejects electrons when hitted by green light If the maximum kinetic energies of the photoelectrons
but not when hitted by yellow light. Will electrons be in the two cases are in the ratio 1:k then the threshold
ejected if the surface is hitted by red light. frequency v0 is given by.
(a) yes ν −ν k ν − ν2
(b) no (a) 2 1 (b) 1
k −1 k −1
(c) yes, if the red beam is quite intense
(d) yes, if the red beam continues to fall upon the k ν 2 − ν1 ν 2 − ν1
(c) (d)
surface for a long time. k −1 k
Chapter_01.indd 48 8/17/2013 3:42:58 PM

20. The ratio of the different in energy of electron 29. If ‘RH’ is the Rydberg constant, then the energy of an
between the first and second Bohr’s orbits to that electron in the ground state of hydrogen atom is
between second and third Bohr’s orbit is. R C 1
(a) H (b)
1 27 h RH ch
(a) (b)
3 5 hc
(c) (d) − RH hc
9 4 RH
(c) (d)
4 9 30. When atoms are bombared with α-particles, only a
21. The wavelength of a moving body of mass 0.1 mg few in a million of the α-particles suffer deflections
is 3.31 × 10−29 m. The kinetic energy of the body in while others pass through undeflected. This is because
J would be (a) the force of attraction on the α-particles by the
(a) 2.0 × 10−6 (b) 1.0 × 10−3 oppositely charged electrons is not sufficient
(c) 4.0 × 10
−3
(d) 2.0 × 10−4 (b) the nucleus occupies much smaller volume com-
22. If the speed of electron in the Bohr’s first orbit of pared to the volume of the atom
hydrogen atom is x, the speed of the electron in the (c) the force of repulsion on the fast moving
third orbit is α-particles small
x x (d) the effect in the nucleus do not have any effect on
(a) (b)
9 3 the α-particles
31. The nucleus and an atom can be assumed to be spheri-
(c) 3x (d) 9x
cal. The radius of the nucleus of mass number A is
23. If each hydrogen atom is excited by giving 8.4 eV of given by 1.25 × 10 −13 × A1/3cm. The atomic radius of
energy, then the number of spectral lines emitted is atom is one A0. If the mass number is 64, the fraction
equal to. of the atomic volume that is occupied by the nucleus is.
−5
(a) none (b) two (a) 1.0 × 10−3 (b) 5.0 × 10 −5
−2
(c) three (d) four (c) 2.5 × 10 (d) 1.25 × 10 −13
24. When 4f- level of an atom is completely filled with 32. The nucleus of an atom is located at x = y = z = 0. If
electrons, the next electron will enter the probability of finding an s-orbital electron in a tiny
(a) 5 s (b) 6 s volume around x = a, y = z = 0 is 1 × 10 −5. What is the
(c) 5d (d) 5p probability of finding the electron in the same sized
25. The electron identified by quantum numbers n and 1, volume around x = z = 0, y = a?
(i) n = 4, l = 1 (ii) n = 4, l = 0 (a) 1 × 10 −5 (b) 1 × 10 −5 x a
(iii) n = 3, l = 2 (iv) n = 3, l = 1 −5
(c) 1 × 10 x a 2
(d) 1 × 10 −5 x a−1
can be placed in order of increasing energy from the 33. What is the probability at the second site if the electron
lowest to highest were in a pz orbital for data in (Q. No. 32) above?
(a) iv < ii < iii < i (b) ii < iv < i < iii (a) 1 × 10 −5 (b) 2 × 10 −5
−5
(c) i < iii < ii < iv (d) iii < i < iv < ii (c) 4 × 10 (d) 0
 1 1
26. The energy of an electron in the Bohr’s orbit of H 34. If there are three possible values  − , 0, +  for the
atom is −13.6 eV. The possible energy value (s) of the  2 2
excited state (s) for electrons in Bohr’s orbits of hydro- spin quantum number ms, then the electronic config of
gen is (are) K(19) will be
(a) −3.4 eV (b) −4.2 eV (a) 1s 2 2s3 2p9 3s3 3p1
(c) −6.8 eV (d) +6.8 eV (b) 1s 2 2s 2 2p6 3s 2 4s1
27. The number of d-electrons in Fe+2 (at no of Fe = 26) (c) 1s 2 2s 2 2p9 3s 2 4p4
is not equal to that of the (d) None is correct
(a) p-electrons in Ne (at. no = 10) 35. If the Aufbau rule is not followed in filling of subor-
(b) s-electrons in Mg (at. no = 12) bitals then block of the element will change in
(c) d-electrons in Fe (a) K (19) (b) Sc (21)
(d) p-electrons in Cl− (at. no = 17) (c) V(23) (d) Ni (28)
28. Which have the same number of s-electrons as the 36. If Hund’s rule is not followed, magnetic moment of Fe2+,
d-electrons in Fe2+ Mn+ and Cr all having 24 electrons will be in order
(a) Li (b) Na (a) Fe2+ < Mn + < Cr (b) Fe2+ = Cr < Mn +
(c) N (d) P (c) Fe2+ = Mn + < Cr (d) Mn + = Cr < Fe2+
Chapter_01.indd 49 8/17/2013 3:43:00 PM

37. Following ions will be be coloured if Aufbau rule is (a) 0,2 (b) 2,0
not followed. (c) 1,2 (d) 2,2
(a) Cu2+ (b) Fe2+ 49. Each orbital has a nodal plane. Which of the following
3+
(c) Sc (d) 1,2 true statements about nodal planes are not true?
38. The wavelength is equal to the distance travelled by the (a) a plane on which there is zero probability that the
electron in one second, then electron will be found
(a) λ = h / ν (b) λ = h / m (b) a plane on which there is maximum probability
(c) λ = h / p (d) λ = h / m that the electron will be found
39. Magnitude of the charge on the helium ion is. (c) both
(a) 4.8 × 10−10 esu (b) 2.4 × 1010 esu (d) none
(c) 9.6 × 10−10 esu (d) 1.6 × 10−10 esu 50. The radial distribution curve of 2s sublevel consists of
40. A photon was absorbed by a hydrogen atom in its x nodes, x is
ground state and the electron was promoted to the fifth (a) 1 (b) 3
orbit, then the excited atom returned to its ground state, (c) 2 (d) 0
visible and other quanta were emitted, other quanta are 51. Magnetic moments of V (z = 23), Cr (z = 24), Mn
(a) 2  →1 (b) 5  →2 (z = 25) are x, y, z Hence
(c) 3  →1 (d) 4  →1 (a) x = y = z (b) x < y < z
41. Consider the following ions (c) x < z < y (d) z < y < x
(i) Ni 2+ (ii) Co 2+ 52. Uncertainty in position and momentum are equal.
2+
(iii) Cr (iv) Fe3+ Uncertainty in velocity is.
(atomic numbers: Cr = 24, Fe = 26, Co = 27, Ni = 28) (a) h/π (b) h / 2π
The correct sequence of the increasing order of the
number of unpaired electrons in these ions is 1 h
(c) (d) none
(a) a, b, c, d (b) d, b, c, a 2m π
(c) a, c, b, d (d) c, d, b, a 53. If Aufbau principle is not used, 19 th electron in Sc
42. The ratio of the energy of the electron in ground state of (z = 21) will have
hydrogen to the electron in first excited state of Be3+ is (a) n = 3, l = 0 (b) n = 3, l = 1
(a) 1:4 (b) 1:8 (c) 1:16 (d) 16:1 (c) n = 3, l = 2 (d) n = 4, l = 0
43. Bohr model can explain spectrum of 54. Number of electrons that F(z=9) has in p-orbitals, is
(a) the hydrogen atom only equal to
(b) the hydrogen molecule only (a) number of electrons in s-orbitals in Na (11e)
(c) an atom or iron having one electron only (b) number of electrons in d-orbitals in Fe3+ (23e)
(d) the sodium atom only (c) number of electrons in d-orbitals in Mn (25e)
44. Of the following radiation with maximum wavelength is. (d) 1, 2, 3 are true
(a) UV (b) radio wave 55. If each orbital can hold a maximum of 3 electrons,
(c) X-ray (d) IR the number of elements in 4th period of periodic table
45. Zeeman effect explains splitting of lines in (long form) is.
(a) magnetic field (b) electric field (a) 48 (b) 54
(c) both (d) none (c) 27 (d) 36
46. In presence of magnetic field d-suborbit is. 56. If the radius of first Bohr orbit is x, then de Broglie
(a) 5-fold degenerate wavelength of electron in 3rd orbit is nearly
(b) 3-fold degenerate (a) 2π x (b) 6π x
(c) 7-fold degenerate x
(c) 9x (d)
(d) 2-fold degenerate 3
47. Size of the nucleus is 57. The series of lines present in the visible region of the
(a) 10−13 cm (b) 10−10 cm hydrogen spectrum is
−1
(c) 10 mm (d) all correct (a) Balmer (b) Lyman
48. The orbit and orbital angular momentum of an electron (c) Paschen (d) Brackett
3h 3 h 58. Which orbital gives an electron a greater probability of
are and . respectively. The number of radial
2π 2 π being found close to the nucleus
and angular nodes for the orbital in which the electron (a) 3p (b) 3d
is present are respectively (c) 3s (d) equal
Chapter_01.indd 50 8/17/2013 3:43:01 PM

59. Hund’s rule deals with the distribution of electrons in 69. The value of charge on the oil droplets experimentally
(a) quantum shell (b) an orbit observed were −1.6 × 10−19 and −4 × 10−19 coulomb.
(c) an orbital (d) degenerate orbitals The value of the electronic charge, indicated by these
60. s-orbital is spherically symmetrical hence results is.
(a) it is directional independent (a) 1.6 × 10−19 (b) −2.4 × 10−19
(b) angular dependent (c) −0.4 × 10
−19
(d) −0.8 × 10−19
(c) both correct 70. The ratio of energy of a photon of 2000 A0 wave length
(d) both incorrect radiation to that of 4000 A0 radiation is
61. In centro-symmetrical system, the orbital angular momen-
1 1
tum, a measure of the momentum of a particle travelling (a) (b)
around the nucleus, is quantized. Its magnitude is. 4 2
h h (c) 2 (d) 4
(a) l (l + 1) (b) l (l − 1) 71. Atomic weight of Ne is 20.2. Ne is a mixture of
2π 2π 20
Ne and 22Ne. Relative abundance of heavier
h h isotope is.
(c) s( s + 1) (d) s( s − 1) (a) 90 (b) 20
2π 2π
(c) 40 (d) 10
62. If travelling at equal speeds, the longest wavelength of 72. The velocity of electron in the hydrogen atom is
the following matter is that of 2.2 × 106 m / s. The de Broglie wavelength for this
(a) electron (b) proton electron is.
(c) neutron (d) alpha particle. (a) 33 nm (b) 45.6 nm
63. The line spectra are the characteristics of (c) 23.3 nm (d) 0.33 nm
(a) atoms in the excited state 73. What is the energy in joule of a photon of light with
(b) molecules in the excited state wavelength 4.0 × 103 nm
(c) atoms in ground state (a) 7.5 × 10−20 (b) 5.0 × 10−20
(d) molecules in ground state (c) 2.0 × 10
−10
(d) 2.5 × 10−10
64. In the Bohr model of the hydrogen atom, the ratio of 74. The maximum wavelength of light that can excite
the kinetic energy to the total energy of the electron in an electron from first to third orbit of hydrogen
quantum state is. atom is.
(a) 1 (b) 2 (a) 487 nm (b) 170 nm
(c) −1 (d) −2 (c) 103 nm (d) 17 nm
65. The number of waves made by a Bohr electron in an 75. The specific charge of a proton is 9.6 × 107 C kg−1, then
orbit of maximum magnetic quantum number +2 for an α-particles it will be
(a) 3 (b) 4
(a) 2.4 × 107 C kg−1 (b) 4.8 × 107 C kg−1
(c) 2 (d) 1
66. The distance of closest approach of an α-particle fired
(c) 19.2 × 107 C kg−1 (d) 38.4 × 107 C kg−1
towards a nucleus with momentum p is r. What will be
the distance of closest approach when the momentum 76. The work function for a metal is 4 eV. To emit a
of the α-particle is 2p? photo electron of zero velocity from the surface of
(a) 2r (b) 4r the metal, the wavelength of incident light should be
(c) r/2 (d) r/4 (a) 2700 A0 (b) 1700 A0
67. The radius of Bohr’s first orbit in H atom is 0.53 mm. 0
(c) 5900 A (d) 3100 A0
the radius of second orbit in He+ would be 77. Ultraviolet light of 6.2 eV falls on aluminum
(a) 0.0265 mm surface (work function = 4.2 eV). The kinetic
(b) 0.0530 mm energy (in joule) of the fastest electron emitted is
(c) 0.1060 mm approximately
(d) 0.2120 mm (a) 3 × 10−21 (b) 3 × 10−19
68. The ionization potential of hydrogen atom is 13.6 eV. (c) 3 × 10
−17
(d) 3 × 10−15
The energy required to remove an electron from the n 78. The threshold wavelength for photoelectric effect on
= 2 state of hydrogen atom is. sodium is 5000 A0. Its work function is.
(a) 27.2 eV (b) 13.6 eV (a) 4 × 10−19 J (b) 1 J
(c) 6.8 eV (d) 3.4 eV (c) 2 × 10−19 J (d) 3 × 10−10 J
Chapter_01.indd 51 8/17/2013 3:43:02 PM

79. Photons of energy 6 eV are incident on a potassium 86. Suppose 10-17 J of light energy is needed by the inte-
surface of work function 2.1 eV. what is the stopping rior of human eye to see an object. The photons of
potential? green light (λ = 550 nm) needed to see that object are
(a) −6V (b) −2.1 V (a) 27 (b) 28
(c) −3.9 V (d) −8.1 V (c) 29 (d) 30
80. In an atom two electrons move around the nucleus in 87. A photon of 300 nm is absorbed by a gas and then
circular orbits of radii R and 4R. The ratio of the time reemits two photons. One reemitted photon has wave-
taken by them to complete one revolution is. length 496 nm, the wavelength of second reemitted
(a) 1:4 (b) 4:1 photon is.
(c) 1:8 (d) 8:7 (a) 757 (b) 857
81. In the series limit of wavelength of the Lyman series (c) 957 (d) 657
for the hydrogen atom is 912 A0, then the series limit 88. The shortest λ for the Lyman series is ……. (given (RH
of wavelength for the Balmer series of the hydrogen = 109678 cm-1)
atom is. (a) 912 A0 (b) 700 A0
(a) 912 A0 (b) 912 × 2A 0 0
(c) 600 A (d) 811 A0
0
(c) 912 × 4A (d) 912/2A0 89. The longest λ for the Lyman series is…….. (given
82. The difference in angular momentum associated (RH = 109678 cm-1)
with the electron in two successive orbits of hydro- (a) 1215 A0 (b) 1315 A0
gen atom is (c) 1415 A 0
(d) 1515 A0
h h 90. The λ for Hα line of Balmer series is 6500 A0. Thus λ
(a) (b)
π 2π for Hβ line of Balmer series is.
h (a) 4864 A0 (b) 4914 A0
h
(c) (d) ( n − 1) (c) 5014 A 0
(d) 4714 A0
2 2π
91. The momentum of particle of wavelength 0.33 nm
83. Ionization potential of hydrogen atom is 13.6 eV. is…..kg m sec-1
Hydrogen atom in the ground state are excited by mon- (a) 2 × 10−24 (b) 2 × 10−12
ochromatic light of energy 12.1 eV. The spectral lines (c) 2 × 10
−6
(d) 2 × 10−48
emitted by hydrogen according to Bohr’s theory will be 92. An oil drop has charge 6.39 × 10−19 C. The total
(a) one (b) two number of electrons on oil drop are
(c) three (d) four (a) 1 (b) 2
84. Energy levels A, B, C of a certain atom corresponding (c) 3 (d) 4
to increasing values of energy, i.e; EA < EB < EC. If λ1,
λ2 and λ3 are the wavelengths of radiations correspond-
ing to the transitions C to B, B to A and C to A respec- Multiple Choice Questions with Only
tively, which of the following statement is correct One Answer
C Level II
λ1
1. Select the correct statement.
B h
λ2 (a) Orbital angular momentum is for the electron
λ3 π
having n = 5 and lower value of the azimuthal
A quantum number.
(b) If n = 3, l = 0, m = 0 for the last valence shell electron,
λ1λ 2 then the possible atomic number may be 12 or 13.
(a) λ3 = λ1 + λ2 (b) λ3 = (c) Total spin of electrons for the atom (Z = 25) Mn is
λ1 + λ 2
7
(c) λ1 + λ2 + λ3 = 0 (d) λ 32 = λ12 + λ 22 ± .
5
85. The ratio of the radius of the orbit for the electron
orbiting the hydrogen nucleus to that of an electron (d) Magnetic moment due to spin for noble gas is zero.
orbiting a deuterium nucleus is. 2. Identify the correct statement (s)
(a) 1:1 (b) 1:2 I. The radial probability distribution curves for 1s,
(c) 2:1 (d) 1:3 2s, 2p and 3d are identical.
Chapter_01.indd 52 8/17/2013 3:43:04 PM

