Atomic Strcture

Rankers - JEE | DLP | Chemistry | www.myranker.
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Rankers - JEE | DLP | Chemistry | www.myranker.com
ATOMIC STRUCTURE
By convention there is color,
by convention sweetness,
by convention bitterness,
but in reality there are
atoms and space.
Democritus (400 BC)
JEE-Syllabus
Electron, proton and neutron; constitution of nucleus , properties of alpha, beta and
gamma rays : Rutherford’s scattering experiment ; Bohr’s atomic model (mathematical
details excluded ): quantum numbers; Pauli’s exculsion principle; Hund’s rule; Aufbau
principle ; electronic configuration of elements (upto atomic number 36); shapes of s, p
and d orbitals.
Fundamental Particles
Atoms are made up- essentially, of three fundamental particles, which differ in mass and electric
charge as follows :
Electron Proton Neutron
Symbol e or e- p n
Approximate relative 1/1836 of mass of 1 1

mass proton
Approximate relative -1 +1 0
charge
Mass in Kg 9.109534x 10-31 1.6726485 x 10-27 1.6749543 x 10-27
Mass in amu 5.4858026 x 10-4 1.007276471 1.008665012
Actual charge /C 1.6021892 x 10-19 1.6021892 x 10-19 0
The atomic mass unit (amu) is 1/12th of the mass of an individual atom 6C12, i. e., 1.660565 x 10-27
Kg. The neutron and proton have approximately equal masses of 1 amu and the electron is
about 1836 times lighter ; its mass can sometimes be neglected as an approximation . The
electron and proton have equal , but opposite, electric charges; the neutron is not charged.
The existence of electrons in atoms was first suggested, by J. J. Thomson, as a result of experimental
work on the conduction of electricity through gases at low pressure , which produces cathode rays
and x-rays, and a study of radioactivity by Becquerel, the Curies and Rutherford.
An atom is electrically neutral, and if it contains negatively charged electrons it must also
contain some positively charged particles, and the supposition that they existed within atoms came
about as a result of Rutherford’s experiments in which the bombarded elements with the 

- and - rays were given off by radioactive elements . The neutron was discovered in 1932 by
James Chadwick by bombardindng beryllium with  rays.
Atomic Terms
Nuclide : Various species of atoms in general.
Nucleons : Sub-atomic particles in the nucleus of an atom , i. e protons and neutrons.
Isotopes : Atoms of an element with the same atomc number but different mass number.
Mass number (A) : Sum of the number of protons and neutrons ,i. e, the total number of nucleons.
Atomic number (Z) : The number of protons in the nucleus of an atom. This when subtracted
from A, gives the nubmer of neutrons.
Isobars : Atoms, having the same mass number but different atomic numbers ,e. g.
15
P32 and 16S32.
Isotones : Atoms having the same number of neutrons but different number of protons
or mass number , e.g , 14 16 15
6 C, 8 O, 7 N
Isoelectronic : Atoms molecules or ions having the same number of electrons, e. g N 2,

CO, CN-
Nuclear isomers : Atoms with the same atomic and mass numbers but different radioactive
properties, e. g., uranium X ( half life1.4 min ) & uranium Z (half life 6.7 hours).
Atomic mass unit :Exactly equal to 1/12th of the mass of 6C12 atom.
(a. m. u) :1 a. m. u = 1.66 x 10-24 g  931.5 MeV
Rutherford’s -rays scattering experimet : A beam of alpha particles, (dipositive helium

ions) was obtained from a source containing the element polonium. Rutherford’s experiment
was to place thin sheets of metal in the path of the alpha ray in order to see how various
metals would affect the alpha-particle trajectory . Rutherford found that some of the alpha
particles were deflected at astonishingly large angles. A few were actually reflected bakc
towards the source. According to Rutheford, the only way to account for the large deflections
would be to say that the positve charge and mass in the metal foil are concentrated in very small
regions.
Although most of the alpha particles go through without any deflection , occasionally one
comes very close to a high concentration of positive charge.
The positive charge is essentially immovable because it contains practically all the mass of the
atom. As like charges get closer together, they repel each other ,and the repulsion between alpha
particles and nucleus may be great enough to cause the relatively light alpha particle to deflect
considerably from its original path. Hence, to explain his observations, Rutherford suggested that
an atom has a nucleus, or centre , in which its positive charge and mass are concentrated . The
quantitative results of scattering experiments such as Rutherfor’s indicate that the nucleus of
an atom has a radius of about 10-13 cm, which is only about one hundred thousandth size
generally ascribed to atoms. Later wheh neutrons and protons were discovered, it was noted that
the radius of a particular nucleus can be expressed roughly as r ( in centimetres ) ~ 1 x 10 -13 A1/3,
where A is the total number of neutrons and protons in that nucleus.

