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 MARKS 1

ATOMIC STRUCTURE

1 . A T OM I C ST RU CT U RE
An atom is the smallest building block of matter. Atoms are made of neutrons, protons and
electrons. The nucleus of an atom is extremely small in comparison to the atom.
Scientists use the Periodic Table in order to find out important information about various elements.
Created by Dmitri Mendeleev (1834-1907), the periodic table orders all known elements in accordance
to their similarities. When Mendeleev began grouping elements, he noticed the Law of Chemical
Periodicity. This law states, „the properties of the elements are periodic functions of atomic number.‰
The periodic table is a chart that categorizes elements by „groups‰ and „periods.‰ All elements are
ordered by their atomic number. The a tomic number is the number of protons per a tom. In a
neutral atom, the number of electrons equals the number of protons. The periodic table represents
neutral atoms. The atomic number is typically located above the element symbol. Beneath the element
symbol is the atomic mass. Atomic mass is measured in Atomic Mass Units where 1 amu = (1/12) mass
of carbon measured in grams. The a tomic ma ss number is equa l to the number of pr otons plus
neutrons, which provides the average weight of all isotopes of any given element. This number is
typically found beneath the element symbol. Atoms with the same atomic number, but different
ma ss numbers a re ca lled isotopes. Below is a diagram of a typical cells on the periodic table.

Atomic Number
A

Element Symbol

Atomic Mass
Z

1 .1 Da l t o n ’s A t o m i c T h e o r y
John Dalton ERS (6 September 1766 ă 27 July 1844) was an English chemist meterologist and
physicist. He is best known for his pioneering work in the development of modern atomic theory, and
his research into colour blindness (sometimes referred to as Daltonism, in his honour).
Five main points of DaltonÊs Atomic Theory
Ć Elements are made of tiny particles called atoms.
Ć All atoms of a given element are identical.
Ć The atoms of a given element are different from those of any other element, the atoms of
different elements can be distinguished from one another by their respective relative weights.
Ć Atoms of one element can combine with atoms of other elements to form chemical compounds;
a given compound always has the same relative numbers of types of atoms.

ATOMIC STRUCTURE
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Ć Atoms cannot be created, divided into smaller particles, nor destroyed in the chemical process;
a chemical reaction simply changes the way atoms are grouped together.

1 .1 .1 Dr a w b a c k s o f Da l t o n ’s a t o m i c t h e o r y
Ć Ability of an atom was proved wrong, for, an atom can be further subdivided into protons,
neutrons and electrons. However an atom is the smallest particle, which takes part in chemical
ability.
Ć According to Dalton, the atoms of same element are similar in all respects. This is wrong
because atoms of some elements vary in their mass and density. Such atoms of the same
element having are called isotopes. For example, chlorine has two isotopes having mass numbers
35 and 37 a.m.u.
Ć Dalton also said atoms of different elements are different in all respects. This has been proved
wrong in certain cases like Argon and Calcium atoms, which have the same atomic mass of 40.
Such elements that have the same atomic mass are called isobar.
Ć According to Dalton, atoms of different elements combine in simple whole number ratio to form
compounds. This is not seen in complex organic compounds like sugar C12H22O13.
Ć The theory completely fails to explain the existence of allotropes. The difference in properties
of charcoal, graphite, diamond went unexplained in spite of being made up of same kind of
atoms.

1 .1 .2 M e r i t s o f Da l t o n ’s a t o m i c t h e o r y
Despite the uncertainty at the heart of DaltonÊs atomic theory, the principles of the theory survived.
To be sure, the conviction that atoms cannot be subdivided, created, or destroyed into smaller particles when
they are combined, separated or rearranged in chemical reactions is inconsistent with the existence of
nuclear fusion and nuclear fission, but such processes are nuclear reactions and not chemical reactions. In
addition, the idea that all atoms of a given element are identical in their physical and chemical properties
is not precisely true, as we know that different isotopes of an element have slightly varying weights.
Ć It has enabled us to explain the laws of chemical combination.
Ć Dalton was the first person to recognize a workable distinction between the ultimate particle
of an element (atom) and that of a compound (molecule).

1 .2 T h o m s o n ’s Ca t h o d e Ra y Ex p e r i m e n t
Even without consciously realizing it, most of us are already aware of what a cathode ray tube is.
Looking at any glowing neon sign or any Âold fashionedÊ television set, and you are looking at the modern
descendents of the cathode ray tube.
Physicists in the 19th century found out that if they constructed a glass tube with wires inserted
in both ends, and pumped out as much of the air as they could, an electric charge passed across the tube
from the wires would create a fluorescent glow. This cathode ray also became known as an Âelectron gunÊ.
Later and improved cathode ray experiments found that certain types of glass produced a fluorescent
glow at the positive end of the tube. William Crookes discovered that a tube coated in a fluorescing
material at the positive end, would produce a focused ÂdotÊ when rays from the electron gun hit it.
With more experimentation, researchers found that the Âcathode raysÊ emitted from the cathode
could not move around solid objects and so traveled in straight lines, a property of waves. However,
ATOMIC STRUCTURE
 MARKS 3

other researchers, notably Crookes, argued that the focused nature of the beam meant that they had
to be particles.
Physicists knew that the ray carried a negative charge but were not sure whether the charge could
be separated from the ray. They debated whether the rays were waves or particles, as they seemed to
exhibit some of the properties of both. In response, JJ Thomson constructed some elegant experiments
to find a definitive and comprehensive answer about the nature of cathode rays.

1 .2 .1 T h o m s o n ’s Fi r s t Ca t h o d e Ra y Ex p e r i m e n t
Ć Thomson had an inkling that the ÂraysÊ emitted from the electron gun were inseparable from
the latent charge, and decided to try and prove this by using a magnetic field.
Ć His first experiment was to build a cathode ray tube with a metal cylinder on the end. This
cylinder had two slits in it, leading to electrometers, which could measure small electric charges.
Ć He found that by applying a magnetic field across the tube, there was no activity recorded by
the electrometers and so the charge had been bent away by the magnet. This proved that the
negative charge and the ray were inseparable and interwined.

1 .2 .2 T h o m s o n ’s Ca t h o d e Ra y Se c o n d Ex p e r i m e n t
Ć Like all great scientists, he did not stop there, and developed the second stage of the experiment,
to prove that the rays carried a negative charge. To prove this hypothesis, he attempted to
deflect them with an electric field.
Ć Earlier experiments has failed to back this up, but Thomson thought that the vacuum in the
tube was not good enough, and found ways to improve greatly the quality.
Ć For this, he constructed a slightly different cathode ray tube, with a fluorescent coating at one
end and a near perfect vacuum. Halfway down the tube were two electric plates, producing a
positive anode and a negative cathode, which he hoped would deflect the rays.
Ć As he expected, the rays were deflected by the electric charge, proving beyond doubt that the
rays were made up of charged particles carrying a negative charge. This result was a major
discovery in itself, but Thomson resolved to understand more about the nature of these particles.

1 .2 .3 T h o m s o n ’s T h i r d Ex p e r i m e n t
Ć The third experiment was a brilliant piece of scientific deduction and shows how a series of
experiments can gradually uncover truths. Many great scientific discoveries involve performing
a series of interconnected experiments, gradually accumulating data and proving a hypothesis.
Ć He decided to try to work out the nature of the particles. They were too small to have their
mass or charge calculated directly, but he attempted to deduce this from how much the particles
were bent by electrical currents, of varying strengths.
Ć He found out that the mass to charge ratio was so high that the particles either carried a huge
charge, or were a thousand time smaller than a hydrogen ion. He decided upon the later and
came up with the idea that the cathode rays were made of particles that emanated from within
the atoms themselves, a very bold and innovative idea.
Ć Julius Plucker and his student Johann Hittorf were experimenting with a Geissler tube. Plucker
and Hittorf placed two electrodes at each end of the tube.

ATOMIC STRUCTURE
4 MARKS

Ć The positive plate was called the anode

Ć The negative plate was called the cathode
Ć Pumped all the air from the tube, creating a vacuum
Ć Connected wires from the electrodes to a battery

ANODE CATHODE
(+) (ă)

AMMETER

Plucker and Hittorf discovered that when electricity flowed through the Geissler
tube, a mysterious greenish glow was produced around the tube.
Sir William Crookes gained more knowledge about the mysterious green glow (ă)
when he created a bent Geissler tube in 1875. He noticed that the glow was the (+)
most intense opposite to the negative electrode, also called the cathode. Crookes
Bent Geisster Tube
reasoned that rays traveled from the cathode and then hit the end of the tube.
Because of this, Crookes named these rays cathode rays.
In later experiments Crookes placed barriers in the path of cathode rays :

(+)

Crookes Tube with Maltese Cross

Because a shadow was produced behind the barrier, Crookes reasoned that cathode rays.
Ć Acted like light
Ć Seemed to travel in straight lines
Next, Crookes was able to change the path of the rays with a magnet. This meant
Ć The cathode rays were NOT light (light is not affected my magnets or magnetic fields)
Ć Cathode rays had some sort of charge.

A f t e r f u r t h e r e x p e r i m e n t s , Cr o o k e s p r o v e d :
(1) All cathode rays have identical properties-the material the cathode is made of does not matter.
(2) Cathode rays normally travel in straight lines perpendicular to the cathode.
(3) Magnetic fields change the path of the cathode rays. (Crookes suspected that any charged
object, not just magnets, could change the path of cathode rays.)
(4) Rays caused reactions similar to those caused by light.
(5) Scientists could not decide if cathode rays were electromagnetic waves or negatively charged
particles.