II. The number of nodal planes for 2p, 3d and 4p (d) The radius of first Bohr orbit of hydrogen atom is
orbitals is the same. 2.116 × 10−8 cm.
III. Theoretically calculated spin only magnetic 8. Which one of the following statement is correct?
moment is same for Ti2+ and Ni2+. (a) 2s orbital is spherical with two nodal planes.
IV. A ‘p’ orbital can accommodate a maximum of (b) The de Broglie wavelength (l) of a particle of
six electrons. mv
mass m and velocity v is equal to .
(a) I and II are correct. h
(b) II and III are correct.
(c) The principal quantum number n indicates the
(c) III and IV are correct.
shape of an orbital.
(d) Only IV is correct.
(d) The electronic configuration of phosphorus is
3. The magnetic moment of two ions Mx+ and My+ of
given by Ne 3s 2 3 p1x p1y p1z .
the element M(Z = 26) is found to be 5.916 BM.
9. What is true regarding the length of photographic
If x > y, then which of the following statement is
film occupied by various series in hydrogen emission
correct?
spectrum?
(a) M y+ is more stable than M x+.
(L1: Length of Lyman series; L2: Length of Balmer
(b) M y+ is less stable than M x+.
series; L3 Length of Paschen series)
(c) Both are equal stable.
(a) L1 = L2 = L3 (b) L1 < L2 < L3
(d) Cannot be predicted exactly.
(c) L1 < L2 > L3 (d) L1 > L2 > L3
4. If l0 is threshold wavelength for photo electronic
10. Photons having energy equivalent to binding energy
emission, l is the wavelength of light falling on the
of 4th state of He+ ion are used the metal surface of
surface of metal, and m, mass of electron, then de
work function 1.4 eV. If electrons are further acceler-
Broglie wavelength of the emitted electron is
1 1
ated through the potential difference of 4V, then the
 h(λλ 0 )  2  h(λ 0 − λ)  2 minimum value of de Broglie’s wavelength associated
(a)   (b)   with the electron is
 2 mc ( λ 0 − λ )   2mcλλ 0 
1 (a) 1.1 Å (b) 9.15 Å
1
 h(λ − λ 0 )  2  hλλ 0 )  2 (c) 5 Å (d) 11 Å
(c)   (d)   11. If the angular momentum of an electron changes from
 2mcλλ 0   2mc 
2h h
5. From the following observation of Mr. Gupta, Mr. Agar- to during a transition in a hydrogen atom, it
π π
wal and Mr. Maheshwari, predict the type of orbital. results in the formation of spectral lines in
Mr. Gupta: The angular function of the orbital inter- (a) UV region (b) visible region
sect the three axes at the origin only. (c) IR region (d) Far IR region
Mr. Agarwal: XY plane acts as a nodal plane. 12. Proton, alpha particles are accelerated with same
Mr. Maheshwari: The graph of radial probability vs potential. The de Broglie wavelength ratio is
‘r’ intersects the radial axis at three separate regions,
points including origin. (a) 2 2 :1 (b) 1: 2 2
(a) 5dyz (c) 4: 1 (d) 1: 4
(b) 4pz
13. A stationary He+ ion emitted a photon correspond-
(c) 6dyz (d) 6dxy
ing to the first line of the Lyman series. The photon
6. The probability of finding the electron is maximum for
d x2 − y2 orbital liberates a photo electron from a stationary hydrogen
atom in ground state. The kinetic energy of the elec-
(a) along x-axis only tron is
(b) along y-axis only (a) 10.2 eV (b) 13.6 eV
(c) along x, y-axis only (c) 20.4 eV (d) 27.2 eV
(d) between x, y axes 14. The uncertainty in position is of the order of 1 Å. The
7. Which one of the following statement is not correct? uncertainty in velocity of a cricket ball
(a) Rydberg’s constant and wave number have same (a) 1.7 K × 10−23 m/s (b) 1.7 × 10−24 m/s
units. (c) 3.4 × 10−23 m/s (d) 3.4 × 10−24 m/s
(b) Lyman series of hydrogen spectrum occurs in the
15. A standing wave in a string 35 cm long has a total of
UV region.
six nodes including ends. Hence, the wavelength is
(c) The angular momentum of the electron into the
h (a) 14 cm (b) 5.82 cm
ground state hydrogen atom is equal to . (c) 7 cm (d) 17.5 cm
2π
Chapter_01.indd 53 8/17/2013 3:43:05 PM

16. The m value for an electron in an atom is equal to the (a) 1 (b) 3
number of m values for l = 1. The electron may be present in (c) 6 (d) 10
(a) 3d x2 − y2 (b) 5fxyz 23. The ratio between the wave numbers of spectral lines
(c) 2px (d) 3 S of Balmer series of hydrogen having the least and the
17. An electron travels with velocity of v ms−1. For a pro- highest wavelength values is
ton to have same de Broglie wavelength, the velocity (a) 5: 27 (b) 27: 5
will be approximately (c) 5: 9 (d) 9: 5
(a) v ms−1 (b) 1840 v ms−1 24. The number of nodal planes, radial nodes and peaks
−1
(c) v/1840 ms (d) 1840 v ms−1 in the radial probability curve of 5d orbital are
18. The dye Acriflavine, when dissolved in water, has its respectively
maximum light absorption at 4530 Å and the maxi- (a) 5, 2, 3 (b) 4, 3, 2
mum fluorescence emission at 5080 Å. The number of (c) 2, 3, 2 (d) 2, 2, 3
fluorescence quanta is, on the average 53 per cent of 25. The number of revolutions made by electron in Bohr’s
the number of quanta absorbed. Using the wavelengths 2nd orbit of hydrogen atom in one second is
of maximum absorption and emission, what percent- (a) 6.55 × 1015 (b) 8.2 × 1014
age of absorbed energy is emitted as fluorescence? (c) 1.64 × 10
15
(d) 2.62 × 1016
(a) 100% (b) 47% 26. When an excited state of H-atom emits a photon of
(c) 36% (d) 12% wavelength l and returns to the ground state, the prin-
19. A gaseous particle ‘X’ has a proton (atomic) number cipal quantum number of the excited state is given by
‘n’ and a charge of +1. An another gaseous particle ‘Y’ (λR − 1)
has a proton (atomic number) of (n + 1) and is isoelec- (a) (b) λR(λR − 1)
λR
tronic with X.
Which of the following statements correctly describes λR
X and Y? (c) (d) λR(λR + 1)
(λR − 1)
(a) X has larger radius than Y.
(b) X requires more energy than Y when a further 27. What is the maximum number of electrons in an atom
electron is removed from each particle. that can have the quantum numbers n = 4, ml = +1?
(c) X releases more energy than Y when an electron is (a) 4 (b) 15
added to each particle. (c) 3 (d) 6
(d) X and Y both have the same electro negativity. 28. The wave function (y) of 2s is given by
20. When an electron is transited from 2E to E energy level,  1
1/ 2

1 r  − r / 2 a0
the wavelength of photon produced is l1. If electronic (ψ)2 s =   2 − e . At r = r0,
transition involves 4/3 E to E level, the wavelength of 2 2λ  a0   a0 
resultant photon is l2. Which of the following is a cor- radial node is formed. Thus, for 2s, r0 in terms of
rect relation? a0 is
(a) r0 = a0 (b) r0 = 2a0
(a) λ 2 = λ1 (b) λ 2 = 3λ1
(c) r0 = a0/2 (d) r0 = 4a0
3 4 29. Which of the following statements in relation to the
(c) λ 2 = λ1 (d) λ 2 = λ1
4 2 hydrogen atom is correct?
21. If a certain metal was irradiated by using two differ- (a) 3s, 3p and 3d orbitals all have the same energy.
ent light radiations of frequency ‘x’ and ‘2x’ the kinetic (b) 3s and 3p orbitals are of lower energy than 3d
energies of the ejected electrons are ‘y’ and ‘3y’ respec- orbital.
tively. The threshold frequency of the metal will be (c) 3p orbital is lower in energy than 3d orbital.
x (d) 3s orbital is lower in energy than 3p orbital.
x
(a) (b) 30. Choose the wrong statement.
3 2 (a) The shape of an atomic orbital depends upon the
3x 2x azimuthal quantum number.
(c) (d)
2 3 (b) The orientation of an atomic orbital depends upon
22. During the excitation of an electron, it travels at a dis- the magnetic quantum number.
tance of nearly 0.7935 nm in the hydrogen atom. The (c) The energy of an electron in an atomic orbital of
maximum number of spectral lines formed during the multi-electron atom depends upon the principal
deexcitation is number only.
Chapter_01.indd 54 8/17/2013 3:43:06 PM

(d) The number of degenerate atomic orbital of one (a) 2.07 Å (b) 1.59 Å
type depends upon the value of azimuthal and (c) 0.53 Å (d) 2.12 Å
magnetic quantum number only. 35. An electron is continuously accelerated in a vacuum
31. The ground state electronic configurations of the ele- tube by applying a potential difference. If the de Bro-
ments, U, V, W, X and Y (the symbols do not have any glie’s wavelength is decrease by 10 per cent the change
chemical significance) are as follows: in the kinetic energy of the electron is nearly
U 1s2 2s2 2p3 (a) decreased by 11%
V 1s2 2s2 2p6 3s1 (b) increased by 23.4%
W 1s2 2s2 2p6 3s2 3p2 (c) increased by 10%
X 1s2 2s2 2p6 3s2 3p6 3d5 4s2 (d) increased by 11.1%
Y 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 36. The angular momentum of electron in Li2+ was found
Determine which sequence of elements that satisfy the to be (7h/11). The distance of the electron from
following statements? nucleus is
I. Element forms a carbonate which is not decom- (a) 1.69 Å (b) 0.68 Å
posed by heating. (c) 2.82 Å (d) 8.19 Å
II. Element is most likely to form coloured ionic 37. The frequency ‘v’ of certain line of the Lyman series of
compounds. the atomic spectrum of hydrogen satisfies the follow-
III. Element has largest atomic radius. ing conditions
IV. Element forms only acidic oxide. I. It is the sum of the frequencies of another Lyman
(a) VWYU (b) VXYW and a Balmer line
(c) VWYX (d) VXWU II. It is the sum of the frequencies of a certain line,
32. If the quantum numbers are defined as follows, n = 1, a Balmer line and a Paschen line
2, 3...., l = 0, 1, 2,...(n − 1), m = −l in integral steps to III. It is the sum of the frequencies of a Lyman and a
+l, how many electrons could be fitted in Ist shell? Paschen line but no Brackett line
(a) 2 (b) 8 To which transition does v correspond?
(c) 10 (d) 18 (a) n2 = 3 to n1 = 1 (b) n2 = 3 to n1 = 2
33. If electrons were to fill up progressively with orbit satu- (c) n2 = 2 to n1 = 1 (d) n2 = 4 to n1 = 1
ration (neglecting Aufbau rule) and each orbital were to 38. A hydrogen atom sample in the ground state is excited
accommodate the three electrons, instead of two; which by monochromatic light radiation of wavelength l Å.
of the following would NOT hold correct for the new The resulting spectrum consists of maximum 15 dif-
electronic arrangement in zirconium atom (Z = 40)? ferent lines. What is l?
(a) The number of p-electrons would be double the (RH = 109677 cm−1)
number of s-electrons. (a) 937.3 Å (b) 1025 Å
(b) Spin quantum number would become super flows. (c) 1236 Å (d) None of these
(c) Zirconium would continue to belong to the 4th
39. The ratio between time periods taken by electron in
period (in new Periodic Table)
Bohr’s 2nd and 3rd orbits for each revolution is
(d) Zirconium would show retention of block.
(a) 9: 4 (b) 4: 9
34. If the above radial probability curve indicates 2s
(c) 8: 27 (d) 27: 8
orbital, the distance between the peak points x, y is
40. The velocity of an electron in nth orbit of hydrogen
atom bears the ratio 1: 411 to the velocity of light. The
Radial probability (D)
number of coloured lines formed when electron jumps

from (n + 3) state to ground state, is
(a) 4 (b) 3
(c) 5 (d) 6
41. The de Broglie wavelength (l) of electron is related to
its accelerating potential (V) by the equation
12.27
(a) λ =
( A) V
x y
Distance from the nucleus 12.27
(b) λ ( nm ) =
V
Chapter_01.indd 55 8/17/2013 3:43:07 PM