Atomic number and relative atomic mass : The value of the positive charge on the nucleus,or of
the number of electrons, in the atom of any element is equal to the ordinal number of that element
in the periodic table arrangement .This number is called the atomic number (Z).
In passing from one atom to the next in the periodic table there is a unit increase of positive
charge on the nucleus of the atoms concerned and a consequent additon of one electron.
The approximate relative atomic mass, of an element is obtained by adding up the number of
protons and neutrons in the atom concerned for , by comparison, the mass of the electrons in an atom
is very samll. IUPAC notation for an atom ( Nuclide) is zXA where X is the symbol for the element, Z
= Atomic number , A = mass number.
Typical atomic structures may be represented as follows :
A =1 A=4 A =7
Hydrogen helium lithium
Z=1 Z=2 Z=3
2e
2p + 2n 2e 3p + 4n
1p e e
Line Spectrum of Hydrogen Atom
The spectrum of hydrogen consists of lines corresponding to widely different frequencies.

It was found that many of the numerous lines could be fitted into series . These series , known
after thier discoveres as the Balmer (1885) , Paschen ( 1896). Lyman (1915 ), Brackett) 1922 and
Pfund (1925) series , can be expressed in one overall formula :
1 /   R  (1 / n 2  1 / m 2 ) or v = R  C(1 / n 2  1 / m 2 )
Where  is the wavelength , v is frequency, c is the velocity of light, R  a constant known as

Rydberg constant (109737 cm-1) , and n and m have integral values as follows :
Series n m Position in solar Spectrum
Lyman 1 2,3, 4 etc ultra-violet
Balmer 2 3,4, 5 etc Visible
Paschen 3 4, 5, 6 etc infra-red
Brackett 4 5, 6, 7 etc infra-red
Pfund 5 6, 7, 8 etc infra-red
It is a remarkable experimental fact that so many unrelated lines in a spectrum can be expressed
by a simple formula. Line spectra of the alkali metals are also made up of similar series of lines
known as the sharp, principal diffuse and fundamental series . The lines in these series can be
related in a single formula as for the hydrogen spectrum.

Planck’s quantum theory : Progress in working out the arrangement of electrons in an atom came
first when Bohr in 1914, applied the ideas of the quantum theory, put forward by Planck in 1900, for
interpretation of hydrogen spectrum.
The essential idea of the quantum theorgy is that the energy of a body can only change by some
definite whole- number multiple of a unit of energy known as the quantum. This means that the
energy of a body can increase or decrease by 1, 2, 3, 4, .....n quanta, but never by 1 1/2 , 2 1/2 , 107
. 3 etc. quanta
However, the value of the quantum is not fixed ,but is related to the frequency of radiation which , by
its emission or absorption, causes the change in energy . This relationship is expressed as
E  h or E  hc / 
Where E is the value of the quantum (J), h is the planck constant (6.626176 x 10 -34) J. s).is the
frequency (S-1 or Hz) , is the wavelength and c is velocity of light (ms-1). It is then a simple matter
to calculate the value of the quantum corresponding to any known frequency.
When radiation of frequency , v or wavelength , ,is absorbed by a body, there will be an energy
increase, from E1 to E2 , where
E2 - E1 = nh = nhc/
and n is an integer. Emission of similar radiation would cause an equal decrease in energy.
The Bohr Atom
Bohr developed a model for hydrogen atom and hydrogen like one electron species. He applied the
quantum theory in considering the energy of an electron bound to the nucleus. He developed an expres-
sion for the energy of the electron in hydrogen atom, and hence derived the value for R (Reydberg
constant) from fundamental constants.
Bohr’s model of an atom can be described as follows
1. The electron in an atom has only certain definite stationary states of motion allowed to it;
each of these stationary state has a definite, fixed shell or energy . These stationary
states are known as orbits.
2. When an atom is in one of these states it does not radiate; but when changing from a
high-energy state to a state of lower energy, the atom emits a quantum of radiation whose
energy h is equal to the difference of the energies of these two orbits.
3. In any of these states the electron moves in a circular orbit about the necleus.
4. The states of allowed electronic motion are those in which the angular momentum of the
electron (mvr) is an integral multiple of h/2 . (angular momentum quantization postulate)
Radius & Energy Levels of Hydrogen Atom

The mechanical stability of the electron orbit requires that the coulomb force between the electron
and nucleus be balanced by the centrifugal force due to the circular motion.
Coulombic force = Centrifugal force

KZe 2 mv 2
 .
r2 r

KZe2
 v2 
mr
where m and v are the mass and velocity of the electron, Z is the number of units of elementary
charge e and r is the electron - nucleus separation. K is Coulomb’s fundamental constant ( 9.0 x 109
J - m C2). In C. G. S system the value of K = 1.
Bohr’s postulate for the angualr momentum, mvr, was
h
mvr  n , n  1, 2, 3.....
2
nh n2h2
v  v2 
2mr
4 2m2r 2
Where h is Planck’s constant, 6.626 x 10-27 erg sec. That is, the angular momentum had to be
integral multiple of h/2. Eliminating v between
KZe2 n2h 2
mr 4 2m 2r 2
n 2h 2
r , n  1, 2 ,3....
(2 )2 mZe2K
Hence only certain orbits whose radii are given by the above equation are allowed to the elec-
tron. The total energy, E of the electron , is the sum of the kinetic energy, mv2 / 2, and potential
energy , - Ze2/ r :
1 KZe 2
E mv 2 
2 r
But we can write
1 Ze2K Ze2K 1 Ze2K
E  
2 r r 2 r
Substituting for r give us
2  2mZ 2 e4k 2
E , n  1, 2, 3....
n2h2
The expression shows that the consequence of the postulates is that, only certain energies are
allowed to the electron.
N KJ/mole. Ergs/ molecules