ATOMIC STRUCTURE
 MARKS 5

1 .3 .1 Pl u m -Pu d d i n g M o d e l
The Plum pudding model of the atom by JJ Thomson, who discovered
the electron in 1897, was proposed in 1904 before the discovery of the
atomic nucleus. In this model, the atom is compared of electrons (which
Thomson still called „corpuscles,‰ though G.J. Stoney had proposed that
atoms of electricity be called electrons in 1894), surrounded by a soup of
positive charge to balance the electronÊs negative charge, like negatively-
charged „plums‰ surrounded by positively-charged „pudding‰. The electrons
(as we know then today) were thought to be positioned throughout the
atom, but with many structures possible for positioning multiple electrons.
A schematic representation of the plum pudding model of the atom. In ThomsonÊs mathematical
model the „corpuscles‰ (or modern electrons) were arranged non-randomly, in rotating rings.

1 .3 .2 Ru t h e r f o r d ’s M o d e l
In the year 1898 Thomson created the idea of atom as the positive charged ball in which there are
negative charges placed-the „plum cake‰ model. So summing up the whole atom were to be neutral.
In the years 1909-1911 Ernest Rutherford and his students-Hans Geiger (1882-1945) and Ernest
Marsden conducted some experiment to search the problem of alpha particles scattering by the thin
gold-leaf. Rutherford knew that the particles contain the 2e charge. The experiment caused the creation
of the new model of atom-the “planetary” model. Rutherford suggested to hit the gold-leaf with fast alpha
particles from the source 214Po. (The source R was in the lead lining F). The particles felt from the

The incident
alpha particles

The structure of the gold foil acording to

the Rutherford's atomic model.

The alpha particles propagated on the atomic nucleuses of the gold foil

ATOMIC STRUCTURE
6 MARKS

source on the gold-leaf E and were observed by the microscope M. The whole experiment was in the
metal lining A and was covered with the glass plate P. The instrument was attached to the footing B.
The gold leaf was about 5*10ă7 meter thick. The scientist knew that reckoning the scattering angle could
say much about the structure of atoms of the gold-leaf.
Rutherford made a theoretical analysis of angles of scattering in accordance with ThomsonÊs
theory of atom in accordance with his own theory. He assumed that atom consisted of positive charged
nucleus and negative charged electrons circling around the nucleus. Then his theoretic calculations he
compared with the experiment result. Alpha particles going through atom created in accordance with the
„plum cake‰ model wouldnÊt be strong abberated because the electric field in that atom wouldnÊt be
strong. In the model created by Rutherford the field is much stronger near to the nucleus, so some of alpha
particles are much more abberated. The other going in the far distance to the nucleus are almost at all
abberated. The probability that any alpha particle will hit the nucleus is small but there is such a chance.
P

R
E
F
M

Fig. 1. Marsden-Geiger experiment

The alpha particle

The alpha particle

ă ă

ă
ă ă
ă
ă
ă

Thomson's model of atom

Rutherford's model of atom

The models of the ThomsonÊs atom and RurtherfordÊs atom; and the expected aberration of alpha particle in both cases

ATOMIC STRUCTURE
 MARKS 7

The experiment showed that there are some not much abberated alpha particles but also some
abberated of a very big angle (135-150 degree). That occurrence couldnÊt be explained by some small,
added aberrations. Experiment data proved the „planetary‰ model of atom.
Between an alpha particle and an atomic nucleus there subsist an interaction - the repulsing -
according to Coulomb force :
1 2.Z e2
F . (1)
4.  . 0 r2
where (2*e)-alpha particle charged, (Ze)-atomic nucleus charged, 0 -permittivity of free space,
r-distance between the nucleus and the particle.

1 .3 .2 .1 Co n c l u s i o n s
Summarising the results of his work Rutherford came to the opinion that atom consisted of a
nucleus (of size 10ă15 to 10ă14 meter). The nucleus contains the whole positive charge and almost the
whole atomÊs mass. Around the nucleus, on the area of the size of the order of 10ă10 meter, light
electrons are circling. Electrons have to circle around the nucleus on orbits, not to fell down on the
nucleus. The orbits depend on electrons energy. In atoms of the same element, electrons circle on the
same characteristic, for that element, orbits i.e. the optical spectrum of atoms of the same element is
the same.

The proton (the nucleus)

The electron
v

The Rutherford's atomic model. The electron circulating on the orbit

around the nucleus with the velocity v is attracted by it with the force F
1 .3 .2 .2 Dr a w b a c k s
The model created by Rutherford had still some serious discordance. According to the classic
science, electron moving around the nucleus should emit an electromagnetic wave. That kind of emission
is connected with the escape of some energy from the electron-ion circuit. Electron should then move
not by the circle but helical and finally collide with the nucleus. But atom is stable. Other discordance
regarded the radiation-it were to be constant (because the time of electronÊs cycle in accordance with
the lost of energy should change constantly) and spectral lines shouldnÊt occur.

v
The nucleus
The electron

In the planetary model of atom, the electron should

emit energy and spirally fall on the nucleus.
ATOMIC STRUCTURE
8 MARKS

1 .3 .3 B o h r ’s M o d e l o f a n A t o m
RutherfordÊs model had a major drawback. It could not explain why ultimately electrons did not
fall into the nucleus by taking a spiral path. This was in concurrence with the electromagnetic theory
that states Âif a charged particle undergoes accelerated motion then it must radiate energy
(lose) continuouslyÊ.
In order to explain the stability of an atom Neils Bohr in 1913 gave a new arrangement of electrons
in the atom. According to Neils Bohr, the electrons could revolve around the nucleus in only
Âcertain orbitsÊ (energy levels), each orbit having a different radius. When an electron is revolving
in a particular orbit or particular energy level around the nucleus, the electron does not radiate energy
(lose energy) even though it has accelerated motion around the nucleus.
Arrangement of energy levels around the nucleus
4 N Shell
3 M Shell
2 L Shell
1 K Shell
+ Positively charged
Nucleus
K
L
M
N
Arrangement of energy levels around the nucleus

1 .3 .3 .1 Co n c e p t i n v o l v e d
An atom is made up of three particles, electrons, protons and neutrons. Electrons have a negative
charge and protons have a positive charge whereas neutrons have no charge. They are neutral. Due to
the presence of equal number of negative electrons and positive protons the atom as a whole is electrically
neutral.
Ć The protons and neutrons are located in a small nucleus at the centre of the atom. Due to the
presence of protons the nucleus is positively charged.
Ć The electrons revolve around the nucleus in fixed circular paths called energy levels or shells.
The Âenergy levelsÊ or ÂshellsÊ or ÂorbitsÊ are represented in two ways : either by the numbers
1, 2, 3, 4, 5 and 6 or by letters K, L, M, N, O and P. The energy levels are counted from centre
outwards.
Ć Each energy level is associated with a fixed amount of energy. The shell nearest to the nucleus
having minimum energy and the shell farthest from the nucleus having maximum energy.
Ć There is no change in the energy of electrons s long as they keep revolving in the same energy
level. But when an electron jumps from a lower level to a higher one, some energy is absorbed
while some energy is emitted. When an electron jumps from a higher energy level to a lower
one, the amount of energy absorbed or emitted is given by the difference of energies associated
with the two levels. Thus if an electron jumps from orbit 1 (energy E1) to orbit 2 (energy E2)
the change in energy is given by E2 ă E 1. The energy change is accompanied by absorption of
radiation energy of E = E2 ă E1 = h  where h is a constant called ÂPlanckÊs constantÊ and 

ATOMIC STRUCTURE
 MARKS 9

is the frequency of radiation absorbed or emitted. The value of h is 6.626 ï 10ă34 J-s. The
absorption and emission of light due to electron jumps are measured by use of spectrometers.
This model of the atom was able to explain the stability of the atom. It also explained the phenomenon
of atomic spectra and ionization of gases.
Combining of energy of the classical electron orbit with the quantization of angular momentum, the
Bohr approach yields expressions for the electrons orbit radii and energies.

mv2  mv2 n2 h2 Ze2

  
2 2mr2 82 mr2 8 0 r
This is for hydrogenic atoms; the
kinetic expressed Use quantization Set equal to use of the atomic number Z is
energy of in terms of of angular total energy appropriate only if there is only
electron angular momentum of classical
momentum orbit
one electron.

Substitution for r gives the Bohr energies and radii :

Z 2 me4  13.6Z 2 n 2h 2 0 n 2a0

E   eV & rn  
8n 2h 202 n 2
zxme2 z

a0 = 0.0529 nm = Bohr radius

1 .3 .3 .3 A n g u l a r M o m e n t u m Qu a n t i za t i o n
In the Bohr model, the wavelength associated with the electron is given by the DeBroglie relationship.

h

mv
and the standing wave condition that circumference = whole number of wavelengths. In the hydrogenic
case, the number n is the principal quantum number.
2r = n n
These can be combined to get an expression for the angular momentum of the electron in orbit. (Note
that this assumes a circular orbit, a generally unwarranted assumption.)

hr hr nh
L  mvr   
  2r  2 (used in Bohr orbit)
 n 

Thus L is not only conserved, but constrained to discrete values by the quantum number n. This
quantization of angular momentum is a crucial result and can be used in determining the Bohr orbit
radii and Bohr energies.
The velocity of an electron in the nth state V n is :

2KZe2 z
Vn   2.165  106 m/s
nh n

ATOMIC STRUCTURE
10 MARKS

1 .3 .3 .3 En e r g y Co n s i d e r a t i o n s
Classical Electron Orbit
NewtonÊs Second Law Kinetic Energy T
e
ă
mv2 Ze 2 mv2 Ze2
= r  So T 
F 4 0 r2 2 8 0 r
centripetal
+ Ze Potential Energy Total Energy

 Ze 2  Ze2
U T U 
4 0 r 8 0 r

The orbit energy is negative This is the energy of a single electron

because this is a bound state. in orbit around a bare nucleus.

Note : The total energy of the electron is negative because of attraction of electron by the nucleus.
In the Bohr theory, this classical result was combined with the quantization of angular momentum
to get an expression for quantized energy levels.
Substituting the value of r and x, we get the following reaction.