150 (a) 2π / n (b) 2πr ⋅ n

(c) λ =

( A) V (c) 2πr / n2 (d) 2πrn2
150 49. When two electrons are present in two degenerate
(d) λ ( nm ) = orbitals of an atom, the energy is lower if their spin is
V
parallel. The statement is based upon
42. Hydrogen-like ion has the wavelength difference (a) Pauli’s exclusion principle
between the first lines of Balmer and Lyman series (b) Aufbau principle
equal to 33.4 nm. The atomic number of that ion is (c) Hund’s rule
equal to (d) Bohr’s rule
(a) 4 (b) 3
50. If the nitrogen atom had electronic configuration 1s7,
(c) 2 (d) 5
it would have energy lower than that of the normal
43. When a certain metal was irradiated with light of fre-
ground state configuration 1s22s22p3, because the
quency 3.2 × 1016 Hz, the photo electrons emitted has
electrons would be closer to the nucleus. yet 1s7 is not
twice the kinetic energy as did photoelectrons emitted
observed because it violates.
when the same metal was irradiated with light of fre-
(a) Heisenberg uncertainly principle
quency 2.5 × 1016 Hz. The threshold frequency of the
(b) Hund’s rule
metal is ........1015 Hz.
(c) Pauli exclusion principle
(a) 18 (b) 20
(d) Bohr’s postulate of stationary orbits
(c) 22 (d) 16
44. What is the wavelength of the photon emitted by a 51. If RH be the Rydberg constant, then the energy of an
hydrogen atom when an electron makes transition electron in the ground state of hydrogen atom is
from n = 2 to n = 1? Given that ionization potential is RH C hC
13.786 V. (Answer expressed in Angstrom units) (a) (b)
h RH
(a) 1200 (b) 900 1
(c) 800 (d) 1000 (c) (d) − RH hC
RH Ch
45. The ratio of the energy of the electron in ground state
of hydrogen to the electron in first excited state of 52. When electronic transition occurs from higher energy
Be3+ is state to a lower energy state with energy difference
(a) 1: 4 (b) 1: 8 equal to DE eV, the wavelength of the line emitted is
(c) 1: 16 (d) 16: 1 approximately equal to
46. The configuration of Cr atom is 3d5 4s1 but not 3d4 4s2 12400 × 10 −10 13397 × 10 −10
due to reason R1 and the configuration of Cu atom 3d10 (a) m (b) m
∆E ∆E
4s1 but not 3d9 4s2 due to Reason R2. R1 and R2 are
(a) R1: The exchange energy of 3d5 4s1 is greater than 14322 × 10 −10 12387 × 10 −10
that of 3d4 4s2. (c) m (d) m
∆E ∆E
R2: The exchange energy of 3d10 4s1 is greater than
that of 3d9 4s2. 53. In Mosley’s equation given constants a = b = 1 then the
(b) R1: 3d5 4s1 and 3d4 4s2 have same exchange energy frequency is 100s−1. The element will be
but 3d5 4s1 is spherically symmetrical. (a) K (b) Na
R2: 3d10 4s1 is also spherically symmetrical. (c) Rb (d) Cs
(c) R1: 3d5 4s1 has a greater exchange energy than 54. Which of the pair of orbitals have electronic density
3d4 4s2. along the axis?
R2: 3d10 4s1 has a spherical symmetry. (a) dxydyz (b) d x2 − y2 d z 2
(d) R1: 3d5 4s1 has greater energy than 3d4 4s2. (c) dxydxz (d) d xy d z 2
R1: 3d10 4s1 has a greater energy than 3d9 4s2.
47. Maximum value (n + 1 + m) for unpaired electrons in 55. If azimuthal quantum number could have value of
second excited state of chlorine 17Cl is n also in addition to normal value, then E. C. of Cr
(a) 28 (b) 25 (z = 24) would have been
(c) 20 (d) None of these (a) 1s2 2s2 2p6 3s2 3p6 4s2 3d4
48. If r be the radius of first Bohr’s orbit for hydrogen (b) 1s2 2s2 2p6 3s2 3p6 4s1 3d5
atom, the de Broglie wavelength in the nth orbit of (c) 1s2 1p6 2s2 2p6 3s2 2d6
hydrogen atom is given by (d) 1s2 1p6 2s2 2p6 2d6
Chapter_01.indd 56 8/17/2013 3:43:08 PM

56. In radial probability distribution curve of 2s orbital, when electron falls from this level is
the distance between the two peaks is (a) 4 (b) 3
(a) 0.53 (b) 2.1 (c) 2 (d) 6
(c) 1.1 (d) 1.57 65. What transition in the hydrogen spectrum would have
57. If n and l are respectively principal and azimuthal the same wavelength as the transition n = 4, n = 2 in
quantum numbers, then the expression for calculating He+ ion?
the total number of electrons in any energy level is (a) 4 → 2 (b) 3 → 1
l = n −1 l =n
(c) 3 → 2 (d) 2 → 1
(a) ∑
l =0
2(2l + 1) (b) ∑ 2(2l + 1)
l =1
66. If the radius of first Bohr orbit is X1, then the de
l = n −1 l =n Broglie wavelength of electron in 3rd orbit is nearly
(c) ∑ 2(2l + 1) (d) ∑ 2(2l + 1) (a) 2 π x (b) 6 π x
l =1 l =0 (c) 9 x (d) x/3
58. Consider the following statements concerning the sub 67. The angular speed of the electron in nth orbit of Bohr
shells: hydrogen atom is
I. The maximum value of m for g sub shell is 4 (a) directly proportional to n
II. The maximum value number of unpaired elec- (b) inversely proportional to n
trons in g sub shell is 9 (c) inversely proportional to n2
III. The lowest value for the shell having g sub (d) inversely proportional to n3
shell is 5 68. In hydrogen atom, the electronic motion is represented
Select correct statements as follows. The number of revolutions made by that
(a) II, I only (b) II, III only electron in one second is equal to
(c) I, III only (d) I, II, III
59. If a 1 g body is travelling along the X-axis at 100 cm
s−1 within 1 cm s−1 than 4 uncertainty in its position is
(a) 2.64 × 10−30 m (b) 5.28 × 10−30 m
(c) 1.32 × 10−30 m (d) 0.66 × 10−30 m
60. The photoelectric emission requires a threshold fre- (a) 6.5 × 1015 (b) 2 × 1014
quency V0 for a certain metal l1 = 2000 Å and l2 = (c) 2 × 10
13
(d) 1.01 × 1014
1660 Å produce electrons with kinetic energy KE1 and 69. The length of the minor axis corresponding to the
KE2 of KE2 = 2KE1. The threshold frequency V0 is elliptical path for which n = 4 and k = 2.
(a) 1.15 × 1015 s−1 (b) 1.15 × 1014 s−1 (a) 8.464 Å (b) 16.92 Å
(c) 1.19 × 1015 s−1 (d) 1.19 × 1014 s−1 (c) 2.116 Å (d) 4.23 Å
61. Calculate the wavelength emitted during the transition
70. In which quantum level does the electron jumps in He+
of electrons in between two levels of Li2+ ion whose
ion to ground state if it is given an energy correspond-
sum is 4 and the difference is 2.
ing to 99 per cent of the ionisation potential of He+ ion.
(a) 1.14 × 10−6 cm (b) 1.14 × 10−5 cm
(a) 4 (b) 6
(c) 2.12 × 10−6 cm (d) 2.14 × 10−5 cm
(c) 8 (d) 10
62. A certain dye absorbs light of l = 4700 Å and then
fluorescence a light X Å. Assuming that 47 per cent of 71. Which among the following is correct of 5B in normal state?
absorbed light is reemitted as fluorescence, the ratio of
quanta out to the number of quanta absorbed is 0.5. The (a) ↑↑ ↑ ↑ : Against Hund’s rule
value of X is
(a) 4000 Å (b) 5000 Å (b) ↑ ↑ ↑ : Against Aufbau principle as
(c) 5500 Å (d) 6000 Å well as Hund’s rule
63. The bond dissociation energy of H—H bond is 400 (c) ↑↑ ↑ : Violation of Pauli’s exclusion
KJ/mol. The energy required to excite 0.04 moles of principle and not Hund’s rule
H2 gas to the first excited state is (d) ↑↓ : Against Aufbau principle
(a) 94.6 KJ (b) 47.3 KJ
(c) 70.9 KJ (d) 80.4 KJ 72. How many times does light travel faster in vacuum
64. The angular momentum of an electron in a Bohr’s than an electron in Bohr’s first orbit of hydrogen atom?
orbit of hydrogen atom is 4.217 × 10−34 kg-m2/s. The (a) 13.7 times (b) 67 times
number of specified lines formed in visible region (c) 137 times (d) 97 times
Chapter_01.indd 57 8/17/2013 3:43:09 PM

73. When a hydrogen atom emits a photon of energy 12.1 (a) 4 λ (b) 8 λ
eV. The orbit angular momentum changes by (c) 16 λ (d) 2 λ
(a) 1.05 × 10−34 J-s (b) 2.11 × 10−34 J-s 82. What hydrogen like ion has the wavelength difference
(c) 3.16 × 10−34 J-s (d) 4.22 × 10−34 J-s between the first line of Balmer and Lyman series
74. If kinetic energy of a particle is doubled; de Broglie equal to 133 nm:
wavelength becomes (a) He+ (b) Li2+
(a) 2 times (b) 4 times 3+
(c) Be (d) B4+
(c) 2 times (d) 1/ 2 times 83. The shortest wavelength of hydrogen atom in Lyman
75. Imagine an atom made up of a proton and a hypo- series is X. The longest wavelength in Balmer series of
thetical particle of double the mass of the electron He+ is?
but having the same charge as the electron. Apply the 9x 36 x
(a) (b)
Bohr atomic model and consider possible transitions 5 5
of this hypothetical particle to the first excited level. x 5x
The largest wavelength of the photon that will be (c) (d)
emitted has wavelength λ equal to (R is the Rydberg 4 9
84. Pick out the correct option. Where T stands for True
constant.)
9 36 and F stands for False.
(a) (b) I. The energy of the 3d orbital is high compared to
5R 5R
the 4s orbital in hydrogen atom.
18 27 II. The electron density in xy plane in d x2 − y2 orbital is zero.
(c) (d)
5R 5R III. 24th electron in Cr goes to 3d orbital.
76. When a certain metal was irradiated with light having IV. The three quantum numbers were clearly explained
a frequency of 3.0 × 1016 s−1, the photo electrons emit- in terms of Schrodinger wave equation.
ted had twice the kinetic energy as did photoelectrons (a) TTFF (b) TFTT
emitted when the same metal was irradiated with light (c) TFTF (d) FFTT
having a frequency of 2.0 × 1016 s−1. The threshold fre- 85. Who modified Bohr’s theory by introducing elliptical
quency of the metal (in 1016 s−1) is orbits for electron path?
(a) 1 (b) 2 (a) Hund
(c) 3 (d) 4 (b) Thomson
77. Given that ionisation potential of hydrogen atom is (c) Rutherford
2.0 × 10−18 J, Planck’s constant is 6.0 × 10−34 J-s. The (d) Sommerfeld
frequency Hb line in Balmer series is in the values of 86. The velocity of electron in a certain Bohr orbit of
(1012 Hz) is hydrogen atom bears the ratio 1: 275 to the velocity of
(a) 625 (b) 840 light. So the number of orbits is
(c) 925 (d) 520 (a) 1 (b) 2
78. The radius of the orbit in hydrogen atom is 0.8464 nm. (c) 3 (d) 4
The velocity of electron in this orbit (in the order of 87. If there were three possibilities of electron spin, K (19)
103 m/s), is would be placed in
(a) 547 (b) 637 (a) s-block (b) p-block
(c) 342 (d) 832 (c) d-block (d) f-block
79. The calculated magnetic moment of Cr2+ is 88. Consider the following plots for 2s-orbitals
(a) 1.73 BM
(b) 2.8 BM x x z
(c) 4.8 BM
(d) 5.9 BM
80. The number of d electrons in Fe2+ is not equal to that of
(a) p-electrons in Ne r r r
(b) s-elelctrons in Mg (I) (II) (III)
(c) p-electrons in Cl−
(d) p-electrons in Mg x, y and z are respectively,
81. de Broglie wavelength of the Bohr’s first orbit is l. The (a) y, y2 and 4pr2 y2
circumference of the Bohr fourth orbit is (b) y2, y and 4pr2 y2
Chapter_01.indd 58 8/17/2013 3:43:11 PM

(c) 4pr2 y2 and y2 and y (a) 1 (b) 2

(d) y2, 4pr2 y2 and y (c) 3 (d) 4
89. For a hypothetical H-like atom which follows Bohr’s 94. Which orbital is represented by complete wave
model, some spectral lines were observed as shown. If function y420?
it is known that line ‘E’ belongs to the visible region, (a) 4 d z 2 (b) 3d x2 − y2
then the lines possibly belonging to ultraviolet region (c) 4px (d) 4dyz
will be (n1 is not necessarily ground state) [Assume for 95. The wave function of the atomic orbital of an H-like
this atom, no spectral series shows overlaps with other species is given as
series in the emission spectrum] 1
ψ2s = Z 1/2 (2 − Zr )e − Zr /2
n5 4 2π
The radius for nodal surface for He+ ion in Å is
n4
(a) 1.5 Å (b) 1 Å
B
C (c) 2 Å (d) 4 Å
n3
96. For the photoelectric effect, the maximum kinetic
D A n2 energy EK of the emitted photo electrons is plotted
against the frequency v of the incident photons as
E shown in figure. The slope of the curve gives
n1
(a) B and D (b) D only
(c) C only (d) A only
90. In any sub shell, the maximum number of electrons Ex
having same value of spin quantum number is
(a) l (l + 1)
(b) l +2
(c) 2l +1
(d) 4l +2 V
91. Given the wave function of an orbital of hydrogen (a) charge of the electron
 1  (b) work function of the metal
atom; ψ1.0 =   e − r / a0 , the most probable
3/2  (c) Planck’s constant
 πa0  (d) ratio of the Planck’s constant to electronic charge
distance of the electron present in the given orbital 97. de Broglie wavelength of two particles A and B are
from the nucleus is
 1 
(a) a0 × e−2r (b) a0 plotted against   ; where V is the potential on the
(c) (3/2)a0 (d) 2a0  V 
92. Given the correct order of initials T (True) or F (False) particles. Which of the following relation is correct
for following statements: about the mass or the particles?
(i) Maximum kinetic energy a photoelectron emit-
ted from a metal [work function = 2 eV] by a
photon of wavelength 310 nm is 3.2 × 10−19 J. B
(ii) The ratio of magnitude of total energy; kinetic λ
A
energy: Potential energy for any orbit is 1: 1: 2.
(iii) Number of maxima for the curve 4pr2 R2 (r) vs
are three for the 5px orbital.
(iv) The ratio of de Broglie wavelength of a ‘H’ atom,
1
‘He’ atom and CH4 molecule moving with equal √V
kinetic energies 4: 2: 1.
(a) FFTT (b) TTFT (a) mA = mB (b) mA > mB
(c) TFTF (d) FTTT (c) mA < mB (d) mA ≤ mB
93. The difference of nth and (n + 1)th Bohr’s radius of 98. Which of the following curves represent the speed of
H-atoms is equal to (n − 1)th Bohr’s radius. Hence, the the electron of hydrogen atom as a function of princi-
value of ‘n’ is pal quantum number ‘n’?
Chapter_01.indd 59 8/17/2013 3:43:13 PM

3 4 3. In a photoelectric experiment, the stopping potential is

1
plotted against of incident radiation for two different
λ
V
metals, the curve is like as shown in figure. Predict
2 which of the following statements are correct?
1
V0
(volts)
n Metal I
(a) 1 (b) 2 Metal II

(c) 3 (d) 4
99. In the graph between v and Z for the Mosley’s equa-
tion, v = a (Z – b), the intercept OX is 1 on v axis.
X _
1 (m–1)
λ
√V (a) Slope of the curves for both the metals is 1.212 ×