 0 0
4 -82 -1.36 x 10-12

E
3 -145. 8 -2.41 x 10-12
2 -328 -5.42 x 10-12
1 -1312 -21.8 x 10-12

Z2
En = . x 10 12 x
218 erg per atom ( 1 erg = 6.2419 x 1011 ev )
n2
Z2
= 13.6 x eV per atom
n2
Z2
= 313.6 x K cal per mole
n2
Z2
= 2.18 x 10 -18 J per atom
n2
The energies are negative only because the energy of the electron in the atom is less than
the energy of a free electron , which is taken as zero.The lowest energy level of the atom corresponds
to n = 1 , and as the quantum number increases, E be comes less negative . When n =  , E = 0,
which corresponds to an ionized atom : the electron and nucleus are infinitely separated , and
at rest .
 H  e  ]
lonisation
[H  
According to Bohr’s second postualte, the energy of any photon radiated by the atom should
be equal to the difference in the energy of two levels. To ensure that the energy of the photon is
positive, we take the absolute value of the energy difference and write ;
2  2 mZ 2 e 4K 2 L
M 1 1 O
P
h= Ef  Ei  
h 2
M
Nn n P
2
f Q 2
i
v
2  2 mZ 2 e 4K 2 L
M 1

1 O
P
h 3
M
Nn n P Q
2
f
2
i
If nf is set equal to 2, and the constant term evaluated, this expression is in numerical
agreement with the formula which Balmer had found from the experimental hydrogen atom
spectrum. In other words , the Bohr expression is in agreement with the known experimental spec-
trum of the hydrogen atom.
n= 
; ; ;
n =5 ; ; ; ; Pfund series
n=4
; ; ; ; Brackett series
n=3 Paschen xeries
; ; ; ;
n=2 Balmer series
; ; ; ; ; ;
n =1 Lyman series
if n, the quantum number of the final state is set equal to 1, Bohr’s formula predicts
a set of spectral lines for which n1  2, , nf = 1. Similarly, if nf = 3, there should be a series of lines
for which ni  4. . These predicted transitions between states of different n are shown in fig.
subsequent to Bohr’s work, all the predicted spectral lines havebeen found at the expected
frequencies . Further application of Bohr’s work, formula was made , to other one electron species
, such as He+ and Li++ . In each cases

of this kind , Bohr’s prediction of the spectrum was correct . At the possible number of lines pro-
duced by an electron in nth orbit
n(n  1)
  (n  1)or 2
Hydrogenic lons
If we remove all the electrons from an atom except one we get hydrogenic ion. e. g. . He +,
Li , Pb+81, Au+78 -------------
++
Illustration 1 : A doubly ionised 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 H atom
equal 13.6 eV).
ii) How many spectral lines are observed in the emission spectrum of
the above excited system ?
13.6 Z 2
Solution : i) En 
n2
Excitation energy = E  E3  E1  13.6 x 3

2 L
M
1 1O
 P
N3 1 Q
2 2
= + 13.6 x 9 [ 1 - 1/9 ] = 13. 6 x 9 x 8/9 = 108.8 ev .

hc 6.63 x 1034 x 3 x 108
Wavelength   
E 13.6 x 8 x 1.6 x 10 -19
F6.63 x 3 x 10 I 7
=G
H13.6 x 8 x 1.6 J
K
= 114. 26 x 10-10m
= 114. 3 Å
ii) From the excited state (E3), coming back to ground state, there can be 3
possible radiations.
Illustration 2 : Ionisation energy of hydrogen atom is 13.6 eV.Calculate the ionisation

energy for Li2+ and Be3+ in the first excited state.
Solution : Ionization energy of hydrogen = - E1 ( Energy of first Bohr orbit )

F Z2 I  13.6 x 1 2
G
l.E  E1   13.6
H n2
J
K 1 2
 13.6eV
Ionization energy of Li2+

Z =3
n = 2 ( for 1st excited state )
F 32I  30.6eV
G
 l. E   13.6 x
H J
2 K2
Ionization energy of Be3+

Z =4
n =2 ( for 1st excited state )