 2 2 K2 e4 m Z2 Z2
En   2.178  10 18 J/atom
n2h 2 n2

Z2
Also En  13.6
n2 
e V 1eV =1.6 1019 J 
Note : The value of En in terms of eV is more important.

1 .3 .3 .4 El e c t ro n T r a n s i t i o n s
The Bohr model for an electron transition in hydrogen between quantized energy levels with
different quantum numbers n yields a photon by emission with quantum energy.
E2 Ephoton = hv = E2 ă E 1
n2 A downward transition involves emission of a
photon of energy
n1 E1

Given the expression for the energies of the hydrogen electron states :
2 2 me2 k2  1 1   1 1 
hv    2  2    13.6Z2  2  2  eV
h2  n1 n2   n1 n2 
This is often expressed in terms of the inverse wavelength or „wave number‰ as follows :

1  1 1  22 me4 k2
= R H  2  2  where R H  is called the Rydberg constant.
  n 1 n 2  C h3
RH = 1.0973731 ï 10 7 m ă1 .
ATOMIC STRUCTURE
 MARKS 11

Ex a m p l e 1
Determine the frequency of revolution of the electron in 2nd BohrÊs orbit in hydrogen atom.
Solution :

1
The frequency of revolution of electron is given by : frequency =
time period

total distance covered in 1 revolution 2 r

Time period = 
velocity v
v
Hence frequency =
2 r
First we will have to calculate velocity (v) and radius (r) of electron in second BohrÊs orbit by using
the standard relations for v and r. (Z = 1 for H-atom)

n2h2
rn   (0.53  10 10 n 2 )m
2 2
4 me K
Now, n = 2
r2 = 0.53 ï 10 ă10 (2)2m = 2.12 ï 10 ă10 m

2Ke2 2.165 106

vn = = m/s
nh n

2.165 106
v2 = = 1.082 ï 10 6
n
v2 1.082  10 6
Hence frequency = 
2r2 2()(2.12  1010 )
 = 8.13 ï 1014 Hz.

Ex a m p l e 2
The Velocity of electron in a certain BohrÊs orbit of H atom bears the ratio 1:275 to the
Velocity of Light :
(a) What is the quantum number (n) of the orbit ?
(b) Calculate the wave number of radiations emitted when electron jumps from (n + 1)
state to ground state.
Solution :

1
Velocity of electron =  velocity of light
275

1
=  3 ï 1010 = 1.09 ï 108 cm secă1
275
2 e2
Since, un =
nh
ATOMIC STRUCTURE
12 MARKS

2  3.14  (4.803  10 10) 2

 1.09 ï 108 =
6.625 10 27 n

n = 20.06 ï 10ă1  2
Also when electron jumps from (n + 1) i.e. 3, to ground state

v 1 1 1 
=  RH  
2
(wave number)  1 32 

1 1 
= 109678   
1 9 

= 9.75 ï 10 4 cmă1

1 .3 .3 .5 En e r g y L e v e l s o f H y d ro g e n A t o m
The spectrum of H-atom studied by Lyman, Balmer, Paschen, Brackett and Pfund can now be
explained on the basis of BohrÊs Model.
It is now clear that when an electron jumps from a higher energy state to a lower energy state,
the radiation is emitted in form of photons. The radiation emitted in such a transition corresponds to
the spectral line in the atomic spectra of H-atom.

Spectral Lines & Energy Levels of H-atom

n = 6
n = 5
p fund n = 4
Brackett n = 3
Paschen n = 2
Balmer

Lyman
n=1

L y m a n Se r i e s
When an electron jumps from any of the higher state to the ground state or Ist state (n = 1), the
series of spectral lines emitted lies in ultra-violet region and are called as Lyman Series. The
wavelength (or wave number) of any line of the series can be given by using the relation :

 1 1 
v  RZ 2  2  2  n2 = 2, 3, 4, 5, ...
1 n2 


Note : For H-atom, Z = 1, He + ion, Z = 2 & Li2+, Z = 3

ATOMIC STRUCTURE
 MARKS 13

B a l m e r Se r i e s
When an electron jumps from any of the higher states to the state with n = 2 (IInd state), the series
of spectral lines emitted lies in visible region and are called as Balmer Series. The wave number
of any spectral line can be given by using the relation :

 1 1 
v  RZ2  2  2  n2 = 3, 4, 5, ...
2 n
 2 

Pa sc h e n Ser ie s
When an electron jumps from any of the higher states to the state with n = 3 (IIIrd state), the
series of spectral lines emitted lies in near infra-red region and are called as Paschen Series. The
wave number of any spectral line can be given by using the relation :

 1 1 
v  RZ2  2  2  n2 = 4, 5, 6 ...
3 n 
 2 

B r a c k e t t Se r i e s
When an electron jumps from any of the higher states to the state with n = 4 (IVth state), the
series of spectral lines emitted lies in near in far infra-red region and are called as Brackett
Series. The wave number of any spectral line can be given by using the relation :

 1 1 
v  RZ2  2  2  n2 = 5, 6, 7 ...
4 n 
 2 

Pf u n d Se r i e s
When an elelctron jumps from any of the higher states to the state with n = 5 (Vth state), the series
of spectral lines emitted lies in far infra-red region and are called as P fund Series. The wave
number of any spectral line can be given by using the relation :

 1 1 
v  RZ2  2  2  n2 = 6, 7 ...
5 n 
 2 

Ex a m p l e 3
Estimate the wavelength of second line in Balmer series.
Solution :
The transition responsible for second Balmer line is
4  2, so n1 = 2, n 2 = 4

 1 1 
   2.55e V
E = 13.6 Z  n2 
2
2
 1  n2



ATOMIC STRUCTURE
14 MARKS

hc 6.63  10 34  3  108

Now  
E 2.55  1.6  10 19
  = 4.862 ï 10ă7 m = 4862 Å
Important Note : In any series,
first line = transition from (n1 + 1)  n 1; also called as -line & so on.
For example : In Lyman series -line = 2  1; -line = 3  1; -line = 4  1

Ex a m p l e 4
Calculate the shortest and longest warelength in H speetrum of lyman series RH = 109678 cm ă1
Solution :
For lyman series n 1 = 1
For shortest of lyman series; energy difference in two levels showing transition should be maximum,
i.e., nz = 

1
= RH  1  1 
 

  2 
1
= 109678

  = 911.7 ï 10ă8 cm = 911.7AĈ
For longest of lyman series; energy difference in two levels showing transition should be minimum,
i.e., n2 = 2

1
= RH  1  1   109678  3
 
 2 2 4
1 2 
  = 1215.67 ï 10 cm = 1215.67 AĈ
ă8

1 .3 .3 .6 H y d r o g e n En e r g y L e v e l s
The basic hydrogen energy level structure is in agreement with the Bohr model. Common pictures
are those of a shell structure with each main shell associated with a value of the principal quantum
number n.
Electron energy Electron
Orbit Radius
ă13.6eV Wavelength Ionization
E= r = n 2 a0 = 2na0 n=5 energy
n2
n=4
n=3 ă1.5 eV
n=2
n=2 ă3.4 eV
n=3 n=4 n=5
n=1

a0 = 0.0529nm = Bohr radius

n=1 ă13.6 eV

ATOMIC STRUCTURE
 MARKS 15

This Bohr model picture of the orbits has some usefulness for visualization so long as it is realized
that the „orbits‰ and the „orbit radius‰ just represent the most probable values of a considerable range
of values. If the radial probabilities for the states are used to make sure you understand the distributions
of the probability, then the Bohr picture can be superimposed on that as a kind of conceptual skeleton.
H y d r o g e n En e r g y L e v e l Pl o t
The basic structure of the hydrogen energy levels can be calculated from the Schrodinger equation.
The energy levels agree with the earlier Bohr model, and agree with experiment within a small fraction
of an electron volt. The significance of the zero in
energy is that the electron is -.278 n=7
free from the hydrogen nucleus. -.378 n=6
Electron is free -.544 n=5
0 n=4 5 6 7 -.850 n=4
n=3 -1.511 n=3
-2.0
n=2 -3.4 n=2
-4.0
Binding energy (eV)

-6.0 Scaled plot of hydrogen levels electron volts.

-8.0 ă13.6eV The levels get closer together

E=
n2 as they approach the lonization
-10.0 energy.

-12.0 Electron is bound in atom

n=1 Ground state of the hydrogen electron
-14.0 -13.6 n=1

HYDROGEN SPECTRUM

Lyman Series Balmer Series

(Ultraviolet) (Visible)
410.2nm
violet

n=2
434.1 nm violet
n=4 n=5
n=1
n=3
656.3 nm
red
Pachen Series
(infrared)
486.1 nm
bluegreen

ATOMIC STRUCTURE
16 MARKS

This spectrum was produced by exciting a glass tube of hydrogen gas with about 5000 volts from
a transformer. It was viewed through a diffraction grating with 600 lines/mm.

Qu a n t i ze d En e r g y St a t e s
The electrons in free atoms can be found in only certain discrete energy states. These sharp energy
states are associated with the orbits or shells of electrons in an atom, e.g., a hydrogen atom. One of the
implications of these quantized energy states is that only certain photon energies are allowed when
electrons jump down from higher levels to lower levels, producing the hydrogen spectrum. The Bohr
model successfully predicted the energies for the hydrogen atom, but had significant failures that were
corrected by solving the Schrodinger equation for the hydrogen atom.

n=4 Energy n=4

n=3
Levels
n=2 of n=3
Hydrogen
n=2
Violet

Red Bluegreen
n=1
Visible light transitions
of the hydrogen atom
shell or
"orbits"
of electron

1 .3 .3 .7 Fa i l u r e s o f t h e B o h r M o d e l
While the Bohr model was a major step toward understanding the quantum theory of the atom,
it is not in fact a correct description of the nature of electron orbits. Some of the shortcomings of the
model are :
1. It fails to provide any understanding of why certain spectral lines are brighter than others.
There is no mechanism for the calculation of transition probabilities.
2. The Bohr model treats the electron as if it were a miniature planet, with definite radius and
momentum. This is an direct violation of the uncertainty principle which dictates that position
and momentum cannot be simultaneously determined.
The Bohr model gives us a basic conceptual model of electrons orbits and energies. The precise
details of spectra and charge distribution must be left to quantum mechanical calculations, as with the
Schrodinger equation.