10−6 Jm C−1
(b) When an electromagnetic radiation of wavelength
450°
100 nm strikes the two metals separately, the stop-
ping potential for metal I is 12.18 V.
O Z (c) The stopping potential for metal I is more than
What is the frequency v when the atomic number Z is 52? that of metal II, if both the metals are exposed to
(a) 7.14 s−1 (b) 7 s−1 electromagnetic radiations of wavelength 200 nm,
(c) 2401 s−1 (d) 2601 s−1 separately.
(d) The stopping potential for metal II is more than
Multiple Choice Questions with One or that of metal I, if both the metals are exposed to
electromagnetic radiation of wavelength 200 nm,
More Than One Answer
separately.
1. Which of the following can be concluded correctly 4. Which of the following are the correct statements?
from the solution of Schrodinger equation? (a) Light waves were considered electromagnetic in
(a) For all orbitals, the radial wave-function (y) nature.
approaches to value zero as r (distance from (b) In vacuum, all types of electromagnetic radiation
nucleus) regardless of their wavelength, travel at the same
(b) The radial probability density (y)2 for 1s orbital is speed, i.e., 3 × 108 ms−1.
maximum at nucleus. (c) The ideal body which emits and absorbs all fre-
(c) The radial distribution function (4pr2, y2) for 1s quencies, is called a black body.
orbital is minimum at nucleus. (d) Quantum is also called photon.
(d) In plot of radial wave function (y), y changes its 5. Which of the following pairs have identical values of
sign at the nodes. magnetic moment?
2. When photons of energy 4.25 eV strike the surface of (a) Zn2+, Cu+ (b) Co2+, Ni2+
a metal A, the ejected photo electrons have maximum 4+
(c) Mn , Co 2+
(d) Mg2+, Sc+
kinetic energy TA (expressed in eV) and de Broglie 6. Which of the following statements are (is) correct?
wavelength lA. The maximum kinetic energy of the (a) Electrons in motion behaves as if they were
photo electrons liberated from another metal ‘B’ by waves.
photons of energy 4.20 eV is TB = TA − 1.5 (expressed (b) s-orbital is non directional.
in eV). If the de Broglie wavelength of these photo (c) An orbital can accommodate a maximum of two
electrons is lB = 2lA, then electrons with parallel spins.
(a) work function of A is 2.25 eV. (d) The energies of the various sub shells in the same
(b) work function of B is 4.20 eV. shell are in the order s > p > d > f.
(c) TA = 2 eV. 7. The nucleus of an atom is located at x = y = z = 0. If the
(d) TB = 2.50 eV. probability of finding an ‘s’ orbital electron in a tiny
Chapter_01.indd 60 8/17/2013 3:43:14 PM

volume around x = a, y = z = 0 is 1.0 × 10−5, choose the (d) ‘2p’ orbital with quantum numbers n = 2, l = 1,
correct statement (s) regarding the probability of e− m = 0, also shows the angular dependence.
(a) The probability of finding the electron in the 12. According to Bohr’s theory,
same-sized volume around x = z = 0, y = a is the (a) When the atom gets the required energy from
same i.e., 1× 10−5. the outside, electrons jump from lower orbits to
(b) The probability of finding the electron in the higher orbits and remain there.
same-sized volume around x = y = 0, z = a is zero. (b) When the atom gets the required energy from out-
(c) The probability at the second site if the electron side, electrons jump from lower orbits to higher
were in a pz orbital is zero. orbits and remain there for very short intervals of
(d) The probability at the second site if the electron time and return back to the lower orbit, radiating
were in a pz orbital is the same i.e., 1.0 × 10−5. the energy.
8. Choose the correct statement (s) regarding Bohr- (c) Angular momentum of the electron is proportional
Sommerfeld’s model. to its quantum number.
(a) All paths around the nucleus are elliptical. (d) Angular momentum of the electron is independent
(b) When an electron revolves around the nucleus of its quantum number.
following circular path, only the angle of rotation 13. Choose the correct statement (s) regarding the photo-
is changed. electric effect:
(c) When an electron revolves around the nucleus (a) No electrons are ejected, regardless of the inten-
following elliptical path, both the angle of rotation sity of the radiation, unless the frequency equals or
and the distance from the nucleus are changed. exceeds a threshold value characteristic of the metal.
(d) For an elliptical path, k < n. (b) The kinetic energy of the ejected electrons varies
 1 1 linearly with the frequency of the incident radia-
9. If there were three possible values  − ,0, +  for
 2 2 tion and its intensity.
the spin magnetic quantum number (ms), which of (c) Even at low intensities, electrons are ejected
the following statement (s) is/are correct regarding a immediately if the frequency is above the thresh-
hypothetical Periodic Table based on this condition? old value.
(a) The first period would have only 2 vertical (d) An intense and a weak beam of monochromatic
columns. radiations differ in having number of photons and
(b) The second period would have 12 elements. not in the energy of photons.
(c) The Periodic Table would contain 27 groups. 14. Mark out the correct statement (s)
(d) The third period would have 12 elements. (a) Electrons within a sub shell for which l > 0 mean
that the relatively greater electrostatic repulsion
10. Select the wrong statements.
between two electrons in the same orbital within
(a) If the shortest wavelength of H-atom in Lyman
a sub shell as compared with occupancy of two
series is ‘x’, then the longest wavelength in
9x orbitals having different ml values.
Balmer series of He+ ion is (b) Electrons in singly occupied orbitals tend to have
5
their spins in the same direction so as to maximize
(b) When an electron jumps from 4th excited state to the net magnetic moment.
ground state, maximum number of phrotons that (c) In the ground state, an atom adopts a configu
may be emitted are 4 ration with the greatest number of unpaired
(c) Number of nodal planes and radial nodes in 5d x2 − y2 electrons.
orbital are 2 and 1 respectively (d) Electrons in different orbitals with parallel spins
(d) All four quantum numbers are obtained from the show mutual attraction, so the electron-nucleus
Schrodinger wave equation when applied on the interaction is improved.
atom 15. Which of the following statement is/are correct?
11. Choose the correct statement among the following. (a) For all values of ‘n’ the p-orbitals have the
(a) Radial distribution function (y24pr2) gives the same shape, but the overall size increases as ‘n’
probability at a particular distance along one cho- increases, for a given atom.
sen direction. (b) The fact that there is a particular direction, along
(b) ‘xz’ plane acts as a nodal plane for 3px orbital. which each p-orbital has maximum electron-
(c) For ‘s’ orbitals wave function is independent of density, plays an important role in determining
q and f. molecular geometries.
Chapter_01.indd 61 8/17/2013 3:43:14 PM

(c) The charge cloud of a single electron in 2px atomic (c) The number of radial nodes is equal to n − l −1.
orbital consists of two lobes of electron-density. (d) The number of maximum peaks in 2s-orbitals are
(d) The very fact that an e− is present in both the lobes two.
at equal times, and the fact that in order to move 21. Select the correct statements about the wave function y.
from one lobe to another, it must cross the node, (a) y must be real.
implies, there is at least some probability of find- (b) y must be single values, continuous.
ing an e− in the node. (c) y has no physical significance.
16. In a hydrogen-like sample electron is in 2nd excited (d) y2 gives the probability of finding the electrons.
state, the binding energy of 4th state of this sample is
13.6 eV, then
(a) A 24.17 eV photon can set free the electron from
Comprehensive Type Questions
the second excited state of this sample.
(b) 3 different types of photons will be observed if Passage-I
electrons make transition up to ground state from
the second excited state. Imagine a universe in which the four quantum numbers
(c) If 23 eV photon is used, then KE of the ejected can have the same possible values as in our universe except
electron is 1 eV. the angular momentum quantum number ‘l’ can have inte-
(d) 2nd line of Balmer series of this sample has gral values of 0, 1, 2,..., n instead of 0, 1, 2,.....(n − 1) and
same energy value as 1st excitation energy of magnetic quantum number ‘m’ can have integral values of
H-atoms. − (l + 1) to 0 to (l + 1) instead of −l to 0 to +l.
17. Identify the correct statement (s) among the following. 1. Electronic configuration of the element with atomic
(a) If Aufbau rule is not followed, then chromium will number 25, based on the above assumption is
still remain in d-block. (a) 1s2 1p6 2s2 1d10 2p5
(b) If there are three possible values for spin quantum (b) 1s2 1p10 2s2 1d11
numbers, then chromium would have been lying in (c) 1s3 1p9 2s3 2p9 3s1
s-block (d) 1s6 1p10 2s6 2p3
(c) If Hund’s rule of maximum multiplicity is not fol- 2. Based on above assumption magnetic moment of the
lowed, then the magnetic moment of chromium element with atomic number 18, is
would be zero. (a) 24 BM (b) 8 BM
(d) If Hund’s rule of maximum multiplicity is not (c) Zero BM (d) 15 BM
followed, then Cr3+ (aq) ion would be colourless.
18. The energy of an electron in the first Bohr orbit of 3. Based on assumption after completion of 3s orbital
H-atom −13.6 eV; then which of the following state- electron enters into .... orbital
ment (s)/are correct for He+? (a) 3p (b) 2d
(a) The energy of electron in second Bohr orbit is (c) 4s (d) 1d
−13.6 eV. 1 1
(b) The KE of electron in the first orbit is 54.46 eV 4. If spin quantum numbers are − , 0, + based on the
2 2
(c) The KE of electron in second orbit is 13.6 eV. above assumption electronic configuration of the
(d) The speed of electron in the second orbit is 2.19 × element with atomic number 30 is
106 m/s. (a) 1s3 2s3 2p9 3s3 3p9 4s3
19. If the electron of the hydrogen atom is replaced by another (b) 1s3 1p15 2s3 1d9
particle of same charge but of the double mass, then (c) 1s9 1p15 2s6
(a) radii of different shells will increase. (d) 1s3 1p9 2s3 2p9 1d6
(b) energy gap between two levels will become
double.
(c) ionization energy of the atom will be double. Passage-II
(d) speed of new particle in a shell will be lesser than
the speed of electron in the same shell. Imagine an atom made up of a proton and a hypothetical
20. Which of the following is/are correct about the radial particle of half the mass of the electron but having the same
probability curves? charge as the electron. Bohr’s model is applicable and all
(a) 3d z2 has three angular nodes. transition of this hypothetical particle from higher level to
(b) The number of angular nodes are l. ground state is possible.
Chapter_01.indd 62 8/17/2013 3:43:15 PM

1. The largest wavelength of photon that will be emit- emitted photons, have energy 2.55 eV. Some have more and
ted when hypothetical particle jumps to first excited some have less than 2.55 eV.
level is 1. The initially excited level B is
18 72 (a) 2nd orbit (b) 3rd orbit
(a) (b) th
5R 5R (c) 4 orbit (d) 5th orbit
2. The ionization energy of the gaseous atom is
36 8
(c) (d) (a) 13.6 eV (b) 14.4 eV
5R R (c) 27.2 eV (d) 54.4 eV
2. The velocity of this particle in second Bohr orbit is 3. The minimum energy of the emitted photon is
(a) 2.188 × 106 m/s (a) 2.7 eV (b) 2.0 eV
(b) 1.094 × 106 m/s (c) 0.66 eV (d) 0.54 eV
(c) 0.547 × 106 m/s
(d) 4.376 × 106 m/s
Passage-V
3. The radius of third Bohr orbit is
(a) 9.522 Å (b) 4.761 Å In the photoelectric effect, an incoming photon brings a
(c) 2.380 Å (d) 1.587 Å definite quantity of energy, hv. It collides with an electron
4. The kinetic energy of the hypothetical particle in first close to the surface of the metal target, and transfers its
orbit is energy to it. The difference between the work function,
(a) −6.8 eV (b) 6.8 eV f, and the energy hv appears as the kinetic energy of the
(c) 27.2 eV (d) −27.2 eV ejected electron.
The minimum potential at which the plate photoelec-
tric potential. If V0 is the stopping potential, then eV0 = hv.
Passage-III
− hv0 current becomes zero is called stoping.
A single electron atom has nuclear charge +Ze. Here,
Z is the atomic number and e is charge. It requires 47.2
eV to excite the electron from second Bohr orbit to third Photoelectrons e–
Bohr orbit. E(e )
–
1. Atomic number of the element is Free, stationary

electorns
(a) 2 (b) 3
Energy
hv Φ
(c) 4 (d) 5
2. The wavelength required to remove electron from the
first Bohr orbit in above data, is Bound electron
(a) 0.22 × 10−7 cm
(b) 1.0 × 10−7 cm
(c) 5.6 × 10−7 cm 1. Light of wavelength 4000 Å is incident on a metal
(d) 3.7 × 10−7 cm whose work function is 2 eV. Then the maximum pos-
3. The kinetic energy of the electron in first Bohr orbit in sible kinetic energy of the photoelectron is
above data, is (a) 3.09 eV (b) 1.9 eV
(a) 1.962 × 10−10 ergs (c) 1.09 eV (d) None of these
(b) 3.48 × 10−10 ergs 2. The threshold frequency for emitting photoelec-
(c) 0.872 × 10−10 ergs trons from a metal surface is 5 × 1014 s−1. Which
(d) 5.45 × 10−10 ergs of the following could be the frequency of radia-
tion to produce photoelectrons having twice the
kinetic energy of those produced by the radiation of
Passage-IV
frequency 1015 s−1?
A gas of identical H-like atom has some atoms in the low- (a) 2.15 × 1014 s−1 (b) 3.70 × 1013 s−1
est energy level A and some atoms in a particular upper (c) 4.11 × 1014 s−1 (d) 15 × 1014 s−1
(excited) energy level B and there are no atoms in any 3. If one photon has 25 eV energy and the work func-
other energy level. The atoms of the gas make transition tion of the material is 7 eV, then value of the stopping
to a higher energy level by absorbing monochromatic light potential will be
of photon of energy 2.55 eV. Subsequently, the atoms emit (a) 32 V (b) 18 V
radiation of only six different photon energies. Some of the (c) 3.3 V (d) Zero
Chapter_01.indd 63 8/17/2013 3:43:16 PM

Passage-VI 2. An electron can be located with an error equal to 10−10

m. What is the uncertainty in its momentum?
According to Planck’s quantum theory of radiation, the
(a) 5.28 × 10−25 kg ms−1 (b) 5.5 × 10−26 kg ms−1
radiant energy is emitted or absorbed discontinuously in
(c) 3.34 × 10−14 kg ms−1 (d) 6.63 × 10−27 kg ms−1
the form of quanta. The energy of a quantum is given by
3. If the uncertainty in the position and momentum for an
E = hv, where ‘v’ is the frequency of radiation. Moreover,
electron are equal, then the uncertainty in its velocity is
a body can emit or absorb energy only in an integral mul- h h
tiples of quanta. (a) (b)
π 2π
1. Planck’s quantum theory of radiation favors the fol-
lowing nature of electromagnetic radiation. 1 h 1 h
(c) (d)
(a) Particle (b) Wave nature m 2π 2m π
(c) Dual nature (d) None of these
2. The energy associated with one photon of wavelength
3000 Å is Passage-VIII
(a) 5.42 × 10−19 J (b) 6.63 × 10−19 J In 1908, W. Ritz introduced his combination principle,
(c) 3.73 × 10 J
−19
(d) 3.73 × 10−19 J which is virtually a generalization of Balmer formula. In
3. Which of the following is not the correct representa- its simplest form the principle states that the wave number
tion of Einstein’s photoelectric equation? of any spectral line may be represented as the combination
1 2
(a) mv = h ( v + v0 ) of two terms, one of which is constant and the other vari-
2 able throughout each spectral series.
1 2 R R
(b) hv = hv0 + mv v = 2 − 2 ; x and y integers for H-atom. The later on
2 x y
1 2 theories have modified the above principle as for H-atom.
(c) hv = W + mv
2 1 1
v = RH  1 − 2 
1 2  n2 n2 
(d) mv = h ( v − v0 )
2 RH is Rydberg number = 109,677.76 cm−1 and n1 and
n2 are lower and higher energy levels of the H-atom.
1. What transition H-spectrum would have the same
Passage-VII l as the Balmer transition n = 4 to n = 2 of He+
The properties of electrons indicate that they have a dual spectrum?
nature, i.e., they behave both as particle and as wave. de (a) 2 → 1 (b) 3 → 1
Broglie suggested that every object which possesses mass (c) 4 → 1 (d) 5 → 1
and velocity behaves both as a particle and as a wave. 2. The wavelength of radiation of the longest transition in
According to de Broglie, the wavelength l of a particle Lyman series of He+ ion is
of mass ‘m’, moving with a velocity ‘v’ is given by l = (a) 22.8 nm (b) 32.2 nm
h/mv. The dual nature of electron further gets support by (c) 40 nm (d) 48 nm
Heisenberg’s uncertainty principle which states that it is 3. If the shortest l of H-atom in Balmer series is l1, the
not possible to determine simultaneously and accurately longest l in Lyman series is
the position and momentum of a moving electron or some (a) 0.14 l1 (b) 0.33 l1
other microscopic particle. (c) 0.44 l1 (d) 0.66 l1
h
According to Heisenberg ∆x∆p ≥ , where Dx and
4π
Passage-IX
Dp respectively represent the uncertainties involved in the
simultaneous determination of position and momentum of A hydrogen-like atom (atomic number Z) is in a higher
a moving particle. excited state of quantum number ‘H’. This excited atom
1. The de Broglie wavelength of a cricket ball of mass 0.2 can make a transition to the first excited state by succes-
kg moving with a velocity of 30 ms−1 would be sively emitting two photons of energies 10.2 eV and 17.00
(a) 1.8 × 10−34 m eV respectively. Alternatively, the atom from the same
(b) 3.6 × 10−34 m excited state can make a transition to the second excited
(c) 2.2 × 10−34 m state by emitting two photons of energy 4.25 eV and
(d) 1.1 × 10−34 m 5.95 eV respectively.
Chapter_01.indd 64 8/17/2013 3:43:17 PM