F 42I  54.4eV
G
l.E  13.6x
H J
2 K
2
Illustration 3 : Calcualate 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 x 107
m-1, c = 3 x 108 m / sec, h = 6. 625 x 10-34 J sec.
Solution : Visible region of H- spectrum correspond to Balmer series n1 = 2, n2 = 3 (

for minimum energy transition )
L
M 1
1 /   RH 
1O 1
 P  R M P
L1 1 O
M
Nn n P Q 2
1
 2
2 N2 3 Q H 2 2
1 L1 1 O 11. x 10 x4
. x10 M P
  11 7
7
 N4 9 Q 4 x 9
  6.55x10 7
hc 6.625x10 34 x3x108
E  = 3. 03 x 10-19 Joule
 6.55x10 7
 Energy released by 1 gm atom of H ( 1 mol )
= En = 3. 03 x 10-19 x 6. 023 x 1023 = 18 . 25 x 104 J = 182. 5 k J
Illustration 4 : How many spectral lines are emitted by atomic hydrogen excited to
nth energy level ?
Solution : n=6
n=5
n =4
n= 3
n =2
n =1
1 1+2=3 1+2 +3 = 6
Thus the number of lines emitted from nth energy level
= 1 + 2 + 3 + ............................. n -1 = (n-1)
n(n  1)
n  2
(n  1)(n  1  1) (n  1)(n)
  (n  1)  
2 2
Number of spectral lines that appear in hydrogen spectrum when an
n(n  1)
electron de excites from nth energy level =
2
Exercise 1
i) A series of lines in the spectrum of atomic hydrogen lies at wavelengths 656.46 ,

482. 7, 434. 17, 410. 29 nm. What is the wave length of next line in this series ?
ii) Calculate of the radiations when the electron jumps from lll to ll orbit of hydrogen

atom. The electronic energy in ll and lll Bohr orbit of hydrogen atoms are -5.42 x
10-12 and -2.41 x 10-12 erg respectively.
iii) Calculate the wavelength for shortest wavelength transition in the Balmer series of
atomic hydrogen.
iv ) Calculate the ratio of the wavelength of first and the ultimate line of Balmer series
of Li2+ ?
Shortcomings of Bohr’s theory

The main shortcomings of Bohr’s theory are as follows :
1. Bohr’s theory failed to explain the spectra of multi- electron atoms.
2. Bohr’s atomic model failed to account for the effect of magnetic field on the
spectra of atoms or ions. It was observed that when the source of a spectrum is placed in a
strong magnetic field, each spectral line is further split into a number of lines . This is
called Zeeman effect. This observation could not be explained on the basis of Bohr’s model.
3. In 1923 , de Broglie suggested that electron , like light has a dual character.It has
particle as well as wave character . Bohr treated the electron only as a particle.
4. Another objection to Bohr’s theory came from Heisenberg’s uncertainty principle .

According to this principle , it is impossible to determine simultaneously the exact position and
momentum of a small moving particle like an electron . The postulate of Bohr, that electron revolve
in well defined orbits around the nucleus with well-defined velocities is, thus , not tenable.
Particle and Wave Character (Dual Character ) of Electrons
Einstein had suggested in 1905 that light has a dual character as ‘wave’ and also as ‘particle’. De
Broglie proposed that matter also has a dual character : as wave and as particle.
In Bohr’s theory, electron is treated as a particle . But according to de Broglie’s theory electron has
a dual character , both as a material particle and as a wave. He derived an expression for calculating
the wave length,  of a particle of mass m, moving with velocity v, according to which
 = h/mv
where h is planck’s constant. Above equation is known as the de Broglie’s equation.
Derivation of de Broglie’s equation .
The de Broglie’s equation can be easily derived by using Einsteins mass-energy relationsship Viz.
E = mc2
In the above equation , c is the velocity of light . Equating this energy with the energy of a photon,
we have
h= mc2
since = c/
 hc /   mc 2
Hence,   h / mc
Replacing c by the velocity v of the subatomic particles,and m its mass, we have
  h / mv  h / p..... de Broglie relation
Where p is the momentum of the particle.

Heisenberg’s Uncertainty Principle
According to this principle , it is not possible to determine simultaneously preecisely both the
position and the momentum (or velocity ) of a microscopic moving particle. This principle is math-
ematically expressed as
 ( x)xmV  h / 4
h
 ( x)x( V ) 
4m
Where x is uncertainty with regard to the position and P is uncerntainty with regard to the
momentum of the particle .Evidently, if x is very small , i.e ., the position of the particle is known
more or less exactly , P would be large , i. e.,uncertainty with regard to momentum will be large .
Similarly,if an attmept is made to measure exactly the velocity (momentum ) of the particle , the
uncertainty with regard to position will become large.
Quantum Numbers
The term quantum number is used to label the various energy levels or orbits;
a) Principle quantum number (n) : This represents a group or shell of orbits, and the total
number of electrons that can occupy any shell is given by 2n 2 ,where n is the principle quantum
number concerned , i. e.
Shell K L M N
principle quantum number(n) 1 2 3 4
maximum number of electrons 2 8 18 32
b) Subsidiary quantum number (or) Azimuthal quantum number (L) : This represents the
various subsidiary orbits within a shell : they may be visualised as elliptical orbits. Thus, in any one
shell there are various subsidiary orbits denoted as the 1, 2, 3 , 4, ... or the s,p, d, f .... orbits.
The orbital angular momentum of the electron is given as = (   1)h / 2 .
= (   1)
c) The Magnetic Quantum Number (m) : An electron with angular momentum can be thought
of as an electric current circulating in a loop, and consequently a magnetic field due to this current
is expected and observed. The observed magnetism is determined by the value of m. Since this
magnetism has its eventual source in the angular momentum of the electron , it is reasonable that
the values allowed to m depend on the value of  , the angular momentum quantum number .
Theory and experiment both show that m can assume all integral values between -  and + 
including zero. Thus, m can be -1, 0 + 1 for  = 1.
d) The Spin Quantum Number (s) : Besides the magnetic effect produced by its angular
motion, the electron itself has an intrinsic magnetic property. A charged particle spinining about its
own axis also behaves like a small magnet; hence we say that the electron has a spin. The
quantum number associated with this spin has only two possible values +1/2 and -1/2.
Pauli’s Exclusion Principle
This an important generalisation given by Wolfgang Pauli, in 1925, which determines the maximum
number of electrons that an energy level can accommodte. Pauli’s exclusion principle states that
it is impossible for any two electrons in the same atom to have all the for quantum numbers
identical