ATOMIC STRUCTURE
 MARKS 17

Ex a m p l e 5
Calculate the energy emitted when electrons of 1.0 gm atom of Hydrogen undergo transition
giving the spectral lines of lowest energy in visible region of its atomic spectra. Given that,
RH = 1.1 ï 107 mă1, c = 3 ï 108 m/sec, h = 6.625 ï 10ă34 J sec.
Solution :
Visible region of H-spectrum correspond to Balmer series n1 = 2, n2 = 3 (for minimum energy transition),

 1 1 
1 /   RH  2  2 
 n1 n2 

1 1 1
  RH  2  2 
 2 3 

7
1  1 1  1.1 10  5
  1.1 107    
 4 9  4 9

 = 6.55 ï 10ă7

hc 6.625  10 34  3  108

E 
 6.55 10 7

= 3.03 ï 10ă19 joule / molecule

 Energy released by 1 gm atom of H (1 mol)
= En = 3.03 ï 10 ă19 ï 6.023 ï 1023 = 18.25 ï 104 J = 182.5 kJ

Ex a m p l e 6
A doubly ionized Lithium atom is hydrogen like with atomic number 3.
(i) Find the wavelength of radiation required to excite the electron in Li++ from the first
to the third Bohr Orbit. (Ionization energy of the hydrogen atom equal 13.6 eV).
(ii) How many spectral lines are observed in the emission spectrum of the above excited
system?
Solution :

 13.6Z 2
(i) En  , Z = 3, n2 = 3, n1 = 1
n2

1 1
Excitation energy, E = E 3 ă E1 = ă 13.6 ï 32  2  2 
3 1 
= + 13.6 ï 9 [1 ă 1/9]
= 13.6 ï 9 ï 8/9 = 108.8 eV

ATOMIC STRUCTURE
18 MARKS

hc 6.63 10 34  3  108

Wavelength,  = E 
13.6  8  1.6  10 19
= 114.26 ï 10ă10 m = 114.3 Å
(ii) From the excited state (E3), coming back to ground state, there can be 3 possible radiations.

Ex a m p l e 7
Wavelength of high energy transition of H-atom is 91.2 nm. Calculate the corresponding
wavelength of He+ ion.
Solution :
For H atom

1  1 1
 R H 2  2  ... (i)
n n n2 
 1

1  1 1 
For He + ion   RH Z2  2  2 ... (ii)
n n2 
He  1
By eq. (i) and (ii)

He  1
 2
H Z

1 1
 He+ =  H ï 2 = 91.2 ï
Z 22
= 22.8 nm

Ex a m p l e 8
 21.7  10 12
The electron energy in hydrogen atom is given by E  ergs. Calculate the energy
n2
required to remove an electron completely from n = 2 orbit. What is the longest wavelength
(in cm) of light that can be used to cause this transition?
 21.7  1012
Solution : En  ergs
n2
 21.7  10  12
E2 
22
Removing the electron completely from the atom implies that the electron has been exited to the
level .

 21.7  1012
 E  0
2
21.7  10 12
E = E  E 2  ergs
4

ATOMIC STRUCTURE
 MARKS 19

21.7  10  12
E =  107 Joule = 5.425 ï 10ă19 J
4

hc
E =


hc 6.626  10 34  3  108

        = E   3.66414  10  7
19
5.425  10
        = 3664.14 Å

Ex a m p l e 9

There is a hydrogen atom in the ground state. It is exited to a higher energy level n. When
the electron comes back to the ground state, it emits radiation. What is the maximum number
of unique wavelengths it can emit?

Solution :

n=1

Let us imagine the electron to be in the energy level n. When it comes to the ground state it can come
in many no. of ways. Either it will directly come to n = 1, in which case it will emit only one wavelength
(corresponding to n to 1) or it can fall to n = 2 and then from n = 2 to n = 1, in which case it will emit
two unique wavelengths (one corresponding to n to 2 and the other corresponding to n = 2 to n = 1) and
so on. We have to find how the electron must come back by emitting maximum number of unique
wavelengths. It is very clear that every jump of the electron would radiate a unique wavelength as

1 1 1 
 R 2  2
  n1 n2 

 cannot be same for different sets of n1 and n 2.

The only way maximum wavelengths can be emitted is when the electron comes back to ground
state by maximum jumps. This means the electron must jumps stepwise i.e., n to n ă 1 to n ă 2 to n
ă 3 and so on. This means the total jumps would be n ă 1 and so would be the number of unique
wavelength.

 n ă1

ATOMIC STRUCTURE
20 MARKS

Ex a m p l e 1 0
Calculate the wavelength and wave number of the spectral line when an electron in H-atom
falls from higher energy state n = 3 to a state n = 2. Also determine the energy of a photon
that can remove the electron from state n = 2. Compare it with the energy of photon required
to remove the electron from ground state.
Solution :
Now there are two ways of solving this problem. One by using the relation for the energy emitted
(E) by an electron and then calculating the wavelength and wave number. Other by directly using the
expression for wave number and then calculating wavelength. In the second method, the value of
Rydberg constant (R) is required. The value of R should be given to you otherwise its value cannot be
used and the problem should be done by the former method i.e. by finding E.

 1 1 
E  2.17  10 18 Z 2  2  J
 n1  n  2 
 2 

 1 1
E  2.17  1018  2  2  = 3.04  10 19 J
2 3 

Now E = h = hc / 


hc

 
6.63  10 34 3  10 8 
 19
E 3.04  10
 = 6.59 ï 10ă7 m = 6590 Å

1 1
 v  m 1 = 1.517 ï 106 m ă1
 659  10 7

Alternative Method :
To be used only when the value of R is given.

Using the relation for wave number v : 

 1 1 
v  RZ2   
  n  2  n 2 
 1 2 

 1 1 
= 1.097 ï 107 ï (1)2  2  2  (R = 1.097 ï 10 7 mă1)
2 3 

= 1.52 ï 106 mă1

Hence  = 1/v = 6.56 ï 10ă7 m/s = 6560 Å

ATOMIC STRUCTURE
 MARKS 21

To remove electron from n = 2, the responsible transition will be n = 2  n = .

 1 1  19
E = 2.17 ï 10 ă18  2  2   5.42  10 J
2  

To remove electron from ground state (n = 1), the transition is n = 1  n = .

 1 1  18
E = 2.17 ï 10 ă18  2  2   2.17  10 J
1  

Ex a m p l e 1 1
A hydrogen atom in the ground state is hit by a particle exciting the electron to 4s orbital.
The electron then drops to 2s orbital. What is the frequency of radiation emitted and absorbed
in the process?
Solution :

Energy is absorbed when electron moves from ground state (n = 1) to 4s orbital (n = 4).

 1 1 
  eV
E = 13.6 Z  2 
2
2  (E : energy absorbed)
 n1  n2  

Putting n1 = 1 & n2 = 4 we get,

E = 12.75 eV = 12.75 (1.6 ï 10ă19) J = 2.04 ï 10ă18 J

E 2.04  10 18
frequency () = h   3.07  1015 Hz
6.63  1034

When electron jump from n = 4 to n = 2 (2s), energy is emitted and is given by the same relation :

Put n1 = 2, n2 = 4 in the expression of E.

E = 2.55 eV = 4.08 ï 10ă19 J

  = E/h = 6.15 ï 1015 Hz

ATOMIC STRUCTURE
22 MARKS

Ex a m p l e 1 2
Calculate the wavelength of light radiation that would be emitted, when an electron in the
fourth BohrÊs orbit of He+ ion falls to the second BohrÊs orbit. To what transition does this-
light radiation correspond in the H-atom ?
Solution :
Let us calculate E first

 1 1 
E = 21.7 ï 10ă19 Z2  2  2 
 n1 n2 
substituting n1 = 2 and n 2 = 4, Z = 2 we get;
E = 1.632 ï 10ă18 J
hc
Now   1.218  10 7 m  1218 Å
E
The value of  = 1218 Å implies that, in H-atom this transition would lie in Lyman Series.
Hence our aim is now to find the transition : n2  1

 1 1 
 E = 21.7 ï 10ă19 ï 12  2  2 
 n1 n2 

 1 
 1.632 ï 10ă18 = 21.7 ï 10 ă19  1  2 
 n2 

 n2 = 2
Hence the corresponding transition in H-atom is 2  1.

Ex a m p l e 1 3
1.8 g hydrogen atoms are excited to radiations. The study of spectra indicates that 27% of the
atoms are in IIIrd energy level and 15% of atoms in IInd energy level and the rest in ground
state. IP of H is 13.6 eV. Calculate
(a) No. of atoms present in III and II energy level.
(b) Total energy evolved when all the atoms return to ground state.
Solution : 1 g H contains = N atoms
 1.8 H contains = N ï 1.8 atoms
= 6.023 ï 1023 ï 1.8
= 10.84 ï 1023 atoms

10.84  10 23  27
(a)  No. of atoms in III shell =
100

= 292.68 ï 1021 atoms

ATOMIC STRUCTURE
 MARKS 23

10.84  10 23  15
 No. of atoms in II shell =
100

= 162.6 ï 1021 atoms

10.84  10 23  58
and No. of atoms in I shell =
100

= 628.72 ï 1021 atoms

(b) When all the atoms return to I shell, then

E'   E 3  E1  292.68  1021

 13.6 
=   13.6  1.602  10 19  292.68  1021
 9 

= 5.668 ï 105 Joule

E´´ = (E 2 ă E1 ) ï 162.6 ï 1021

 13.6 
=   13.6   1.602  10 19  162.6  10 21
 4 

= 2.657 ï 105 Joule

 E = E´ + E´´ = 5.668 ï 105 + 2.657 ï 105 Joule
= 832.50 kJ

Ex a m p l e 1 4
Find out the energy of H atom in first excitation state. The value of permittivity factor 4
0
= 1.11264 ï 10ă10 C 2 Nă1 mă2 .