1. The value of n is 2. Match the following

(a) 8 (b) 6
Column I Column II
(c) 5 (d) 4
(a) Emission spectrum (p) Cold nitrogen gas
2. The atomic number Z is
(b) Absorption spectrum (q) Excited atomic hydrogen
(a) 1 (b) 2
(c) Band spectrum (r) Very hot carbon dioxide
(c) 3 (d) 4
(d) Line spectrum (s) Neon gas at room
temperature
Passage-X
3. Match the following
A formula analogous to the Rydberg formula applies to
the series of spectral lines which arise from transitions Column I Column II
from higher energy levels to the lower energy level of the (a) Magnetic moment of an (p) Principle QN
hydrogen atom. atom or ion
A muonic hydrogen ion is like a hydrogen atom in (b) Radial node (q) Azimuthal QN
which the electron is replaced by a heavier particle the (c) Hund’s rule (r) Magnetic QN
muon. The mass of the muon is 207 times the mass of (d) Orbital angular momentum (s) Spin QN
an electron while charge is the double that the electron of electron
(assume charge of proton is same).
1. Radius of first Bohr orbit of muonic hydrogen ion is
4. Match the following
0.529 0.529
(a) Å (b) Å Column I Column II
207 414
(a) Hydrogen atom (p) Principal quantum
0.529 number
(c) Å (d) 0.529 × 828 Å
828 (b) Nitrogen atom (q) Azimuthal quantum
number
2. Ionization energy of muonic hydrogen ion is
(c) Li2+ ion (r) Exchange energy
(a) 13.6 × 207 eV (b) 13.6 × 414 eV
(d) Helium atom (s) Symmetry
(c) 13.6 × 828 eV (d) 13.6 × 3312 eV
3. Distance between 1st and 3rd Bohr orbit of muonic
hydrogen ion will be 5. Match the following
0.529 0.529 Column I Column II
(a) × 8 Å (b) ×8Å
207 414 (a) Magnetic moment (p) Principal quantum
number
0.529 0.529
(c) × 5 Å (d) ×8Å (b) Splitting of spectral lines(q) Azimuthal quantum number
207 828 in magnetic field
(c) Number of spherical nodes (r) Magnetic quantum number
(d) Fine lines spectra (s) Spin quantum number
Matching Type Questions 6. n → orbit no; Z → at no; rn, z → radius Vn, z → veloc-
1. Match the Column I with Column II ity; Tn, z → Time period of revolution Kn, z → kinetic
energy of the electron.
Column I Column II
(Chemical Prop) (Metals) Column I Column II
(of single electron species) (Ratio)
(a) Distance of maximum probabil- (p) 1.1 Å
ity of 1s electron (a) r2,1: r1,2 (p) 9: 1
(b) Radial node of 2s electron is (q) 1.06 Å (b) V1,3: V3,1 (q) 8: 1
(c) Radius of 2nd orbit in He+ ion is (r) 1.59 Å (c) T1,2: T2,1 (r) 16: 1
(d) Radius of 3rd orbit in Li2+ ion is (s) 0.53 Å (d) K1,2: K2,1 (s) 1: 32
Chapter_01.indd 65 8/17/2013 3:43:17 PM

7. Match the following a. If both assertion and reason are true and reason is the
correct explanation of assertion
Column I Column II b. If both assertion and reason are true but reason is not
(a) Violation of Aufbaus rule (p) ↑↑ ↑↑ ↑ the correct explanation of assertion
(b) Violation of Pauli’s Exclusion c. If assertion is true but reason is false
Principle
(q) ↑↑ ↑ ↑ ↓ d. If assertion is false but reason is true
(c) Violation of Hund’s rule (r) ↑ 1. Assertion (A): The wave functions of p-type (l = 1)
↑↑ ↑↑ ↑
(d) Violation of above three with the same value of ‘n’ but with different values of
principles
(s) ↑ ↑↑ ↑ ↓ ‘m’ will have the same radial distribution function.
Reason (R): Radial distribution function depends only
8. Match the following on the values ‘n’ and ‘l’ and not on the value of ‘m’.
2. Assertion (A): According to Bohr IE2 of He is 54.4
Column I Column II eV/atom.
Z2
(a) n (p) Stark effect Reason (R): IE of atom is given by 13.6 eff2 eV/atom
n
(b) l (q) Schrodinger’s equation
(c) m (r) Bohr’s atomic model 3. Assertion (A): An electron can never be found in the
(d) s (s) Pauli’s exclusivity nucleus.
Reason (R): Velocity of the electron wave is less than
(t) Aufbau sequencing
the velocity of light.
4. Assertion (A): No two electrons of an atom can have
9. Match the following the same set of all four quantum numbers.
Column I Column II Reason (R): An orbital can accommodate a maximum
of two electrons.
(a) 2s (p) Sum of (n + l) is 3 5. Assertion (A): 3dxy, 4dxy, 5dxy.......... all are having the
(b) 2p (q) Total number of radial same shape i.e., the double dumb bell.
nodes = 1 Reason (R): The size of orbitals are independent of
(c) 3s (r) no. of peaks in radial the principal quantum number.
probability graph = 2 e−
(d) 5f (s) Spherical symmetry 6. Assertion (A): ratio of anode rays is different for
gasses. m
of orbital around
nucleus Reason (R): Proton is the fundamental particle present
in gases.
10. Match the following Column I with Column II 7. Assertion (A): y2 measures the electron probability
density at a point in an atom.
Column I Column II
Reason (R): y and y2 vary as a function of the three
(a) For transition: n = 5 (p) Only two Balmer lines are coordinates ‘r’ (radial part), q and f (angular part).
to n = 2 obtained 8. Assertion (A): Two orbitals with same value of l but
(b) For transition: n = 5 (q) Total three spectral lines are different values of ml will have same number of angu-
to n = 3 obtained lar nodes.
(c) For transition: n = 4 (r) At least one Lyman line is Reason (R): Angular wave function of an orbital
to n = 2 obtained depends upon its l and ml values.
(d) For transition: n = 4 (s) Hb for Balmer series and Ha 9. Assertion (A): Aufbau principle is violated in writing
to n = 1 for Paschen series both are electronic configuration of Pd.
obtained Reason (R): Pd is diamagnetic in nature.
10. Assertion (A): Spectral lines would not be seen for a
2px – 2py transition.
Assertion (A) and Reason
Reason (R): p-orbitals are degenerate orbitals.
(R) Type Questions 11. Assertion (A): Energy of orbitals in hydrogen
“In each of the following questions a statement of atom is
Assertion (A) is given followed by a corresponding state- 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
ment of Reason (R) just below it. Mark the correct answer Reason (R): The energy of orbitals in hydrogen atom
from the following statements. is determined by using principal quantum number.
Chapter_01.indd 66 8/17/2013 3:43:18 PM

12. Assertion (A): Angular momentum of an electron in 10. In a single hydrogen atom, the electron is excited
an orbit is quantized. to its 6th orbit. The maximum no. of distinct lines
Reason (R): The electron wave propagating around possible, when it comes to the ground state is
the nucleus remains in the same phase, 2pr = nl. ______________.
13. Assertion (A): Fine lines are observed in spectra if an 1
atom is placed in a strong magnetic field. 11. For the hydrogen atom, En = RH .
n2
Reason (R): Degenerate orbitals split in the presence
of a magnetic field. Where, RH = 2.178 × 10−18 J.
14. Assertion (A): Spin quantum number can have the Assuming that the electrons in other shells exert no
value +1/2 or −1/2. effect, find the minimum no. of Z (atomic no.) at which
Reason (R): Sign here signifies the wave function. a transition from the second energy level to the first
15. Assertion (A): The transition of electrons n3 → n2 in results in the emission of an X-ray. Given that the low-
the atom will emit greater energy than n4 → n3. est energy rays have l = 4 × 10−8 m.
Reason (R): n3 and n2 are closer to nucleus than n4. 12. Find the quantum number ‘n’ corresponding to the
excited state of He+ ion if on transition to the ground
state that ion emits two photons in succession with
wavelengths 1078.5 and 30.4 nm.
Integer Type Questions
13. Energy required to stop the ejection of electrons
1. In which quantum level does the electron jumps from Cu-plate 0.27 eV. Calculate the work function
in He+ ion to ground state if it is given an energy (in eV) when radiation of l = 235 nm strikes down
corresponding to 99 per cent of the ionization poten- the plate.
tial of He+ ion? 14. What is the degeneracy of the level of the hydrogen
2. When a certain metal was irradiated with light hav- − RH
ing a frequency of 3.0 × 1016 s−1, the photo electron atom that has the energy ?
9
emitted had twice the kinetic energy as did photo-
electrons emitted when the same metal was irradi- 15. The number of visible lines when an electron returns
ated with light having a frequency of 2.0 × 1016 s−1. from the 5th orbit to ground state in the hydrogen
The threshold frequency of the metal (in 1016 s−1) is spectrum is ______________.
______________. 16. A photon of wavelength 5000 Å strikes a metal sur-
3. Given ionization potential of hydrogen atom is 2.0 face, the work function of the metal being 0.475 eV.
× 10−18 J, Planck’s constant is 6.0 × 10−34 J-s. The The kinetic energy of the emitted photo electron is
frequency of Hb line in Balmer series has the values of ______________ eV.
(1012 Hz) is ______________. 17. The de Broglie wave length of on electron in a certain
4. The radius of the orbit in hydrogen atom is 0.8464 nm. Bohr’s orbit H-atom is 6.64 Å.The quantum number of
The velocity of electron in this orbit (in the order of orbit is.
103 m/s) is ______________. 18. In a nonconventional basis, there are three allowed
5. The velocity of electron in a certain Bohr’s orbit of value of spin quantum numbers, then how many more
hydrogen atom bears in the ratio 1: 275 to the veloc- elements can be accommodated in the second period
ity of light. The qunatum number (n) of the orbit is as compared to convertional periodic table.
___________. 19. The number of revolutions made by electron in 1 sec in
6. The wavelength of a line in Balmer series of hydro- H –atom in its orbit is twice of the number of revolutions
gen atom is 4814 Å. In which orbit deexitation take made by electron in 1 sec in the 2nd orbit of He+ ion, then
place? on is.
7. The de Broglie wave length of an electron in a certain 20. An electron in a hydrogen atom in its ground state has
orbit of hydrogen atom is 13.3 Å. So the number of 1-5 times as much energy as the minimum required for
waves present in an orbit is ______________. its escape from the atom. The velocity of electron in
8. Give the number of angular nodes of orbital belong the scientific notation is x × 10 y m / sec . Then the value
to the subshell for which minimum value of magnetic of Y is ______________.
quantum number is −2. 21. In a collection of H-atoms, all the electrons tend to
9. What will be the number of lines corresponding to flow to n = 5 to ground level finally (directly or indi-
Lyman series when an electron is in 3rd excited state rectly) without emitting any line in Balmer series the
of hydrogen atom? possible different radiations are.
Chapter_01.indd 67 8/17/2013 3:43:18 PM

Previous Years’ IIT Questions ground state configuration ls22s22p3, because the
electrons would be closer to the nucleus. Yet ls7 is not
1. The electrons, identified by quantum numbers n and l,
observed because it violates:
(1999)
(2002S)
I. n = 4, l = 1,
(a) Heisenberg uncertainty principle
II. n = 4, l = 0,
(b) Hund’s rule
III. n = 3, l = 2 and
(c) Pauli exclusion principle
IV. n = 3, l = 1 can be placed in order of increasing
(d) Bohr postulate of stationary orbits
energy, from the lowest to highest as:
8. The radius of which of the following orbit is same as
(a) IV < II < III < I that of first Bohr’s orbit of hydrogen atom?
(b) II < IV < I < III (2004S)
(c) I < III < II < IV (a) He+ (n = 2) (b) Li2+ (n = 3)
(d) III < I < IV < II (c) Li2+ (n = 2) (d) Be3+ (n = 2)
2. The number of nodal planes in a px orbital is: 9. The number of radial nodes of 3s and 2p − orbitals are
(2000S) respectively:
(a) one (b) two (2005S)
(c) three (d) zero (a) 2,0 (b) 0.2
3. The electronic configuration of an element is ls2, (c) 1,2 (d) 2,1
2s22p6, 3s23p63d5, 4s1. This represents its: 10. The kinetic energy of an electron in the second Bohr
(2000S) orbit of a hydrogen atom is [a0 is Bohr radius]
(a) excited state (b) ground state (2012)
h2 h2
(c) cationic form (d) anionic form (a) 2 2 (b)
4. The wavelength associated with a golf ball weigh- 4 π ma0 16π 2 ma02
ing 200 g and moving at a speed of 5 m/h is of the
(c) h2 (d) h2
order: 32π 2 ma02 64π 2 ma02
(2001S)
(a) 10−10 m (b) 10−20 m 11. Match the following:
(c) 10−30 m (d) 10−40 m (2006)
5. The quantum numbers +1/2 and −1/2 for the electron
spin represent: Column I Column II
(2001S) (a) Vn/Kn = ? (p) 0
(a) rotation of the electron in clockwise and anti- (b) If radius of nth orbital ∝ En x; x = ? (q) −1
clockwise direction respectively (c) Angular momentum in (r) −2
(b) rotation of the electron in anticlockwise and lowest orbital
clockwise direction respectively (d) 1 ∝ z y ; y = ? (s) 1
(c) magnetic moment of the electron pointing up and rn
down respectively
(d) two quantum mechanical spin states which have
12. Match the entries in Column-I with the correctly
no classical analogue
related quantum number(s) in column-II
6. Rutherford’s experiment, which established the nuclear
(2008)
model of the atom, used a beam of:
(2002S) Column I Column II
(a) β-particles, which impinged on a metal foil and
(a) Orbital angular momentum of the (p) Principle quantum
got absorbed.
electron in a hydrogen like atomic number
(b) γ-rays, which impinged on a metal foil and ejected
orbital.
electrons.
(b) A hydrogen-like one electron wave (q) Azimuthal quantum
(c) helium atoms, which impinged on a metal foil and
function obeying Pauli principle. number
got scattered.
(c) Shape, size and orientation of (r) Magnetic quantum
(d) helium nuclei, which impinged on a metal foil and
hydrogen like atomic orbitals. number
got scattered.
(d) Probability density of electron at (s) Electron spin
7. If the nitrogen atom has electronic configuration ls7,
the nucleus in hydrogen-like atom. quantum number
it would have energy lower than that of the normal
Chapter_01.indd 68 8/17/2013 3:43:18 PM