Thus, in the same atom, any two electrons may have three quantum numbers identical but the
fourth must be different . This principle is very useful in determining the maximum number of
electrons that can occur in any shell/sub shell. For K-shell , for instance, since n=1 ,  = can
have only one value (viz. 0) and m can also have only one value (viz,.0) . Hence s can be either
+1/2 or -1/2 . Thus there are two combinations of the quantum number, as shown below.
n =1,  = 0 m = 0 s = +1/2
n = 1  = 0 m = 0 s = -1/2
This shows that in the K - shell, there is only one subshell  = 0 and there are are only two
electrons of opposite spins.
For L-shell, since n = 2,  can have two values (0 and 1, ) m can have one value of  = 0 and three
values of  = 1 ( -1, 0 and +1 ) and s can have two values ( = +1/2 and -1/2 ) for each value of
m. These possibilities would give rise to eight combinations of the four quantum number, keeping
in view the exculsion principle. The maximum number of electrons in a shell is given by 2n 2.
Shapes and Sizes of Orbitals
By shape of an orbital we mean the shape of the region in space in which there is probability of
finding an electron. It is basically determined by the azimuthal quantum number (  ) , while the
orientation of an orbital depends on the magnetic quantum number (m). The size of an orbital
increases with the value of the principal quantum number (n). Shapes of orbitals in the various
sub-shells are as discussed below :
s- orbitals (  = 0 ) : The orbitals are spherical and Y

symmetrical about the nucleus . There is vacant
space between two successive s- orbitals known
as ‘radial node’. Due to nucleus symmetricity, these
are non-directional. 1s 2s
nucleus x
p-orbitals (  = 1) : These have a dumb- bell shape,
having three possible mutually perpendicular ori-
ientations . As they are not symmetrical, they have a radial node
directional character. The two lobes of p-orbitals are Z
separated by a nodal plane, where the probability of
finding electron is zero.
Y
X Py PZ
PX
Z
d- orbitals (  = 2 ) : They have relatively complex geometry. Out of the five d- orbitals , the first two
(dz2 & dx2  y2 ) lie along the axes, while the other three (d , d , d ) project in between the axis.
xy zx Yz
Filling of orbitals in Atoms: The distribution of electrons in various orbitals is known as electronic
configuration. The atom is built up by filling electrons in various orbitals one at a time and by
placing each new electron in the lowest available energy orbital . An atom is its lowest energy

state is said to be in the normal state or the ground state. This state is the most stable for the
atom. In representing positions of electrons in various shells and subshells, the following rules are
observed :
1. The major energy shell , 1, 2, 3, 4 etc., is written first.
2. The subshell , Viz, s, p, d and f is written next.
3. The number of electrons in the particular subshell is shown by a superscript placed to

the right of the symbol for that subshell.
For example .ls2 indicates the location of 2 electrons in the s-sub -shell of the first energy shell.
Similarly, 3d6 denotes the location of 6 electrons in the d-sublevel of the third major energy level.
The filling of orbitals in the ground state is determined by the following rules :
1. Aufbau Principle : The aufbau principle states that in the ground state of an atom, the orbital
with a lower energy is filled up first before the filling for the orbital with a higher energy commences. In
other words , the electrons enter the various orbitals in the order of increasing energy.
The increasing order of energy of various orbitals is ;
1s 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f , 6d.....
This order of orbitals is only a guidance and exceptions are known in few cases of atoms.
2. Pauli’s exclusion principle : According to this principle , an orbital can contain a maximum
of two electrons and these two electrons must be of opposite spin.
3. Hund’s rule of maximum multiplicity : This rule states that electron pairing in orbitals
of same energy degnerate orbitals will not take place unless all the available orbitals of a given
subshell contain one electron each with parallel spin. For example, we know that there are three p
orbitals (px, py and pz) of the p-subshell in a principle energy level. According to Hund’s rule, each of
the three p orbitals must get one electron each of parallel spin before any one of them gets the
second electron of opposite spin.
Electronic Configurations of Elements
Based on the rules ,we can easily determine the electronic configurations of most elements . We
just need to know the atomic number of an element, the order in which orbitals are to be filled and
the maximum number of electrons in a shell, sub-shell or orbital.The configuration so obtained can
be represented in two ways . As an illustration, let us consider fluorine (Z= 9):
F( Z = 9 ) 1s2 2s2 2px2 2py2 2p1z or