Solution :

In M.K.S. system

22 Z2 me4
En  2  n = 2
4 0  n2 h2

=
2 2

2   3.14   1  9.108  1031  1.602  10 19 
2 2
 1.11264  10  10 2

  2  6.625  1034 
= 5.443 ï 10ă19 Joule

ATOMIC STRUCTURE
24 MARKS

1 .4 DU A L N A T U RE OF M A T T ER
Wave-particle duality is the concept that all matter and energy exhibits both wave-like and particle-
like properties. A central concept of quantum mechanics, duality addresses the inadquacy of classical
concepts like „particle‰ and „wave‰ in fully describing the behaviour of small-scale objects. Various
interpretations of quantum mechanics attempt to explain this ostensible paradox. Wave-particle duality
should be distinguished from wave-particle complementarity, the latter implying that matter can
demonstrate both particle and wave characteristics, but not both at the same time (that is, not within
one and the same experimental arrangement).

1 .4 .1 d e B r o g l i e Wa v e l e n g t h
The energy of an object (E) in motion is equal to its mass (m) times the square of its speed (s).
E = mc2
The energy of a wave (E) is proportional to its frequency (v) which is proportional to its speed (s)
and inversely proportional to its wavelength () where h is PlanckÊs constant.

hc
E = hv =

If an object acts as both a particle in motion and a wave, then the two equations can be combined :

hc
mc 2 

Cancelling like terms and rearranging the equation to solve for the wavelength results in the
following:

h

mc
By definition, momentum (p) of an object is equal to the product of its mass (m) times its speed (c),
so p can be substituted for mc to get the de Broglie equation.
Ć de Broglie equation ă The wavelength () of an object in motion is inversely proportional to
its momentum (p) where h is PlanckÊs constant (6.626 ï 10ă34 J-S).
h

p
With this equation, if the mass of an object is too large (as it is with most objects), the wavelength
would be negligible. Very small particles such as electrons, however, are small enough to exhibit
the properties of both waves and particles.

1 .5 H EI SEN B ERG’S U N CERT A I N T Y PRI N CI PLE

In this work on formulating quantum mechanics, Werner Heisenberg postulated his uncertainty
principle, which states :

h
xp 
2

ATOMIC STRUCTURE
 MARKS 25

where
 here indicates standard deviation, a measure of spread or uncertainty;
x and p are a particleÊs position and linear momentum respectively.
h is the reduced PlanckÊs constant (PlanckÊs constant divided by 2).
Heisenberg originally explained this as a consequence of the process of measuring : Measuring
position accurately would disturb momentum and vice-versa, offering an example (the „gamma-ray
microscope‰) that depended crucially on the de-Broglie hypothesis. It is now thought, however, that this
only partly explains the phenomenon, but that the uncertainty also exists in the particle itself, even
before the measurement is made.

Ex a m p l e 1 5
An electron is accelerated through a potential difference of V volts. Find the debroglie
wavelength associated with the e.
Solution :
When the electron is accelerated through a potential difference of V volts, it acquires a kinetic
energy given by E = eV, where e is the charge on the electron. Also, if m be its mass and v be the velocity
then,

1 2E
E mv2  v
2 m
h
deBroglie wavelength  
mv
h
 
2 Em

Note : The above result can be used directly, whenever required.

In the given case E = eV
h



2 eV m 

Ex a m p l e 1 6
Calculate the uncertainty in position assuming uncertainty in momentum within 0.1% for :
(a) a tennis ball weighing 0.2 kg and moving with a velocity of 10 m/s
(b) a electron moving in an atom with a velocity of 2 ï 10 6 m/s
Solution : Using Uncertainty Principle,

h
x p 
4

(a) p = mv = 0.2 ï 10 = 2.0 Kgm/s

p = 0.1% of p = 2 ï 10ă3

ATOMIC STRUCTURE
26 MARKS

h 6.63  10  34
 x  
4p 4  3.14  2  10 3

= 2.135 ï 10ă32 m
(b) For an electron, p = m v
= 9.1 ï 10ă31 ï 2 ï 106
= 1.82 ï 10ă24 Kgm/s
p = 0.1% of p = 1.82 ï 10ă27 Kgm/s
h 6.63  10  34
x  
4p 2  3.14  1.82  10 21
 x = 2.89 ï 10ă8 m

Ex a m p l e 1 7
Show that the circumferenceof an orbit of Bohr hydrogen atom is an integral multiple the
de Broglie wavelength associates with the electron revolving round the nucleus.
Solution :
According to BohrÊs postulates,

nh
mvr 
2

nh
 the circumference, 2r =
mv

h
From de BroglieÊs equation 
mv

 2r = n

Ex a m p l e 1 8
(a) If a 1 g body is travelling along the x-axis with an uncertainity in veocityof 1 cm/s, what
is theoretical uncertainty in its position ? (b) If an electron is traveling with uncertainity
in velocity of 1 m/s, what is the theoretical uncertainity in its position ?
Solution :
(a) According the uncertainity
h
x  m v 
4

x 
4 mv

ATOMIC STRUCTURE
 MARKS 27

6.626  10 27 ergs sec

=
4  3.14 1g 1cms  1
= 5.275 ï 10ă28 cm = 5.275 ï 10ă30 m

6.626 10  34 Js
(b) x 
4 3.14  9.110 31 kg 1 ms 1

= 5.797 ï 10ă5 m

1 .6 PH OT OEL ECT RI C EFFECT

1 .6 .1 I n t r o d u c t i o n
The photoelectric effect is a phenomenon in which electrons are emitted from matter after the absorption
of energy from electromagnetic radiation such as X-rays or visible light. The emitted electrons can be
referred to as photoelectrons in this context. The effect is also termed the Hertz Effect, due to its
discovery by Heinrich Rudolf Hertz, although the term has generally fallen out of use.
Photoelectric effect takes place with photons with energies of about a few electronvolts. If the
photon has sufficiently high energy, Compton scattering (ă keV) or pair production (ă MeV) may take
place.
Study of the photoelectric effect led to important steps in understanding the quantum nature of
light and electrons and influenced the formation of the concept of wave-particle duality.

Photoelectric effect

- -

- - - - - -
-
- - - -

The term may also refer to the photoconductive effect (also known as photoconductivity or
photoresistivity), the photovoltaic effect, or the photoelectrochemical effect.

1 .6 .2 Co n c e p t
When a metallic surface is exposed to electromagnetic radiation above a certain threshold frequency
(typically visible light), the light is absorbed and electrons are emitted. In 1902, Philipp Eduard Anton
von Lenard observed that the energy of individual emitted electrons increased with the frequency, or
color of the light. This was at odds with James Clerkk MaxwellÊs wave theory of light, which predicted
that the electron energy would be proportional to the intensity of the radiation. In 1905, Einstein solved

ATOMIC STRUCTURE
28 MARKS

this paradox by describing light as composed of discrete quanta, now called photons, rather than
continuous waves. Based upon Max PlanckÊs theory of black-body radiation, Einstein theorized that the
energy in each quantum of light was equal to the frequency multiplied by a constant, later called
PlanckÊs constant. A photon above a threshold frequency has the required energy to eject a single
electron, creating the observed effect. This discovery led to the quantum revolution in physics and
earned Einstein the Nobel Prize in 1921.
The photons of a light beam have a characteristic energy determined by the frequency of the light.
In the photoemission process, if an electron within some material absorbs the energy of one photon and
thus has more energy than the work function (the electron binding energy) of the material, it is ejected.
If the photon energy is too low, the electron is unable to escape the material. Increasing the intensity
of the light beam increases the number of photons in the light beam, and thus increases the number
of electrons emitted, but does not increase the energy that each electron possesses. Thus the energy of
the emitted electrons does not depend on the intensity of the incoming light, but only on the energy of
the individual photons.
Electrons can absorb energy from photons when irradiated, but they follow an „all or nothing‰
principle. All of the energy from one photon must be absorbed and used to liberate one electron from
atomic binding, or the energy is re-emitted. If the photon energy is absorbed, some of the energy
liberates the electron from the atom, and the rest contributes to the electronÊs kinetic energy as a free
particle.

1 .6 .3 Ex p e r i m e n t a l r e s u l t s
1. For a given metal and frequency of incident radiation, the rate at which photoelectrons are
ejected is directly proportional to the intensity of the incident light.
2. For a given metal, there exists a certain minimum frequency of incident radiation below which
no photoelectrons can be emitted. This frequency is called the threshold frequency.
3. Above the threshold frequency, the maximum kinetic energy of the emitted photoelectron is
independent of the intensity of the incident light but depends on the frequency of the incident
light.
4. The time lag between the incidence of radiation and the emission of photoelectron is very small,
less than 10ă9 second.
In effect quantitatively using EinsteinÊs method, the following equivalent equations are used :
Energy of photons = Energy needed to remove an electron + Kinetic energy of the emitted electron
Algebraically :
hf =  + Ekmax
where
Ć h is PlanckÊs constant
Ć f is the frequency of the incident photon

ATOMIC STRUCTURE
 MARKS 29

Ć = hf0 is the work function (sometimes denoted W instead), the minimum energy required to
remove a delocalised electron from the surface of any given metal.

1 2
Ek max  mvm is the maximum kinetic energy of ejected electrons.
2

Ć f0 is the threshold frequency for the photoelectric effect to occur.