Comprehensive Type Questions 49. b 50. a 51. b 52. c 53. c 54. d

55. c 56. b 57. a 58. c 59. d 60. a
The hydrogen-like species Li2+ is in spherically symmetri-
61. a 62. a 63. a 64. c 65. a 66. d
cal state S1, with one radial node. Upon absorbing light
67. c 68. d 69. d 70. c 71. d 72. d
the ion undergoes transition to a state S2. The state S2 has
73. b 74. c 75. b 76. d 77. b 78. a
one radial node and its energy is equal to the ground state
79. c 80. c 81. c 82. b 83. c 84. b
energy of the hydrogen atom.
85. a 86. b 87. a 88. a 89. a 90. c
(2010)
91. a 92. d
Answer the following questions:
13. The state S1 is:
(a) 1s (b) 2s Multiple Choice Questions with Only
(c) 2p (d) 3s One Answer
14. Energy of the state S1 in units of the hydrogen atom
ground state energy is: Level-II
(a) 0.75 (b) 1.50 1. d 2. b 3. b 4. a 5. a 6. c
(c) 2.25 (d) 4.50 7. d 8. d 9. b 10. c 11. b 12. a
15. The orbital angular momentum quantum number of 13. d 14. d 15. a 16. b 17. c 18. b
the state S2 is: 19. a 20. b 21. b 22. c 23. d 24. d
(a) 0 (b) 1 25. b 26. c 27. d 28. b 29. a 30. c
(c) 2 (d) 3 31. b 32. d 33. c 34. a 35. b 36. c
37. d 38. a 39. c 40. a 41. a 42. a
43. a 44. a 45. a 46. c 47. b 48. b
Integer Type Questions 49. c 50. c 51. d 52. a 53. b 54. b
Answer to the following question in a single digit integer, 55. c 56. b 57. a 58. d 59. a 60. c
ranging from 0 to 9. 61. a 62. b 63. a 64. c 65. d 66. b
16. The maximum number of electrons that can have 67. d 68. d 69. a 70. d 71. c 72. c
principle quantum number, n = 3 and spin quantum 73. b 74. d 75. c 76. a 77. a 78. a
1 79. c 80. c 81. c 82. b 83. a 84. d
numbers ms = − is ______. 85. d 86. b 87. b 88. b 89. d 90. c
2 (2011) 91. b 92. b 93. d 94. a 95. b 96. c
17. The work function of some metals is listed below. The 97. b 98. a 99. d
number of metals which will show photoelectric effect
when light of 300 nm wavelength falls on the metal is
______. Multiple Choice Questions with One or More
(2011) than One Answer
Metal Li Na K Mg Cu Ag Fe Pt W 1. a, b, c, d 2. a, c 3. a, b, c
4. a, b, c, d 5. a, c 6. a, b
eV 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75
7. a, c 8. b, c, d 9. b, c, d
10. b, c, d 11. c, d 12. b, c
Answer Keys 13. a, c, d 14. a, b, c 15. a, b, c
16. a, b 17. a, c 18. a, b, c, d
Multiple Choice Questions with Only 19. b, c 20. b, c, d 21. a, b, c, d
One Answer
Level-I Comprehensive Type Questions
1. d 2. c 3. b 4. c 5. c 6. d
7. c 8. c 9. b 10. a 11. b 12. d Passage – I 1. d 2. b 3. b 4. c
13. d 14. d 15. b 16. b 17. c 18. d Passage – II 1. b 2. b 3. a 4. b
19. b 20. b 21. d 22. b 23. a 24. c Passage – III 1. d 2. d 3. d
25. a 26. a 27. d 28. d 29. d 30. b Passage – IV 1. a 2. a 3. c
31. d 32. a 33. d 34. d 35. a 36. b Passage – V 1. c 2. d 3. b
37. d 38. d 39. c 40. a 41. a 42. a Passage – VI 1. a 2. b 3. a
43. c 44. b 45. a 46. d 47. a 48. a Passage – VII 1. d 2. a 3. d
Chapter_01.indd 69 8/17/2013 3:43:19 PM

Passage – VIII 1. a 2. a 3. b h
Passage – IX 1. b 2. c 10. λ =
2KEm
Passage – X 1. b 2. c 3. b V
12. Angular speed =
r
h
Matching Type Questions 16. Orbital angular momentum = l (l +1)
2π
1. a-s b-p c-q d-r
19. h v1 = h vo + x
2. a-r, s b-p, s c-p, s d-q, s
3. a-q, s b-p, q c-p, q, r, s d-q, r h v2 = hvo + kx
4. a-p b-p, q, r, s c-p d-p, q v1 − vo 1
=
5. a-q, s b-r c-p, q d-q v2 − vo k
6. a-q b-p c-s d-r
kv1 − v2
7. a-r, s b-p, q, r c-p, q, r d-r vo =
8. a-q, s, r, t b-q, s, t c-p, q, s d-s k −1
9. a-q, r, s b-p c-p, s d-q, r
−13.6 −13.6
10. a-s b-q, c c-pq, s-d d-p, r, s −
E2 − E1 1 = 27
20. = 4
E3 − E2 −13.6 − −13.6 5
Assertion (A) and Reason (R) Type Questions 9 4
1. a 2. a 3. a 4. b h
21. λ =
5. c 6. b 7. b 8. b 2 KEm
9. b 10. a 11. a 12. a
6.625 × 10 −34
13. c 14. c 15. b 3.31× 10 −29 =
2( KE ) × 0.1× 10 −5
∴KE = 2 × 10 −4 J
1. 10 2. 1 3. 625 4. 547 5. 2 31. Radius of nucleus = 1.25 × 10 −13 × (64)1/3 = 5 × 10 −13 cm
6. 4 7. 4 8. 2 9. 3 10. 5
11. 2 12. 5 13. 5 14. 9 15. 3 4
π(5 × 10 −13 )3
16. 2 17. 2 18. 4 19. 1 20. 6 Fraction of volume = 3 = 1.25 × 10 −13
21. 6 4 −8 3
π (10 )
3
Previous Years’ IIT Questions 32. The probability of finding election in all directions
1. a 2. a 3. b 4. c 5. d are same
6. d 7. c 8. d 9. a 10. c
38. V = λ
11. (a) r (b) q (c) p (d) s
12. (a) q, r (b) p, q, r, s (c) p, q, r (d) p, q h
∴λ =
13. 2 14. 3 15. 2 16. 9 17. 4 mλ
h
∴λ =
m
HINTS and solutions
48. n = 3, l = 2
Multiple Choice Questions with Only One So orbital is 3d
Answer
52. ∆χ = ∆p
Level-I
2. Mass of electron is less when compared to mass of h
∆p =
positive rays 4π
5. y = e r/ao 1 h
∴∆V =
Probability density means y2 m 4π
Chapter_01.indd 70 8/17/2013 3:43:21 PM

56. 2πr = nλ e−. It is possible only if x and y are +3 and +1. Electron
2πx = λ configuration corresponding to these two oxidation
In third orbit states are
2π(9x) = 3λ M+x → 3s2 3p6 3d5
∴ λ = 6πx M+y → 4s1 3d6
So, M+x is more stable due to the half-filled
66. When reaches nucleus kinetic energy converted to configuration.
potential energy 4. According to photoelectric effect eq.
mv = p hc hc
= + E where E = KE
p λ λ0
v=
m
λ −λ
1 P2 E = hc  0 
∴ mV 2 =  λλ 0 
2 2m
p 2
Ze 2 de Broglie’s wavelength
∴ = h
2 m r , where M = mass of e− and E = KE
2mE
∴If momentumis 2 P
h h2 (λλ 0 )
4 P 2 Ze 2 or =
= λ −λ 2mhc(λ 0 − λ)
2m r1 2mhc  0 
Ze 2 Ze 2  λλ 0 
∴4 =
r r1 1/ 2
 hλλ 0 
r = 
∴r1 =  2mhc(λ 0 − λ) 
4
5. From the observations no of nodal regions for that orbital
2πr n − l − 1 = 2. xy is a nodal plane. So orbital is dyz
80. The time taken by one revolution = 6. Along x, y axis the shape of orbital is as shown below:
V
y
2πr 2π(4 r )
∴ Ratio = −8
:
2.188 × 10 2.188 × 158 / 2
dx -y
∴1: 8
2 2
Multiple Choice Questions with Only

One Answer
Level-II 8. (i) No. of nodal planes = l = 0
h
1. Orbital angular momentum = l (l + 1) . For n h h
2π (ii) de Broglie’s wavelength λ = =
= 5l values are 0, 1, 2, 3, 4 and these cannot satisfy the mv p
given condition.
(iii) The principal quantum no. n indicates the size and
2. (i) The no. of peaks in a radial probability curve is
energy of orbit.
equal to n – l.
(iv) p has electronic configuration 3s2 3p3.
So, no. of peaks in 1s and 2s are not equal.
9. The length of a series depends on the difference
(ii) No. of nodal planes equals to l, so it is same for
between wavelength of successive lines. It is more in
2p, 3p and 4p orbitals.
Lyman series.
(iii) Ti2+ and Ni2+ both have same no. of unpaired e–
and have same magnetic moments. 13.6 2
10. Energy given to the e− =× 2 = 3.4 eV
(iv) Any orbital of any sub shell can accommodate 42
only two e–. Work function = 1.4 eV
3. M and M+y both have same magnetic moment 5.916
+x The additional energy supplied due to
which means that both have same no. (5) of unpaired acceleration is 4 eV.
Chapter_01.indd 71 8/17/2013 3:43:23 PM

So, net resultant KE = (3.4 − 1.4) + 4 = 6 eV 18. Let us suppose that ‘na’ is the no. of quanta absorbed
and ‘ne’ is the no. of quanta emitted. na and ne were
12.27 12.27
de Broglie’s wavelength = Å= 5Å related as
V 6 ne = 0.53 na hc
nh So, the absorbed energy Ea = na ×
11. Angular momentum of e– = 4530
2π
hc
So the transition occurs from 4 → 2; that means the Emitted energy Ee = ne ×
5080
transition lies in Balmer series and will be observed in
the visible region. ne hc 4530
⇒ 0.53na ⋅ ×
h na 5080 na hc
12. de Broglie’s wavelength =
2meV = 0.4726
where m is mass of particle, e is charge and V is stop-
ping potential. 19. From the data no. of e− in both cases is (n − 1). So, x
has +1 charge and y has +2 charge.
h k
So, λ p : λ a = :
2m p × e × 0 2 × 4 m p × 2e × v 20. Energy involved in transition E1 = 2E – E = E =
hc
1 1 .
or λ p : λ a = = 2 2: 1
: λ
2 4 4E E
Energy involved in transition E1 = – E = = 1.
13. Energy of emitted photon 3 3
E1 E hc / λ1 λ2
=  2 × 4 − 2 × 4  eV
13.6 13.6 \ = = ⇒ =3
 1  E2 E / 3 hc / λ 2 λ1
2
= 3 × 13.6 eV 21. From the photoelectric effect
\ KE of e− = [3 × 13.6 − 13.6] = 27.2 eV h(x) = hv0 + y (1)
h h(2x) = hv0 + 3y (2)
14. DX × DV = from Eq. (1) → y = hx − hv0
4 πm
⇒ h (2x) = hv0 + 3[h(x) − h(v0)]
6.625 × 10 −34 1 x
\ DV = × −10 ⇒ v0 =
4 × 3.142 × 0.1505 10 2
≅ 3.4 × 10 −24 m/s 22. From the data the difference between radii of ground
state and excited state orbit radius
15. Six nodes are as shown: ⇒ rn − r1 = 0.7935 × 10−9 m
⇒ rn − (0.0529 × 10−9 m) = 0.7935 × 10−9 m
2 4 6 ⇒ rn = 0.8464 × 10−9 m = 0.0529 × 10−9 × n2
3 5 ⇒ n = 4
So, the maximum spectral lines formed
35
So, it has 2.5 waves, so wavelength = = 14 cm. ( n − n )( n − n + 1)
2.5 = 2 1 2 1 =6
2
16. No. of m values = 2l + 1
So, no. of m values for l = 1 is 3 23. For Balmer series n1 = 2 and for the least wavelength
This value is possible for m in case of f and higher sub n2 = ∞ and for the highest wavelength n2 = 3.
shells only. So, wave no. for spectral line with least wavelength,
v1 = RH  2 − 2  = H
1 1 R
17. To have the same de Broglie’s wavelength they must  2 ∞  4
have the same momentum. wave no. for spectral line highest wavelength
⇒ Pp = Pe ⇒ mp × vp = me ve
v2 = RH  2 − 2  = H
1 1 5R
⇒ 1837 me × vp = me ve  2 3  36
ve
So, vp = RH 5 RH
1837 So, v1 : v2 = : = 9: 5
4 36
Chapter_01.indd 72 8/17/2013 3:43:26 PM

24. No. of nodal planes = l = 2 λ1 1 E2

No. of Radial nodes = n − l − 1 = 5 − 2 − 1 = 2 ⇒ = =
λ 2 0.9 E1
No. of peaks = n − l = 5 − 2 = 3
25. No. of revolutions made by one e– per sec ⇒ E2 = 1.23456 E1
So, E2 is 23.456 per cent is more than that of E1.
velocity of e − z 2
= ≅ 3 × 6.66 × 1015 nh 7h
2πrn n 36. Angular momentum = =
2π 11
26. From Rydberg’s equation ⇒ = n = 4
1 1 1  0.529 × n2
= R  2 − 2  Radius of nth orbit rn =
λ 1 n  2
⇒ rn = 2.82 Å
1 1 λR
⇒ 2 = 1 − ⇒ n2 = 37. The data indicates that the transition is only possible
n λR λR − 1 with Lyman, Balmer, Paschen series that means
transition to 4th orbit is not possible which means that
28. At radial node i.e., at r = r0, y2 = 0.
2
transition from 4th orbit occurs.
 1  1 1/ 2  r0  − r0 / 2 a0  38. Maximum no. of spectral lines possible
⇒   2 − e  =0
 2 2 π a
 0  a0   = Σ (n − 1) = 15
⇒ n = 6
r So, from Rydberg’s equation
⇒ 2 − 0 = 0 ⇒ r0 2a0
a0
v =
1 1 1 
29. In case of unielectron systems energy can be deter- = RH  2 − 2 
λ 1 6 
mined only from n values i.e., orbital of same shell
have same energy. 36  1 
λ = × 912 Å  = 912 Å 
30. The energy of an e– in a multielectronic atom can be 35  RH 
determined from (n + l) value. = 938.05
31. (i) Carbonates with thermal stability can be produced n3
by alkali metals. So, — V. 39. Time period ∝
Z2
(ii) Coloured compounds will be formed by transition
T1 Z 22 n13
elements. So, — X. ⇒ = ×
(iii) Largest atomic radius is possible with maximum T2 Z12 n23
no. of shells. So, — Y. [z is the same]
(iv) Acidic oxides will be formed by non-metals. So,
— W. 23
⇒ = 8 : 27
33
32. No. of l values possible for first shell 40. Velocity of an e– in nth orbit
= 3 (0, 1, 2)
So, the total possible no. of m values are 2.17 × 106
= m/s
nm = 9(1 + 3 + 5) n
[No. of m values for given l = 2l +1] From the data
So, the no. of e– that can be fitted = 2 × n.18e–. 2.17 × 106 3 × 108
=
33. According to the given rules n 4
Zr (40) has electronic configuration as follows; ⇒ n = 3
1s3 2s3 2p9 3s3 3p9 3d13 No. of lines in Balmer series is 6 − 2 = 4
35. l1 is the wavelength corresponding to initial kinetic h
energy E1. 41. λ =
2meV0
l2 is the wavelength corresponding to final kinetic
energy E2 and l2 = 0.9l1. 42. Wavelength of first line in Lyman series
hc hc
λ1 = : λ2 = 1 3 1
2mE1 2mE2 λ1 = ⋅ ×
RH 4 Z 2
Chapter_01.indd 73 8/17/2013 3:43:28 PM