1s2 2s2 2px2 2py2 2p1z
Importance of knowing the exact electronic configuration of an element lie in the fact that the
chemical properties of an element are dependent on the behaviour and relative arrangement of its
electrons.
Electronic configurations of heavier elements (beyond Z = 56 ) deviate a little from the order
mentioned previously. These are brief listed below .

a) Lanthanides La(Z = 57 ) : [Xe] 6s25d1 ( not 4f1)
Ce(Z = 58 ) : [Xe] 6s2 5d1 4f1
Pr(Z = 59 ) : [Xe] 6s2 5d1 4f2
b) Actinides Ac(Z = 89) : [Rn] 7s2 6d1( not 5f1)

Th (Z = 90 ) : [Rn] 7s2 6d1 5f1
Pa( Z = 91 ) : [Rn] 7s2 6d15f2
c) Beyond Z = 103 Z= 104 : [Rn] 5f146d27s2

Z= 105 : [Rn] 5f146d37s2
Z= 106 : [Rn] 5f146d47s2
Z= 112 : [Rn] 5f146d107s2
Illustration 5 : a) A compound of vanadium has a magnetic moment of 1.73 BM.

Find the electronic configuration of vanadium ion in the compound.
b) Name the orbitals corresponding to given set of quantum

numbers
(i) n = 3,  = 2 , m =  2 (ii) n = 4 ,  = 0 ,m = 0
(iii) n = 3,  = 1, m =  1 (iv) n = 2,  = 1 , m = 1
Solution : a) Magnetic moment =  n(n  2) where n = number of unpaired

electrons.
.  n2  2n  (173
 n(n  2)  173 . )2
n  1
therefore vanadium atom must have one unaired electron and thus
its electronic configuration.
4
23V : 1s2 2s2 2p6 3s2 3p63d1
b) i) 3dx2 - y2 or 3dxy
ii) 4s
iii) 4px or 4py
iv) 2px or 2py
Illustration 6 : 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 number in decreasing order of energy.
i) n  4,   0, m  0, s  1 / 2
ii) n  3,   2, m  0, s  1 / 2
iii) n  3,   1, m  1, s   1 / 2
iv) n  3,   0, m  0, s  1 / 2

h
Solution : a)   (   1)  (   1)
2
i) For 3p,   1    1(1  1)  2
h
ii) For 3d,   2    2(2  1)   6
2
iii) For 3s,  = 0,  1  0
b) Higher is the value of (n  ) higher is the energy and if (n  ) are

same than , higher the n values, higher the energy
For (i) (n  ) = 4 4s orbital
For (ii), (n  ) = 5, 3d orbital
For (iii) (n  ) = 4, 3p orbital
For (iv) , (n  ) = 3 3s orbital
Decreasing order of energy = (ii) > (i) > (iii) > iv)
Illustration 7 : Why electron cannot exist inside the nucleus according to

Heisenberg’s uncertainty principle ?
Solution : Diameter of the atomic nucleus is the order of 10-15 m The maximum
uncertainty in the position of electron is 10-15 m.
Mass of electron = 9.1 x 10-31 Kg.
h
x. p 
4
x.(m. V )  h / 4
h 1 6.63x10 34 1
v  x  x 15
4  x. m
4x
22 10 x 9.1 x 10 31
7
v  5.80 x 1010 ms 1
This value is much higher than the velocity of light and hence not possible
.
Illustration 8 : Calculate the de Broglie wavelength of a ball of mass 0.1 kg moving

with a speed of 60 ms-1.
h 6.6 x 1034
Solution :  
mv . x 60
01
. x 10 34 m.
  11
Can we measure this ?
Illustration 9 : How many 7s electrons are there in an atom with Z = 104 ?
Solution : The electronic configuration of the said element is :

1s2,2s2,2p6,3s2,3p6,3d10, 4s2, 4p6, 4d10,4f14, 5s2, 5p6, 5d10, 5f14, 6s2, 6p6, 6d2, 7s2

Hence there are two 7s electrons.
Exercise 2
i) Two particles A and B are in motion. If the wavelength associated with particle A is
5 x 10-8 m, calculate the wavelength associated with particle B if its momentum is
half of A.
ii) Calculate the de Broglie wavelength of an electron that has been accelerated from
rest through a potential difference of 1 kv.
iii) Calculate the uncertainty in position of a particle when uncertainty in the momentum
is (a) 1 x 10-2 gm cm sec-1 and (b) zero.
Photo Electric Effect
Let us try to analyse the Einsteins experiment.He irradiated sodium metal with visible/ultraviolet
light and observed.
1. Electrons came out as soon as the light was irradiated on the surface.
2. There was no emission of electrons for light having frequency less than a certain
frequency,irrespective of the intensity of light used.
3. Photoelectric current increased with increase in intensity of light of same frequency if

emission is permitted.
On the basis of this Einstein had concluded that light must have streams of energy particles
or quanta of energy.
K .E.max = Energy of incident photon- Energy required to liberate an electron.
1/2 mv2max = h- h
h = work function
= Minimum energy of the photon to liberate an electron.
 = Threshold frequency
= Frequency of incident radiation
For electrons to be emitted the frequency of incident light should be  Threshold frequency
 Threshold frequency  0  work function of the metal
Also , h  K.E  
K.E  h  h 0  h(    0 )(   work function)
1
mv 2  h(    0 )
2