Ć m is the rest mass of the ejected electron, and
Ć vm is the speed of the ejected electron.
Since an emitted electron cannot have negative kinetic energy, the equation implies that if the
photonÊs energy (hf) is less than the work function (), no electron will be emitted.

Ex a m p l e 1 9
Find the ratio of frequencies of violet light (  = 4.10 ï 10 ă5 cm) to that of red light
(
 = 6.56 ï 10ă5 cm). Also determine the ratio of energies carried by them.
Solution :
Using c = v ;
c : speed of light; v = frequency &  : wavelength

v1 2
 1 : red & 2 : violet
v2 1

v1 6.56  105
   1.6
v2 4.10  105

Now the energy associated with electromagnetic radiation is given by E = hv.

E1 v 
  1  2  1.6
E 2 v2  1

Hence the ratio of energies is same as that of frequencies.

Ex a m p l e 2 0
A bulb exits light of  = 4500 AĈ. The bulb is rated as 150 watt and 8% of the energy is emitted
as light. How many photons are emitted by the bulb per second ?
Solution :
hc
Energy of one photon =


6.625  10 34  3 108

=
4500  10 10
= 4.42 ï 10ă19 J

ATOMIC STRUCTURE
30 MARKS

8
Energy emitted by bulb = 150 ï J
100

= 12 J
 n ï 4.42 ï 10ă19 = 12 (n = no. of photons)

12
n =
4.42  10 19

= 2.72 ï 1019

Ex a m p l e 2 1
An electronic beam can under go diffraction by crystals. Through what potential should a
beams of electrons be accelerated so that its wave length becomes equal to 1.54 AĈ
Solution :
We know that

1
mv2 = eV
2

h h
and  = or v =
mv m

2 h2
or v =
m 2 2

1 h2
or m = eV
2 m2 2

1 h2
or V = m
2 m 2 2  e

1 h2
= 
2 m2 e

34 2
1 (6.62  10  )
Substituting the values, we get V = 
2 9.108  10 31  (1.54  10 10 ) 2  1.602  10 19

= 63.3 volt.

ATOMIC STRUCTURE
 MARKS 31

Ex a m p l e 2 2
A photon of light with  = 470 nm falls on a metal surface. As a result, photoelectrons are
ejected with a velocity of 6.4 ï 10 4 m/s. Find :
(a) the kinetic energy of emitted photoelectrons;
(b) the work function (in eV) of the metal surface.
Solution :
(a) Kinetic energy of electron = ó mv2
KE = ó (9.1 ï 10 ă31)(6.4 ï 10 4) 2 = 7.45 ï 10ă22 J
(b) From EinsteinÊs photoelectric equation, we have,
Kinetic energy = incident energy ă work function
KE = E incident ă  (= work function)
 = E incident ă KE

hc 6.63  1034  3  108

  KE =  7.45  10 22
 9
470  10

= 4.224 ï 10ă19 J
  = 4.224 ï 10ă19 J
= 2.64 eV
Note : More tough problems on photoeletric effect will be dealt with in Modern Physics.

Ex a m p l e 2 3
The dissociation energy of H 2 is 430.53 KJ molă1. If H2 is exposed to radiation energy of wave
length 253.7 nm. What % of radiant energy will be converted into kinetic energy ?
Solution :

430.53  103
Energy required to break HăH bond = J/molecule
6.023  1023
= 7.15 ï 10ă19 J
hc
Energy of photon used for this purpose =


6.625  10 34  3.0  108

=
253.7 109
= 7.83 ï 10ă19 J
 Energy left after dissociation of bond
= (7.83 ă 7.15) ï 10ă19
or Energy converted into K.E. = 0.68 ï 10 ă19 J

0.68  10 19
 % of energy used in kinetic energy =  100
7.83  10 19
= 8.68%
ATOMIC STRUCTURE
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Ex a m p l e 2 4
Find out the number of waves made by a Bohr electron in one complete revolution in its 3rd
orbit.
Solution :
For an electron to be in a particular energy level of radius r, with de Broglie wavelength  :
2r = n
(where n = number of waves in one revolution)

h 2r mv
  n
mv h
for third orbit;
r = 0.53 ï 10ă10(3) 2 m; v = 2.165 ï 106 (1/3)
substituting the value of r, v, m and h, we get,
n= 3

Ex a m p l e 2 5
An electron in the first excited state of H-atom absorbs a photon and is further excited. The
debroglie wavelength of the electronic this state is found to 13.4 A0 . Find the wavelength of
photon absorbed by the electron in A0 . Also find the longest wavelength emitted when this
electron de-excites back to ground state.
Solution :
First excited state refers to the energy level n = 2
The electron from n = 2 absorbs a photon and is further excited to an higher energy level (let us
say n)
The electron in this energy level (n) has de Broglie wavelength () = 13.4 Å.

h Z
 & v n = 2.165 ï 106
mv n

6.63  10 34 1
h
 2.165  10 6 
1  2.165  10 6 

m n

13.4  10    9.1  10 
 10  31 n

 n = 4
First find the wavelength of the photon responsible for the excitation from n = 2 to n = 4
Using the relation :

hc  1 1 
E =  2.17  10 18 Z 2  2  2 
  n2 
 n1
    = 4861.33 Å
The longest wavelength emitted when this electron (from n = 4) falls back to the ground state will
corresponds to the minimum energy transition.

ATOMIC STRUCTURE
 MARKS 33

The transition corresponding to minimum energy will be 4  3

Note : The transition corresponding to maximum energy will be 4  1
Using the same relation :

hc 1 1 
E  2.17 1018 Z2  2  2 
 n n2 
 1
    = 18750.85 Å
Note : If the value of R is given then use :

1  1 1 
v  R Z2    R = 1.097 ï 107 mă1.
 n 2
n22
 1 

Ex a m p l e 2 6
The IP, of H is 13.6 eV. It is exposed to electromagnetic waves of 1028AĈ and gives out induced
radiations. Find the wave length of these induced radiations.
Solution :
E 1 of H atom = ă13.6 eV

6.625 1034  3 108

Energy given to H atom =
1028 10  10
= 1.933 ï 10ă18 J
= 12.07 eV
 Energy of H atom after exitation = ă13.6 + 12.07
= ă 1.53 eV

E1
En =
n2

13.6
n2 =  9
1.53
n =3
rd
Thus, electron in H atom is excited to 3 shell

hc
 induced 1 =
(E3  E1 )

E1 = ă 13.6 eV
E3 = ă1.53 eV

6.625  10 34  3  108

1 =
( 1.53  13.6) 1.602  1019
= 1028 ï 10 ă10m.
 = 1028 AĈ

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34 MARKS

1 .7 .1 Qu a n t u m N u m b e r s
To understand the concept of Quantum Numbers, we must know the meaning of some terms
clearly so as to avoid any confusion.
Energy Level :
The non-radiating energy paths around the nucleus are called as Energy Levels or Shells. These
are specified by numbers having values 1, 2, 3, 4,... or K, L, M, N, ... corresponding to 1, 2, 3, 4, ... in
order of increasing energies. The energy of a particular energy level is fixed.
Sub-Energy Level :
The phenomenon of splitting of spectral lines in electric and magnetic fields reveals that there
must be extra energy levels with-in a definite energy level. These were called as Sub-Energy Levels or
Sub-Shells. There are four types of sub-shells namely; s, p, d, f.
First energy level (K or 1) has on sub-shell designed as 1s, the second energy level (L or 2) has
two sub-shells as 2s & 2p, the third energy level (M or 3) has three sub-shells as 3s, 3p & 3d, and the
fourth energy level (N or 4) has four sub-shells s 4s, 4p, 4d & 4f. The energy sub-shells increases roughly
in the order : s < p < d < f.
Orbital :
Each sub-energy level (sub-shell) is composed of one or more orbitals. These orbitals belonging to
a particular sub-shell have equal energies and are called as degenerate orbitals. Sub-shell s has one
orbital, p has three orbitals, d has five orbitals and f has seven orbitals.
To describe or to characterise the electrons around, the nucleus in an atom, a set of four numbers
is used, called as Quantum Numbers. These are specified such that the states available to the electrons
should follow the laws of quantum mechanics or wave mechanics.

Principal Quantum Number : (n)

This number represents the main energy levels (principal energy levels) designated as n = 1, 2, 3,
... or the corresponding shells are named as K, L, M, N, ... respectively. It gives an idea of position and
energy of an electron. The energy level n = 1 corresponds to minimum energy and subsequently n = 2,
3, 4, ... are arranged in order of increasing energy.
Ć Higher is the value of n, greater is its distance from the nucleus, greater is its size and also
greater is its energy.
Ć It also gives the total electrons that may be accommodated in each shell, the capacity of each
shell is given by the formula 2n2, where n : principal quantum number.

Azimuthal Quantum Number : (l)

This number determines the energy associated with the angular momentum of the electron about
the nucleus. It is also called as the angular momentum quantum number. It accounts for the appearance
of groups of closely packed spectral lines in electric field (Zeeman Lines).
Ć It can assume all integral values from 0 to n-1. The possible values of l are :
1, 2, 3, ...., n - 1.

ATOMIC STRUCTURE
 MARKS 35

Ć Each value of l describes a particular sub-shell with in the main energy level and determines
the shape of the electron cloud.
Ć When n = 1, l = 0, i.e., its energy level contains one sub-shell which is called as a sub-shell.
So for l = 0, the corresponding sub-shell is s sub-shell. Similarly when l = 1, 2, 3, the sub-shells
are called as p, d, f sub-shells respectively.
Ć As you know for n = 1, l = 0, there is only one sub-shell. It is represented by 1s. Now for n =
2, l can take two values (the total number of values taken by l is equal to the value of n in a
particular energy level). The possible values of l are 0, 1. The two sub-shells representing the
IInd energy level are 2s, 2p. In the same manner, for n = 3, three sub-shells are designated as
3s, 3p, 3d corresponding to l = 0, 1, 2 and for n = 4, four sub-shells are designated as 4s, 4p,
4d 4f corresponding to l = 0, 1, 2, 3.

h
Ć The orbital Angular momentum of electron = l  l  1
2

Note that its value does not depend upon value of n.