1 1 1 
⇒ = 109677 × 9  2 − 2  By comparison
λ 1 3 
2
⇒ l = 114 Å = 1.14 × 10−6 cm  2 1
  = 2 ⇒ n1 = 1
 2 n1
62. If na is the number of absorbed quanta and ne is the no.
of emitted quanta, then 2 2
 2  1
  =  
ne  4  n2 
= 0.5
na ⇒ n2 = 2
Emitted energy Ee is 47 per cent of the absorbed energy 66. de Broglie’s wavelength in nth orbit is
Ea nl = 2prn
hc ⇒ nl = 2pr1n [for hydrogen]
ne ⋅ ⇒ l = 2pr1n = 2pr (x)3
So, X = 0.47
hc ⇒ l = 6px
na 67. If w is angular velocity and r is radius of orbit, v is
4700
velocity of e–.
4700 ne v = rw
⇒ × = 0.47 v 1
X na ⇒ w = ∞ 3
r n
4700 × 0.5 68. We know that the no. of waves made by an e– in an
⇒ X = = 5000 Å
orbit equals to its principle quantum number ‘n’.
0.47
So, from the figure n = 4
63. Before the excitation the molecule should undergo No. of revolutions made by an e− per sec (or)
the homolytic cleavage. So, energy required for
dissociation Ed = 0.04 × 400 = 16 KJ. On dissociation Z2
Frequency = × 6.66 × 1015 s−1
the sample consists of 0.08 moles of H gas atoms. n3
Energy required for excitation 1
= × 6.66 × 1015 = 1 × 1014 s −1
(4)3
 −13.6  −13.6  
= 0.08 × 6.023 × 1023  −
 4  1   69. In case of an elliptical orbit, we know that
length of major axis n
= 4.914768 × 1023 eV =
length of minor axis k
4.914768 × 10 23 × 1.602 × 10 −19 And length of major axis is double the radius of that
= KJ circular orbit
103
2 × 16 × 0.529 4
= 78.734 KJ ⇒ =
So, total energy required = 16 + 78 . 734 l 2
= 94.7345 KJ ⇒ l = 8.464 Å
64. Angular momentum of e–
70. Ionization potential in H-like system means, it is the
nh energy of e– in ground state.
mvr =
2π E
So, En = (0.01) E1 = 21
nh ⇒ n = 10. n
or = 4.217 × 10 −34 kg . m2/s
2π
73. DE = 12.1 = En2 − En1
⇒ n = 3.999 @ 4
The no. of spectral lines in visible region = n − 2 = 4 −13.6
So, 12.1 = − ( −13.6)
−2=2 n2
65. From the data ⇒ n = 3
Therefore, change in angular momentum
1 1 1 1 h
RH × 4 ×  2 − 2  = RH  2 − 2  = ∆n
 2 4   n1 n2  2π
Chapter_01.indd 75 8/17/2013 3:43:32 PM

(3 − 1) × 6.625 × 10 −34 Configuration of Ne — 1s2 2s2 2p6

= ” ” Mg — 1s2 2s2 2p6 3s2
2π
” ” Cl− — 1s2 2s2 2p6 3s2 3p6
@ 2.11 × 10−34 J s. 81. de Broglie e’s wavelength
74. If E is KE of a particle, de Broglie wavelength ln = 2pr = nl
h λ1 2π r1
λ = So, =
2mE λ 4 2π r1 × 4
1 2π r4
So, if KE doubles, l becomes times
2 λ 4 = 4 λ1 =
4
11 1 ⇒ Circumference of the fourth orbit = 4l4
= RH  2 − 2 
75.
λ  n1 n2  = 16l1
As e− has double the mass in hypothetical system. 83. Shortest wavelength is possible for any series if
Rydberg’s constant in the equality will be equal to 2RH. n2 = ∞.
Longest wavelength is possible for any series if n2 = n1
1 1 1
So, = 2R  2 − 2  [transition is to the first + 1.
λ 2 3  So, for hydrogen
excited level i.e., to 2n orbit] 1 1 1 
= RH  2 − 2 
18 Xx 1 ∞ 
⇒ λ =
5R 1
⇒ RH = (i)
x
77. For, Hb line of Balmer series n1 = 2 and n2 = 4. For helium
E1 E1 1 1 1
So, hv = − = RH ⋅ Z 2  2 − 2  (ii)
n22 n12 λ 2 3 
[Here, E1 is −ve of ionization Energy] From Eqs (i) and (ii),
−34
 −2 × 10 −18  −2 × 10 −18   9x
⇒ 6.000 × 10 × v =  −   λ =
 16  4  5
⇒ v = 6.25 × 1014 = 625 × 1012 Hz 84.
78. Radius of nth orbit rn = 0.529 × n2 Å (a) In H-like systems, energy of electron in an orbital
⇒ 8.464 Å = 0.529 × n2 increases with increase in ‘n’. So, energy of 3d is
⇒ n = 4 less than energy of 4s.
(b) In d x2 − y2 orbitals cloud is along x and y-axes. So,
2π Ze 2
Velocity of e− in nth orbit = it lies in xy plane.
nh (c) Electronic configuration of Cr — 1s2 2s2 2p6 3s2
2.18 × 106 3p6 4s1 3d5
@ m/s
n (d) Except the spin quantum no. the remaining
⇒ Velocity of e−1 in 4th orbit = 545 × 103 m/s Quantum number are obtained from Schrodinger
equation.
79. Electronic configuration of Cr and Cr2+ are as given
below: Velocity of e −1 1
86. From the data = =
Cr → 1s2 2s2 2p6 3s2 3p6 4s1 3d5 Velocity of light 275
Cr+2 → 1s2 2s2 2p6 3s2 3p6 3d4
⇒ V = 1090909 m/s
So, no. of unpaired e− = 4.
Velocity of e− in nth orbit
Magnetic moment m = n( n + 2)
2.18 × 106
Vn = m/s ⇒ n=2
= 4(4 + 2) = 4.89 BM n
80. Electronic configuration of 87. If three spin quantum no. were possible, then
Fe2+ = 1s2 2s2 2p6 3s2 3p6 3d6 each orbital can accommodate 3e–. So, electronic
So, no. of d e− in Fe2+ = 6 configuration of K is 1s3 2s3 2p9 3s3 3p1.
Chapter_01.indd 76 8/17/2013 3:43:34 PM

89. For the line in ultraviolet region, the energy must be 1

more than that corresponding to E. ⇒ v = v0 × ⋅ KE
h
Energy of A > Energy of E or KE = hv − hv0
90. In the given sub shell, half of the max. no. of e– in sub y = mx − c
shell will have the same spin quantum number. So, slope of the curve m = h.
91. To find the distance at which finding probability h
97. de Broglie’ wavelength l =
dψ 2
2meV
of e– is maximum, we have to count = 0.
dr 2 from the curve, we can say that at any point lB > lA,
⇒ e − r / a0
= 0 ⇒ − In ( r / a0 ) = − In 1 means that mB < mA.
⇒ r = a0 2.18 × 106
98. Velocity of e– = m/s
n
hc So, graphic representation must be a hyperbola curve.
92. (i) KE = – Work function
λ
99. v = a (z – b)
6.625 × 10 −34 × 3 × 108
= − (2 × 1.602 × 10−19) v = az − ab
310 × 10 −9
a = slope of the curve = tan 45° = 1
= (2 × 10−19) ab = Intercept on the axis = 1
(ii) Total energy: Kinetic energy: Potential energy
⇒ v = 52 − 1 ⇒ v = 2601 s−1
− mv 2 mv 2 mv 2
:+ : −
2r 2r r Multiple Choice Questions with One
1: −1: 2 or More than One Answer
If magnitude is only considered, ratio, 1: 1: 2.
(iii) No. of maximum (or) no. of peaks 2. (a, c) From the data we can write the expression as
=n−l=5−4=1 follows:
(iv) In terms of KE (E) de Broglie’s wavelength 4.25 = WA + TA (i)
4.20 = WB + TB (ii)
h TB = TA − 1.5 (iii)
λ=
2mE h 2h
=
1 1 1 2mTB 2mTA
So, lH: lHe: λ CH4 = : :
1 4 16 ⇒ TA = 4TB (iv)
1 1 So, from above equations
1: : = 4: 2: 1 TB = 0.5 eV
2 4
TA = 2 eV
93. From the data r(n + 1) – rn = r(n – 1) WA = 2.25 eV
⇒ [(0.529) (n + 1)2] – [0.529 × n2] = (0.529)(n − 1)2 WB = 4.15 eV
⇒ n2 + 2n + 1 − n2 = n2 − 2n + 1 3. hv = hv0 + KE and stopping potential is equal to K.E.
⇒ n2 = 4n ⇒ n = 4
hc hc
94. Orbital can be represented in terms of wave function as ⇒ = + v0
‘ynlm’ and we know that in general, 0 value for m can
λ λ0
be assigned for orbital along with z axis.
hc 1
95. At nodal surface, y2 value must be equal to zero. By v0 = − hc ⋅
λ λ0
equating y2 = 0 we will get the expresion as
(2 − Zr) = 0 hc 1 hc 1
2 2 v0( eV ) = ⋅ − ⋅
⇒ r = = =1Å e λ e λ0
Z 2
y = mx − c
96. Equation for photoelectric effect 6.625 × 10 −34 × 3 × 108

So, slope = m =
hv = hv0 + KE 1.602 × 10 −19
Chapter_01.indd 77 8/17/2013 3:43:36 PM

Work function for metal = 0.24 eV 2π 2 mZ 2 e 4 R

Rydberg’s constant, R = 3 ; So, Rh =
hc ch 2
= w + v0 1. Longest wavelength is possible if transition occurs
λ
from the immediate orbit. So, the given transition is
6.625 × 10 −34 × 3 × 108 3 → 2.
⇒ v0 =
100 × 10 −9 1 1 1
So, = Rn  2 − 2 
−0.24 × 1.602 × 10−19
λ 2 3 
= 1.949 × 10−18 J = 12.1 eV R 9 − 4 72 R
= ⇒ λ=
The work function for metal II is more than metal I. 2  4 × 9  5
So, if both metals were exposed to same light, KE i.e.,
stopping potential for metal II is less than metal I. 2.188 × 106
5. (a, c) For the same magnetic moment ions (a) atoms 2. Vn = V = m/s
n
should contain same no. of unpaired e−.
16. BE = Ionization energy of H-like system 2.188 × 106
= = 1.094 × 106 m/s
2
13.6 13.6 3. r = rn × n2 = (2r) n2 = 0.529 × 2 × 9
= 2
× Z 2 = 2 × Z 2 = 13.6
n 4 = 9.522 Å
⇒ Z = 4 4. We know that KE and total energy are with
opposite sign and are of equal magnitude.
E 13.6
Comprehensive Type Questions So, KEn = − En = = = 6.8 eV/atom
2 2
Passage-I Passage-III
Based on the given conditions, 1. We know that
No. of sub shells = n + 1, and
−13.6 × 22  −13.6 
No. of orbitals in a sub shell = 2l + 3 E3 − E2 = − × Z2
That means 1st orbit consists of s and p sub shells with 9  4 
3 and 5 orbitals and 2nd orbit consists of s, p and d sub
1 1
shells with 3, 5 and 9 orbitals, respectively. So, 47.2 = 13.6 × 2  −  ⇒ Z = 5
1. EC with atomic no. 25 4 9
1s2 1p10 2s6 2p3
hc
2. EC corresponding to atomic No. 18 is 2. = (−13.6 × 25 × 1.602 × 10−19)
1s6 1p10 2s2, so it has two unpaired e− which causes a λ
magnetic moment of 8 BM. ⇒ l = 3.6489 × 10−9 m
3. After 3s, 3p and 2d have the same (n + l) values. So, 3. KE = − E = − (13.6 × 1.602 × 10−12) ergs
because of lower n value e− enters into 2d. = 5.4468 × 10−9 ergs
4. If three spin quantum no. were possible each orbital
can accommodate 3 electrons, So, configuration of Passage-IV
atom with atomic no. is From the data A is the 1st orbit and B is nth orbit. After
1s9 1p15 2s6 absorption of 2.55 eV, e−1 excites to n1 orbit. The possible
no. of spectral lines for de-excitation is Σ (n1 − 1) = 6.
Passage-II Which mass that n1 = 4 and n may be 2 (or) 3.
B ecause of half of the mass of –ve particle in
the hypothetical system. Energy, velocity, radius, From the given data En1 − En = 2.55
expression were as follows: −13.6  −13.6 
−2π 2 Z 2 me 4 E i.e., × Z2 −  2  n2 = 2.55
E = , So Ehypothetical = 16  n 
n22h2 2 The above expression is possible only if n = 2 and Z = 1.
2π Ze
V = , So Vhypothetical = V
nh 3. Minimum energy is possible due to transition of e−
from 4th orbit to 3rd orbit.
n2 h2 13.6  −13.6 
r = , So rh = 2r E = − − = 0.6611 V
4π 2 me 2 4  9 
Chapter_01.indd 78 8/17/2013 3:43:38 PM

Passage-V 3. Shortest wavelength corresponds to the transition

of ∞ → n.
hc
1. = W + KE 1 1 1  R
λ So, = RH  2 − 2  = H
λ1 2 ∞  4
 6.625 × 10 −34 × 3 × 108 1  For the longest wavelength
⇒  −10
× −19  eV
 4000 × 10 1.602 × 10  1  1 1  3R
= RH  2 − 2  = H
⇒ 2 + KE ⇒ KE = 1.10 eV λ 1 2  4
λ1
2. KE1 = hv1 − hv0 = h (10 × 1014 − 5 × 1014) ⇒ λ = = 0.33 l1
3
= h (5 × 1014)
In second case KE2 = 2KE1 Passage-IX
⇒ h (10 × 1014) = hv1 − 5 × 1014 × h The data can be represented in the form of a diagram as
⇒ v1 = 15 × 1014 s−1 follows:
3. Stopping potential is the –ve potential that must be
n
applied on collection plate to stop 1 photoelectrons.
It will be equal to KE of e− in (eV.) 10.2 eV 4.25 eV
So, V0 = 25 − 7 = 18 eV.
Passage-VI 5.95 eV
6.625 × 10 −34 × 3 × 10 2
hc 3
2. E = = = 6.625 × 10−19 J 17 eV
λ 3000 × 10 −80 2
1
Passage-VII So, En − E2 = (10.2 + 17)
1. de Broglie wavelength of a cricket ball
−13.6  −13.6 
h 6.625 × 10 −34 ⇒ × Z 2 −  2  Z 2 = 27.2
= = = 1.1 × 10−34 m n 2
 2 
mV 0.2 × 30
Similarly,
−34
h 6.625 × 10 −13.6  −13.6 
2. ∆P = = = 5.272 × 10−2 × Z 2 −  2  Z 2 = 10.2
4π ⋅ ∆x 4π × 10 −10 n 2
 3 
3. Dx = DP = m × DV By solving Eqs. (i) and (ii),
So, according to Heisenberg’s principle n = 6, Z = 3
h Passage-X
Dx × DP = m2 (DV)2 = n2 h2
4π 1. Radius r = , So for hypothetical, it can be
1 h 4π 2 mZe 2
⇒ ∆V = modified as
2m 2π
n2 h2 0.529
Passage-VIII rm = = Å
2. Longest wavelength corresponding to the transition 4π (207m) (2e)
2
414
(n + 1) → n, so in case of Lyman series the transition 2. Ionization energy is the energy of e− in first orbit with
is 2 → 1. +ve sign.
1 1 1 −2π 2 Z 2 me 4
So, = RH ⋅ Z 2  2 − 2  E = for hypothetical
λ n
 1 n2  n2 h2
1 1 1  −2π 2 Z 2 (207m) (2e)