Concept of Photon
Observation of photelectric effect made by Einstein had confirmed electromagnetic radiation as

streams of particles .When we stop the radiations by any physical obstruction we cannot convert
radiations into matter. Therefore rest mass of photons ought to zero. Besides according to
m0
Einstein’s formula m  , a particle travelling with the speed of light must be massless.
1  v2 / c2
Otherwise its effective mass during motion will be infinite.
 mo  0
Energy of a photon is denoted by ‘h’
E = h= pc
Where  is the frequency of the wave and p is the momentum associated with the particle E=pc is
valid for all the particles which are massless ( travelling with the speed of light ).
Therefore photon behaves as a MECHANICAL PARTICLE Which can exchange momentum with
other particles.
Note : A photon is always absorbed or destroyed completely or remains intact.
Illustration : 10 : Calculate the kinetic energy of an electron emitted from the surface
of a metal by light of w avelength 5. 5 x 10-8 cm. Threshold energy for the
metal is 2. 62 x 10-9 ergs.
C 3 x 1010 cm s 1
Solution :   8
 5.45 x 1017 s 1
 5.5 x 10 cm
1
/2 mv2 = hh
= ( 6 . 63 x 10-27 ergs - sec ) ( 5.45 x 1017 s-1) - 2. 62 x 10-9 ergs
K. E = 9.93 x 10-10 ergs
Exercise 3 :
i) Find the theshold wavelengths for photoelectric effect from a copper surface, a sodium
surface and a caesium surface. The work function of these metals are 4. 5 eV, 2.3 eV
and 1.9 eV respectively.
ii) Energy required to stop the ejection of electrons from Cu plate is 0.24 eV. Calculate the
work function when radiation of  = 253.7 nm strikes the plate ?
Schrodinger Wave Equation and Quantum Mechanics
8 2 m
2   (E  U)  0
h2

This equation implies in essence that a body of mass m, velocity V, potential energy U and total
energy E has a wave associated with it of an amplitude given by wave funciton  . The schrodinger
equation has an infinite many solution. For any physical situation  must be finite, single valued
and continuous . The particular values of  which yield satisfactory solution of abov e equation
are called wave funcitons wave funciton for an electron is called an atomic orbital.
2
Schrodinger solve Wave funciton 
equation   
 Prbability of finding electron

for electron this wave
function is known as
atomic orbital
QUANTUM MECHANICAL TREATMENT OF HYDROGEN ATOM
Hydrogen atom is the simplest system consisting of one electron and one proton. Schrodinger
equation is written in terms of Cartesian coordinates (x, y, z ). If electron moves at a distance from
the stationary nucleus and atom is spherical in shape . If the position of electron is expressed
in polar coordinates ( r, , the schrodinger equation can be solved easily .
The cartesian coordinates can be converted to polar coordinates by following relation.
x = r sin  cos
y = r sin  sin 
z = r cos 
and also x2 + y2 + z2 = r2
When Schrodinger equaiton is solved in polar coordinates for hydrogen atom. It gives the
possible energy states and corresponding wave function [  ( r ,  ] , called atomic orbitals
.The schrodinger equation cannot be exactly solved for a multi electron atom.
Atomic Orbitals and their Pictorial Representation: An atomic orbital is an electron wave
function,  ( r ,  obtained from the solution of the schrodinger equation . Wave function  is
a mathematical function of the three coordinates of electron ( r ,  This wave function  can be
written into three separate parts each of which is a function of only one coordinate
 = f ( r , 
 ( r ,  = R(r) , 
R is function of r ,  is funciton of and  is function of 

Where, R is radial function and are  angular function. The radial function depends on quantum
members n and  . The angular function depends on  and m.
Signficance of Wave function  : The orbital wave function has no physical significance. It is
the square of the absolute value of wave function |  |2, which has a physical signficance. It
measure the electron probability density at a point in an atom.
If the variations of  or |  |2 with r ,  are to be observed graphically. It would need a four
dimensional graph in space but on the plane of paper we can draw only two dimensional graph
to overcome this difficult .

We draw separate diagrams for
i) Variation of radial function
ii) Variation of Angular function
R is known as radial wave function
probability density and 4 r drR is known as radial proability..
2 2 2
R2 is known as radial
FUNCTION VARIATION OF RADIAL FUNCTION
i) Plot of Radial Wave Function (R) vs r : In all cases R approaches zero as r approaches
infinity . There is mode ( the probability of finding electron is zero ) in 2s orbital radial function.
At the node the value of radial function changes from positive to negative for 2s orbital. In general
ns orbitals have (n -1 ) nodes.
2s 2p
Node
R R
R
r
r r
The plots of the radials wave function R Vs. distance r
ii) Radial Probability Desity (R2) vs : r : The square wave function R2 for an orbital gives the radial
density . The radial density gives the probability density of finding the electron at a point along a
particular line.
2s
Node
1s 2p
R 2
R 2
R2
r
r r
The plots of the radials wave function R2 Vs. distance r
iii) Radial Probability Functions ( 4 r drR ) vs r : Radial probability function gives the probability
2 2 2
of finding the electron at a distance r from the nucleus regardless of direction.
2p
dr4r2R2
2s
4r 2drR 2
4r 2drR 2
1s
r
r r
The plots of the radials wave function 4r2R2 Vs. distance r