Magnetic Quantum Number : (m)

An electron with angular quantum number can be thought as an electric current circulating in a
loop. A magnetic field due to this current is observed. This induced magnetism is determined by the
magnetic quantum number. Under the influence of magnetic field, the electrons in a given sub-energy
level prefer to orient themselves in certain specific regions in space around the nucleus. The number
of possible orientations for a sub-energy level is determined by possible values of m (this corresponds
to the number of orbitals in a given sub-energy level).

• m can have any integral values between -l to + l including 0, i.e., m = - l, -l + 1, ......, 0, 1, 2,

3, ......, l - 1, + l. We can say that a total of (2l + 1) values of m are there for a given value
of l.

Ć In s sub-shell, there is only one orbital [l = 0,  m = (2l + 1) = 1].

Ć I p sub-shell, there are three orbitals corresponding to three values of m : - 1, 0, + 1.

[l = 1  m = (2l + 1) = 3]. These three orbitals are represented as px, py , pz along X, Y, Z axes
perpendicular to each other.

Ć In d sub-shell, there are five orbitals corresponding to - 2, - 1, 0, + 1, + 2. [l = 2  m =

(2l + 1) = 5]. These five orbitals are represented as d xy, dyz , d zx, dx2-y 2, d z2.

Ć In f sub-shell there are seven orbitals corresponding to - 3, - 2, - 1, 0, + 1, + 2, +3.

[l = 3  m = (2l + 1) = 7].

Spin Quantum Number : (s)

When an electron rotates around a nucleus it also spins about its axis. If the spin is clockwise, its
spin quantum number is (+ ó ) and is represented as  or 1. If the spin is anti-clockwise, its value is

ATOMIC STRUCTURE
36 MARKS

ă ó and is represented as  or 1. If the value of s is (+ ó ) then by convention, we take that electron

as the first electron in that orbital and if the value of s is (ă ó ) it is taken as second electron.

1 .7 .2 Sh a p e s o f A t o m i c Or b i t a l s
(i) s-orbital : An electron is considered to be smeared out in the form of a z
cloud. The shape of the cloud is the shape of the orbital. The cloud is not
uniform but denser in the region where the probability of finding the
electron in maximum. + x
The orbital with the lowest energy is the 1s orbital. It is a sphere with
its centre at the nucleus of the atom. The s-orbital is said to spherically
symmetrical about the nucleus, so that the electronic charge is not y
concentrated in any particular direction. 2s orbital is also spherically Shape of s-orbital
symmetrical about the nucleus, but it is larger than (i.e., away from) the
1s orbital.
(ii) p-orbitals : There are three p-orbitals :
z
p x, p y and pz . They are dumb-bell shaped, z z
the two levels being separated by a nodal +
+
plane, i.e., a plane where there is no likely ă + x x x
ă
hood of finding the electron. The p-orbitals y px y py
y ă
have a marked directional character, pz
depending on whether px, py and pz orbital Shapes of p-orbital
is being considered. The p-orbitals consist
of two lobes with the atomic nucleus lying between them. The axis of each p-orbital is
perpendicular to the other two. The px, py and pz orbitals are equivalent except for their
directional property. They have the same energy. Orbitals having the same energy are said
to be degenerate.
z z z
(iii) d-orbitals : There are five
d-orbitals. The shapes of four
d-orbitals resemble four leaf
cloves. The fifth d-orbital loops
x x x
differently. The shapes of these
orbitals are given below. y y
3dxy y
3dxz
3dyx

z
z

x x
y y
3dx2 ă y2
3dz2

ATOMIC STRUCTURE
 MARKS 37

Qu a n t u m M e c h a n i c a l M o d e l
In the quantum mechanical model of an atom, there is only a „chance‰ or probability of finding an
electron in space. Where this probability is maximum (over 95%), that region of space is called Âan
orbitalÊ.
The concept of orbital comes from the Schrodinger wave equation.

d2  d2  d2  8 2 m
   E  V    0
dx2 dy2 dz2 h2

The symbols have the following meanings :

m  Mass of an electron
h  PlanckÊs constant
E  Total energy of electron
V  Potential energy of electron
 Wave function
Electrons have associated wave functions denoted by 
 itself has no physical significance. Its square, however, gives the probability of finding an
electron at a given point. More often, we are interested in finding the probability of finding an electron
in a region. For this, consider a sphere of radius r and thickness dr.
The volume of the shell of thickness dr is 4r2dr.
r
This volume multiplied by the probability (2) gives the probability of finding an
electron in the shell of thickness dr.
dr
Thus, p (r) = 4r2dr |2|
Since this function depends only on the value of radial distance from the centre, it is called radial
probability function.
Radial node or Spherical nodes : Now, in any atom, the quantum number n gives the distance
between the nucleus & the outermost shell. So, it is a measure of the radial distance of an electron. It
so happens that for certain orbitals, the probability of finding an electron drops to zero at certain
distances from the nucleus. Such points are called radial nodes. (A node is a region where the probability
of finding an electron is zero).
Following graphs will further illustrate this point
The number of radical nodes increased with the increase in distance between nucleus and the
outermost shell.

s
P(r) P(r) P(r)
= 4r2| 2|dr = 4r2| 2|dr = 4 r2dr | 2 |
2s wide 3s
wide

r wide r
r
ATOMIC STRUCTURE
38 MARKS

Angular or Planar node : This type of node corresponds to the quantum number l. In s orbitals,
due to their spherical symmetry, there are no nodal plane. Consider px orbital.
In the y-z plane, the probability of finding an electron is O. So, y-z is a nodal plane.
Similarly, for d-orbitals there are 2 nodal planes. y

Formulae :
No of radial nodes = n ă l ă 1 x
No. of angular nodes = l
Total no. of nodes = n ă 1

1 .8 EL ECT RON I C CON FI GU RA T I ON OF EL EM EN T S :

Quantum numbers can now characterise the electrons in an atom. To describe the arrangements
and distribution of electrons for different elements, following rules and selective principles are used. The
distribution of electrons in an atom is known as the electronic configuration of that element.

Aufba u P rinc iple

An atom in its lowest state of energy is said to be in ground state. The ground state is the most
stable state in an atom. According to Aufbau principle :
„electrons are added progressively to the various orbitals in their order of increasing energy starting
with the orbital of lowest energy.”
The order of increasing energy may be summed up as follows :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d,.....
As a working rule, a new electron enters an empty orbital for which the value of (n + l) is minimum. If the
value of (n + l) is same for two or more orbitals, the new electron enters an orbital having lower value of n.

Pauli Exclusion Principle

According to this principle :

„no two electrons in an atom can have the same set of all the quantum numbers or one can say that
no two electrons can have the same quantised states.”
Consider an electronic arrangement in Ist energy level (n = 1). For n = 1, l = 0, & m = 0. Now s
can have two values corresponding to each value of m i.e. s = + ó, ă ó. Hence, the possible designation
of an electron in a state with n = 1 is 1, 0, 0, + ó and 1, 0, 0, ă ó (n, l, m, s) i.e., two quantised states.
This implies that an orbital can accommodate (for n = 1, m = 0,  one orbital) maximum of two electrons
having opposite spins.
The maximum number of electrons in the different subshells are :
s sub-shell = 2, p sub-shell = 6, d sub-shell = 10 and f sub-shell = 14.

ATOMIC STRUCTURE
 MARKS 39

Hund’s Rule of Ma ximum Multiplic ity

According to this rule :

„electrons never pair until no available empty degenerate orbitals are left to them.”
This means an electron always occupies a vacant orbital in the same sub-shell (degenerate orbital)
and pairing starts only when all of the degenerate orbitals are filled up. This means that the pairing
starts with 2nd electron in s sub-shell, 4th electron in p sub-shell, 6th electron in d sub-shell and 8th
electron in f sub-shell.
By doing this, the electrons stay as far away from each other as possible. This is highly reasonable
if we consider the electron-electron repulsion. Hence electrons obey HundÊs rule as it results in lower
energy state and hence more stability.

Extra Sta bility of Half a nd Fully Filled Orbita ls

A particularly stable system is obtained when a set of equivalent orbitals (degenerate orbitals) is
either fully filled or half filled, i.e., each containing one or a pair of electrons. This effect is more
dominant in d and f sub-shells.
This means three or six electrons in p sub-shell, five or ten electrons in d sub-shell, and seven or
fourteen electrons in f sub-shell forms a stable arrangement. Note this effect when filling of electrons
takes place in d sub-shells (for atomic numbers Z = 24, 25 and 29, 30).

In the following ta ble you should a na lyse how to employ the a bove rules to write electronic
configura tion of various elements.

Electronic configuration of an element is represented by the notation n lx :

x : number of electrons present in an orbital

l : denotes the sub-shell

n : principal quantum number

ATOMIC STRUCTURE
40 MARKS

Ground-State Electronic Configuration of the Elements

Atomic
Number Symbol 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
1 H
2 He 1
2
3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
10 Ne 2 2 6
11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6
19 K 2 2 6 2 6 1
20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1
30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 Se 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6
Note : In atomic numbers, 24 and 29, observe the rule of extra-stability of half filled and fully filled orbitals.