= RH ⋅  −  Em =
λ 1 α  n2 h2
= 828 × 13.6 eV
1 912 0.529 2 2 0.529
⇒ λ = = Å = 22.8 nm 3. r3 − r1 = 3 − 1  = ×8 Å
4 RH 4 414  414
Chapter_01.indd 79 8/17/2013 3:43:41 PM

Matching Type Questions Integer Type Questions

2. Note: Molecules at very high temperature are mono- 1. After the absorption of energy, energy of
atomic gases that gives a line-spectrum. e− = −0.01 E
6. We know that −E
So −0.01 E = 2
r1 n12 Z 2 n
= × ⇒ n = 10
r2 n22 Z1 2. 1
3. Hb line is due to the transition of e− from 4 to 2
V1 Z1 n2
= × −2 × 10 −18  −2 × 10 −18 
V2 Z 2 n1 So, hv z = − 
16  4
T1 n13 Z 22 v = 6.25 × 1014 or 625
= ×
T2 n23 Z12 4. Radius of orbit rn = 0.529 × n2 = 0.8464
⇒ n = 4
K1 n22
⇒ = 2.188 × 106
K 2 n12 Velocity of e− = m/s
n
Assertion (A) and Reason (R) Type Questions = 547.00 m/s
5. Velocity of e−
1. Peaks in radial distribution curve = n − l
radial nodes = n − l − 1 2.188 × 106 3 × 108
=
Which means that the radial probability curves depend n 275
only on ‘n’ and ‘l’ and not on ‘m’. ⇒ n = 2
3. An electron can never be found in the nucleus and this 1 1 1
can be explained by uncertainty principle. 6. = RH  2 − 2 
Any object can not move with velocity of light. λ 2 n 
4. Reason is the consequence of assertion and it can not
1 1 1 1 
explain assertion. ⇒ = −
5. The shape of orbital is independent of principal 4814 912  4 n2 
quantum number. ⇒ n = 4
6. Anode rays are +ve ions of different gases and they
have different charges and masses. So, e/m ratio for 7. If l is de Broglie’s wavelength and n is principal
anode rays depends on nature of gas. quantum no,
7. y2 is the square of amplitude of e− wave and we know nl = 2prn = 2p × 0.529 × n2
..
that I ∝ a2 where I is intensity and a is amplitude. ⇒ l = 2p × 0.529 × n
8. The no. of angular nodes = l and angular wave functions ⇒ n = 4
depend on ‘I’ and m 8. Minimum value of magnetic quantum no. = −l
9. Diamagnetic nature is due to pairing of e− So, ‘l’ for the given orbital is 2.
10. In the absence of electric and magnetic fields px, py No. of angular nodes = l = 2
and pz orbitals will have same energy and transition in 9. 3rd excited state means 4th orbit. So, spectral lines in
between px and py can not give spectral line. Lyman series = n − 1 = 4 − 1 = 3
11. In case of H like systems, energy of e− can be 10. Max no. of spectral lines = Σ (n2 −n1)
determined only from ‘n’ values and all the sub shells (6 − 1) = 5
with same ‘n’ value will have same energy. hc
12. The electron can revolve in a particular orbit if it’s 11. = En2 − En1
λ
wave is in phase only. For the He, condition is nl
nh hc 1 1 
= 2pr which can be modified as mvr = . = Z 2  −  × 2.178 × 10−8
2π λ 1 4 
14. + (or) − (ve) sign indicates that electrons are with ⇒ Minimum possible number for Z = 2
opposite spins only.
15. As the orbit moves towards the nucleus, the energy hc hc
12. En2 − En1 = +
difference between successive orbits increases. λ1 λ2
Chapter_01.indd 80 8/17/2013 3:43:43 PM

 13.6  −13.6  2 ( iv) n = 3, l = 1 <

−19 
⇒  − 2 −   2 × 1.602 × 10  (ii) n = 4, l = 0 <
 n  1  (iii) n = 3, l = 2 <
(i) n = 4, l = 1
 1 1 
= 6.625 × 10−34 × 3 × 108  + 2. px orbital has only one nodal plane i.e, yz-plane
108.5 × 10
−9
30.4 × 10 −9  3. 1s2, 2s22p6; 3s23p63d5, 4s1 is ground state electronic
⇒ n = 5 configuration of Cr24
13.
hc
= w + eV0 h 6.626 × 10 −34
4. λ = =
λ mv 0.2 × 5 / 3600
⇒ w = 5 eV
6. Beam of ∝α-particles (nuclei of helium) are used in
14. Degeneracy means the total no. of degenerate orbitals.
the Rutherford’s gold leaf experiment
In H-like system all the orbitals present in a particular
7. An orbital can accommodate maximum two electrons
orbit will have the same energy. So, no. of degenerate
with opposite spin and no two electrons in the atom
orbitals (d) degeneracy
can have same values of all four quantum numbers.
n2 = 9
15. No. of visible lines means, lines in Balmer series, n2
= n − 2 = 5 − 2 = 3 8. r = × 0.529 Å
z
16. 16.2
17. l = 2pr1n For Be3+, n = 2, z = 4
\ r = 0.529 Å
6.64
⇒ n = =2 9. Number of radial nodes = (n-l-1)
2π × 0.529 Number of radial nodes for 3s = (3-0-1) = 2
18. In second period 2s, 2p orbital are to be filled with Number of radial nodes for 2p = (2-1-1) = 0
three e− in each orbital. So, total no. of elements in
second will be 12. 2π2 e 4 m h 2 e 4 m π2 m 4
10. KE = = = e
19. No. of revolutions (a) frequency 4h2 2h 2 2h 2
z2 h2
f ∝ ao = 2 2
n3 4h e m
h4
f1 Z12 n23 ∴e =
4
So, = × 16π m 2 a 2
4
f 2 Z 22 n13 h2
∴ KE =
2 1 23 32π ma 2
⇒ = × ⇒n=1
1 4 n2
20. From the data KE of e− Matching Type Questions
= 13.6 × 0.5 eV 11. (a-r) (b-q) (c-p) (d-s)
1
⇒ mv 2 = 13.6 × 0.5 × 1.602 × 10−19 − KZe 2
2 E n ( Total energy ) = ;
⇒ v = 1.5473 × 106 2r
So, the correct answer is 6. Z2 KZe 2
K n ( Kinetic energy ) = − 2 × 2.18 × 10 −18 J =
21. (6) n 2r
KZe 2
Vn = potential energy = −
r
Previous Years’ IIT Questions
n2
1. Smaller is the value of (n+l), lesser is the energy of sub rn = Radius of Orbit = × 0.5529 Å
Z
shell. When (n+l) values are same then energy of sub Vn
shell depends on the principal quantum number ‘n’; =−2
Kn
smaller will be the value of ‘n’ lesser is the energy of
sub shell. rn ∝ En−1
In the lowest orbit (1s), the angular mom
mentum
h
= l (l + 1)
2π
Chapter_01.indd 81
= 0 ( for l = 0) 8/17/2013 3:43:45 PM
n
r
2
n
rn = Radius of Orbit = × 0.5529 Å
Z
Vn
=−2
K n of Atom
1.82 Structure
rn ∝ En−1
In the lowest orbit (1s), the angular mom
mentum 15. E = E
S2 H
h Z2
= l (l + 1) − × 13.6 eV = − 13.6 eV
2π n2
= 0 ( for l = 0) Z 2 = n2
n2 Z = n = 3 for Li 2 +
rn = × 0.529 Å
Z Thus,S2 will be 3p because it has one radial node
1
∝ Z y i.e , ∝ Z 1 i.e., y = 1 For 3 p, n = 3, l = 1
rn
Number of radial node = n − l − 1 = 3 − 1 − 1 = 1
h
12. Orbital angular momentum = l (l + 1) cos θ
2π
i.e., it depends on azimuthal quantum number,
magnetic quantum number 16. Total number of electrons with (n = 3) = 2n2 = 18
Shape, size and orientation of hydrogen like atomic
Out of these 18 electrons, 9 electrons will have
orbitals is determined by principal, azimuthal and
magnetic quantum numbers  1
anticlockwise spin  ms = − 
Probability density of electron at the nucleus is  2
determined by the principal and azimuthal quantum 17. Photoelectrons are ejected only when the energy of
number absorbed quantum is greater than the threshold energy
or work function (∅) of metal.
Comprehensive Type Questions hc 6.626 × 10 −34 × 3 × 108
Absorbed Energy, E = =
13. 2s orbital is spherically symmetrical and it has one λ 300 × 10 −9
−19
radial node. 6.626 × 10
= 6.626 × 10 −19 J = eV = 4.17eV
Number of radial nodes of 2s orbital = n-l-1=2-0-1=1 1.6 × 1019
2 2 Thus, four metals, i.e., Li, Na, K, Mg will show
14. ES = − Z × 13.6 eV = − 3 × 13.6 eV = − 9 × 13.6 eV photoelectron emission.
2
1
n 22 4
2
1
EH = − 2 × 13.6 eV
1
ES1 9
∴ = = 2.25
EH 4
Chapter_01.indd 82 8/17/2013 3:43:47 PM

Wavelength corresponding to Balmer series. 2π 2 nZ 2 e 4

RH = Rydberg constant =
1 36 1 Ch3
λ 2 = × ×
RH 5 Z 2 So, energy of e− in ground state configuration
−RH × ch
1 1  36 3 
⇒ λ 2 − λ1 = ⋅ − hc
RH Z 2  5 4  52. ∆E =
λ
1 129  hc 6.625 × 10 −34 × 3 × 108
⇒ 91.2 × 2  20  = 33.4 ⇒ λ = =
Z ∆E ( ∆Ee .V . ) × 1.602 × 10 −19
⇒ Z @ 4 = 1.2406 × 10−10 m
43. From the data
53. Moseley’s equation is v = a (Z – b).
h (3.2 × 1016) = hv0 + 2E (i)
So, from the data
h (2.5 × 1016) = hv0 + E (ii)
By solving Eqs. (i) and (ii) 100 = 1 (Z − 1) ⇒ Z = 11
v0 = 18 × 1015 Hz 55. By the given condition, each primary shell should
hc consist of (n + 1) subshells. So, configuration will be
44. = E2 – E1 1s2 1p6 2s2 2p6 3s2 2d6
λ
57. No. of e– corresponding for a given l value equals to
6.625 × 10 −34 × 3 × 108 2 (2l + 1). For a given n value the possible ‘l’ values
⇒
λ are 0 to n – 1.
So, total no. of e− in a given orbit
 −13.786  −13.786   n −1
= 1.602 × 10−19  −  I = ∑ 2(2l + 1)

 4  1   i=0
= l = 1.199 × 10 m = 1200 Å −7 58. l value for g sub shell is 4.

(i) Maximum no. of m values = 2l + 1. So, for g = 9
45. Energy of e– in nth orbit of an H (ii) Maximum no. of unpaired e–1 = 2l + 1. So, for g = 9.
like system, (iii) The minimum principal quantum no. of gshell = 5.
−13.6 h
En = × Z 2 eV/atom 59. ∆x ⋅ ∆v =
n2 4π m
6.625 × 10 −27 1 5.272 × 10 −28
E Z 2 n2 ⇒ ∆x = × = cm
So, 1 = 12 × 22 4 × 3.142 × 1 2 2
E2 Z 2 n1
@ 2.64 × 10−30 m
1 4
= × = 1: 4
16 1 60. From the data
47. Electronic configuration in second excited state hc
= hv0 + E1
= 1s2 2s2 2p6 3s2 3p3 3d2 λ1
So, max (n + l + m) value for this configuration
hc
= [[(3 + 1 + (−1)] + (3 + 1 + 0) + (3 + 1 + 1)] + = hv0 + 2E1
(3 + 2 + 2) + (3 + 2 + 1)] = 25 λ2
48. In any orbit the no. of waves by an e– equals to its By substitution and on solving 1/4 and 3/4
principal quantum no. and total length of all the waves ⇒ v0 = 1.19 × 1015 s−1
must equal n circumference of the orbit. 61. From the data n1 + n2 = 4
⇒ nl = 2prn and n1 − n2 = 2
⇒ nl = 2pr (n2) ⇒ n1 = 1 and n2 = 3
51. Energy of e– in ground state So, from Rydberg’s constant
−2π 2 Z 2 me 4 1 1 1
En = = RH ⋅ Z 2  2 − 2 
n2 n2 λ n
 1 n2 
Chapter_01.indd 74 8/17/2013 3:43:30 PM

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1

Chapter_01.indd 1 8/17/2013 3:42:09 PM

exist. As a result of brilliant era in experimental physics To vacuum

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= 9.1094 × 10−31 kg (1.3)

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1.3.3 Discovery of Proton 9

If the conduction of electricity, through gases is due to

In 1898, Sir J.J. Thomson proposed that the electrons

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Chapter_01.indd 5 8/17/2013 3:42:13 PM

++ (i) An atom has a centre of the nucleus, in which posi-

Rutherford, therefore, contemplated the dynamical

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frequency of X-rays produced in this manner was related

1.6.1 Nature of Light and Electromagnetic

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(mm), nanometer (nm), picometer (pm) etc. These

λ 4. Amplitude: It is the height of crest or depth of wave’s

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Z Table 1.2 Some applications of electromagnetic waves

Electric field Name Frequency Wavelength Uses

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Solved Problem 1 1.6.2 Quantum Theory of Radiation

Distance 300 × 1000 m 1750°

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greatest at the middle wavelengths in the spectrum and

Max Planck 1858–1947

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The studies have revealed the following facts: Metal Li Na K Mg Cu Ni

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Since, 1 eV = 1.602 × 10−19 J

1.6.5 Dual Nature of Electromagnetic 1.6.6 Atomic Spectra

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Chapter_01.indd 14 8/17/2013 3:42:23 PM

Since atoms of different elements give characteris- Hydrogen Spectrum

Balmer (1885) discovered a relationship between the

Violet Blue Blue-green Red

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Table 1.3 Solution:

1 1  Born in Denmark in 1885. He received Ph.D. from

Chapter_01.indd 16 8/17/2013 3:42:25 PM

K L M NO P According to Coulomb’s law, the electrostatic force of attraction

Chapter_01.indd 17 8/17/2013 3:42:26 PM

In order that the electron’s orbit may remain stable, it 2π2 me 4 Z 2

and upon solving for r, we obtain r=

mv 2 Ze 2 The energy of an electron is usually expressed in Kcal

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Fig 1.21 Origin of emission spectrum of hydrogen atom

Chapter_01.indd 19 8/17/2013 3:42:29 PM

this work. However, Bohr’s model could not explain the

Chapter_01.indd 20 8/17/2013 3:42:29 PM

de Broglie’s equation is true for material particles of all

Meaning of y and its Significance

the wave is in phase continually. 2 2

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Chapter_01.indd 22 8/17/2013 3:42:31 PM

Chapter_01.indd 23 8/17/2013 3:42:32 PM

1.8.6 The Meaning of Wave Function