ATOMIC STRUCTURE
 MARKS 41

Ex a m p l e 2 7
(a) Find the orbital angular momentum of an electron in the following orbital
(i) 3p (ii) 3d (iii) 3s
(b) Arrange the electrons represented by the following sets of quantum numbers in
decreasing order of energy
(i) n = 4, l = 0, m = 0, s = ó (ii) n = 3, l = 2, m = 0, s = ó
(iii) n = 3, l = 1, m = 1, s = ă ó (iv) n = 3, l = 0, m = 0, s = ă ó
Solution :
h
(a)   l  l  1  l  l  1 h
2

(i) For 3p, l = 1, l  1 1  1  h  2 h

h
(ii) For 3d, l = 2, l  2  2  1  6h
2
(iii) For 3s, l = 0, øl = 0
(b) Higher the value of (n + l) higher will be the energy of orbital. If the two values are same then
one having higher value of n the energy will be higher
For (i) (n + l) = 4 4s orbital
For (ii), (n + l) = 5, 3d orbital
For (iii) (n + l) = 4 3p orbital
For (iv), (n + l) = 3 3s orbital
Decreasing order of energy : (ii) > (i) > (iii) > (iv)

Ex a m p l e 2 8
Consider the following electronic configuration of the element
(i) 1s22s1 (ii) 1s2 3s1
(a) Name the element corresponding to (i)
(b) Does (ii) correspond to the same or different element
(c) How can (ii) be obtained from (i)
(d) Is it easier to remove one electron from (ii) or (i) ? Explain.
Solution :
(a) The element corresponding to (i) is lithium (Li).
(b) This electronic configuration represents the same element in the excited state.
(c) By supplying energy to the element when the electron jumps from the lower energy 2s orbital
to the higher energy 3s orbital.
(d) It is easier to remove an electron from (ii) than from (i) since in the former case the electron
is present in a 3s orbital and hence is less strongly attached by the nucleus than a 2s
orbital.

ATOMIC STRUCTURE
42 MARKS

Ex a m p l e 2 9
A neutral atom of an element has 2K, 8 L, 5M electrons. Find out the following :
(a) Atomic Number
(b) Total number selectrons
(c) Total number of p electrons
(d) Number of protons
(e) Valency
Solution : Electronic configuration of tievtral atom :

1s2 2s2 2P6 3s2 3P3

, ,
K L M
(a) Atomic number = Total number of electrons in neutral atom = 15
(b) Total number of s electrons = 6
(c) Total number of p electrons = 9
(d) Number of protons = 15
(e) Valency = 3

Ex a m p l e 3 0
An electron in a Bohr orbit of hydrogen atom in quantum level n2 has an angular momentum
of 4.276 ï 10ă34 kgm 2 secă1 . If this electron drops from this level to the next lower level, find
the wavelength of this spectral line. (given R H = 109679 cmă1)
Solution : According to BohrÊs theory

nh
mvr 
2
mvr = 4.2176 ï 10ă34 kg m2 să1

n

2  3.14  4.2176  10 34 kg m 2 s 1 
 6.626  10 34

Js

= 3.99
  4
when an electron falls from n = 4 to n = 3 in a hydrogen atom, the wavelength emitted is
calculated as,

1  1 1
 RH   
2
  n1 n22 

1 1
= 109679  2  2 
3 4 

ATOMIC STRUCTURE
 MARKS 43

 = 1.8756 ï 10ă4 cm
= 1.8756 ï 10ă6 m
= 18756 ï 10ă10 m
= 18756 Å

Ex a m p l e 3 1
Calculate the energy emitted when electrons of 1.0 g atom of hydrogen undergo transition
giving the spectral lines of lowest energy in the visible region of its atomic spectra.
RH = 1.1 ï 107 mă1 , c = 3 ï 108 m sec ă1 and h = 6.62 ï 10 ă34 J sec
Solution :
For visible line spectrum, i.e., Balmer series n1 = 2. Also for minimum energy transition n 2 = 3.

1 1 1 
  R H  2  2  for H-atom
  n1 n 2 

1  1 1
  RH 2  2
 2 3 

7 1 1 7 5 1
= 1.1  10     1.1  10  m
 4 9 36

  = 6.55 ï 10ă7 m

hc 6.62  10 34  3.0  108

E 
 6.55  10 7

= 3.037 ï 10ă19 Joule

If N electrons show this transition in 1 g atom of H then
Energy released = E ï N
= 3.03 ï 10ă19 ï 6.023 ï 10 23
= 18.29 ï 104 J
= 182.9 kJ

Ex a m p l e 3 2
Consider the hydrogen atom to be a proton embedded in a cavity of radius (Bohr radius)
whose charge is neutralized by the addition of an electron to the cavity in a vacuum, infinity
slowly. Estimate the average total energy of an electron of an electron in its ground state as
the work done in the above neutralization process. Also, if the magnitude of the average
kinetic energy is half of the magnitude of the average potential energy, find the average
potential energy.

ATOMIC STRUCTURE
44 MARKS

Solution :
The work done in the neutralization process is the energy due to the electrostatic force of attraction
between the electron and the proton.

kZe (  e)
 Potential energy =
a0

 kZe2  ke2
= 
a0 a0

where e is the charge on the electron/proton, a0 is the Bohr radius, k is the coulombic law constant
and Z is the atomic number = 1 ( one proton)
Kinetic energy of the electron moving in the orbit = ó mv2 (m is the mass of electron and v is the
velocity).
 Total energy of the electron

 ke2 1 2
E  mv ... (i)
a0 2

For the electron to stable in the orbit, the electrostatic force of attraction should be equal to the
centripetal force.

ke2 mv 2
 
a 20 a0

ke2
 mv 2
a0

Substituting in (i)

 ke2 1 ke2  ke2

E  
a0 2 a0 2 a0

Ex a m p l e 3 3
Positronium consists of an electron and a positron (same mass, opposite change) orbiting
around their common centre of mass. The spectrum is therefore expected to be hydrogen
like, the difference arising from the mass differences. Calculate the wave number of the first
three lines of Balmer series of positronium.
Solution : The mass of the nucleus and the electron are comparable and in such systems the mass of
the nucleus is also to be taken into account. In the energy equation, instead of the mass of the electron,
the reduced mass is to be taken.
By definition, reduced mass ø is
1 1 1
 
 m M

ATOMIC STRUCTURE
 MARKS 45

m is the mass of the electron and M is the mass of the nucleus

m M

m+M

Since the mass of positron = mass of electron,

m m m
 
2m 2
Therefore with equation for Rydberg constant, for positronium is

2 2 e4 k2 2 2 m / 2  e4 k2
Rpos  
h3 c h3 c

RH
=
2

109737
=  54868.5 cm 1
2
First line of Balmer series :

1 1 
v1  54868.5  2  2   7620.6 cm 1
2 3 
Second line :

 1 1 
v2  54868.5  2  2   10288 cm 1
2 4 

Third line :

 1 1 
v3  54868.5 
2
 2   11522 cm 1
2 5 

Ex a m p l e 3 4
The de Broglie wavelength of electron of He+ ion is 3.329 Å. If the photon emitted upon de-
exiciation of this He+ ion is made to hit H atom in its ground so as to liberate electron from
it, what will be the de BroglieÊs wavelength of photoelectron?

h
Solution : 
2 mE

E 
h2

 6.625 10 
34


2 m 2 2  9.11 10   3.329  10 
31 10
2

= 21.73 ï 10ă19 J = 13.58 eV

ATOMIC STRUCTURE
46 MARKS

this is the K.E. of electron

Therefore, total energy = ă 13.58 eV

Z2
E n   13.6  eV
n2
For H+ ion, Z = 2 and E n = ă13.58 eV

 13.6  4
So, n 2 =  13.58  n = 2

Thus, He+ ion is in the 1 st excited state.

 1 1 
Energy of photon emitted = 13.6 Z2  2  2  eV
 n1 n2 

 1
= 1.36 ï 4  1    40.8 eV
 4

Energy of photon = I.P. of H + K.E. of photoelectron

Thus, K.E. of photoelectron = 40.8 ă 13.6 = 27.2 eV

h 6.625  1034
  = 2.351 ï 10ă10 m = 2.351 Å
2 mE 2  9.11 10 31  27.2 1.602 10 19

Ex a m p l e 3 5
The wavelength of the photoelectric threshold of a metal is 230 nm. Determine the K.E. of
photoelectron ejected from the surface by UV radiation emitted from the second longest
wavelength transition (downward) of electron in Lyman series of the atomic spectrum of
hydrogen. (R = 1.9677 ï 107 mă1 )
Solution :
The minimum energy (E) required to eject an electron per atom from metal surface is given by
PlanckÊs quantum theory as adopted by Einstein to explain photoelectric effect.

hc 6.625  10 34  3  10 8
E 0  hv0  
0 230  10 9

= 8.63 ï 10ă19
For spectral line in Lyman series of H atom

1  1 
R 1  2 
  n 

ATOMIC STRUCTURE
 MARKS 47

For the 2nd longest wavelength transition, n = 3, so

1 8 8
 R   1.09677  10 7 m1
 9 9

9
or 
8 1.09677 10 7

= 1.025 ï 10ă7 m = 102.5 nm

Energy of photon corresponding to this wavelength is as given below

c 6.625 10 34 3 10 8

Eh 
 1.025 10 7

= 1.937 ï 10ă18 J
 K.E. of photoelectron = E ă E 0
= 19.37 ï 10ă19 ă 8.63 ï 10ă19 = 1.074 ï 10ă18 J

Ex a m p l e 3 6
The second ionization potential of Be is 17.98 eV. If the electron in Be3+ is assumed to move
in a spherical orbit with a central field of effective nuclear charge (Zeff ) consisting of the
nucleus and other electrons, by how many units of charge is the nucleus shielded by other
electrons? (The energy of electron in first Bohr orbit of H is ă 13.6 eV). If the extent of
shielding by the K electrons of Li atom is the same as you have calculated above, find the
ionization potential of Li.
Solution :

13.6Z 2eff
I.E.   17.98
n2
 Zeff = 2.3
Shielding extent = Z ă Z eff = 4 ă 2.3 = 1.7
Zeff for lithium = 3 ă 1.7 = 1.3
 I.E. of lithium = 13.6 ï (1.3)2 = 22.984 eV

ATOMIC STRUCTURE
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