ANSWERS TO EXERCISE
Exercise1 : i) 397. 2 nm
ii) 6603 Å
iii) 27434.25 cm-1
iv) 9/5
Exercise2 : i) 10-7
ii) 3.87 x 10 -11 m
iii) (a) 5.27 x 10-28 m
(b) 
Exercise-3 : i) 276 nm, 540 nm, 654 nm
ii) 4.65 eV

SOLVED PROBLEMS
Subjective :
Problem 1 : i) What is the energy and wavelength of photons of frequency 3. 4 MHz ?

ii) Also calculate the energy per mole of photons of the same wavelength.
Solution :   3.4MHz  3.4 x106 HZ  3.4 x106 S1

c 3 x 108 ms 1
   88.2m
 3.4 x 106 s 1
Energy, E  h = 6.626 x 10-34 x 3.4 x 106 J
= 2.253 x 10-27J
Energy per mole of photon = 6.02 x 1023 x 2.53 x 10 -27 J mol-1
= 1. 356 x 10-3 J mol-1
Problem2 : What is the wavelength of the first line in Paschen series of the hydrogen
spectrum ?
F
G 1I
H3  4 J
1
Solution ; V  RZ 2 2 2K
= 109737 x 0.0486 = 5334 cm-1
1
  . x104 cm
 1875

Problem 3: The wave number of the first Balmer line in the hydrogen spectrum is
15200 m-1 .Calculate the wavelength of the first Lyman line in the spectrum
of He+, Li2+.
  RZ 2
L
M
1 1O
 P 1
Solution :
N2 3 Q 15200cm
2 2
36
R  15200x cm 1( Z  1 for hydrogen)
5
 36 1F
G 1 IJ
 2 cm 1(LymanSeries)  328320 cm 1
For He ,   4 x 15200 x
5 12H 2 K
1
 Wavelength of the first Lyman line  cm
328320
= 3.046 x 10-6 cm
= 304,6 Å
36 3
Similarly for Li2+ .,   9 x 15200 x x cm 1 = 738720 cm-1
5 4
  1354
. x 10 6 cm  135.4 Å
Problem:4 What is de Broglie wavelength for a hydrogen atom moving with a velocity of
2000 ms-1 ? (Atomic mass of hydrogen = 1. 00797 a.m. u )

.
10097
Solution : Mass of a hydrogen atom = . x10 24  1673
g  1673 . x 10 27 kg
6.023 x 10 23
h 6.626 x 10 34
  . x 10 10 m  19.8 nm
m  198
mv 1.673x10 27 x 2000
Problem 5 : a) The uncertainties in the position and velocity of a particle are 10 -10 m
and 5.27 x 10-24 m/sec. respectively . Calculate the mass of the particle
b) Find the number of waves made by a Bohr electron in one complete
revolu tion in the 3rd Bohr orbit
h
Solution : a) As x. P 
4
h
 x x mV 
4
h
m 
4 x x x V
6.625 x 10 34
=   010
. kg
. x 10 10 x 5.27 x 10 24
4 x 314
b) Circumference of 3rd orbit = 2 r3 ... (i)

h 3h
Also mvr3  3  ... (ii)
2 2
From de Broglie equation
h

mv
h
  3  2 r3  3x  2r3
3h / 2 r3
or 2 r3  3
Thus the circumference of the 3rd orbit is equal to three times the de-
Brogile wavelength associated the electron
Problem 6 : A gas of identical H - like atom has some atoms in the lowest (ground ) energy
level (A) and some atoms in a particular upper excited energy level (B) and
there are no atoms in any other energy level. The atoms of the gas make
transition to a higher energy level by absorbing monochromatic light of
photon energy 2.7 eV. Subsequently, the atoms emit radiation of only six differ
ent photons energies some of the emitted photons have energy 2.7 eV some
have more and some have less than 2.78 eV.
i) Find the principal quantum number of initially excited level B

ii) Find the ionization energy of the gas atoms
iii) Find the maximum and the minimum energies of the emitted photons.
Solution : i) As electrons are present in ground state and some excited state (say, n1) and after

absorbing 2.7 eV, electrons are excited to another excited state say n 2.
ii) After dexcitation from n2 level radiation of only six photon energies are emitted. n2
comes out be 4
As  (n2  1)  6 , when n2 = 4
iii) Absorption of 2.7 eV energy causing excitation to 4th shell and then reemitting
photons of energu equal to, more than , or less than 2.7 eV, is possible only when
n1 = 2
RHCh
En 
n2
RHCh
n4 E4 
; 42
; RHCh
n3 E3 
32
; RHCh
n2 E2 
22
; RHCh
n1 E2 
12
E4 - E2 = 2. 7 eV
E4 -E1 > 2. 7 eV
E4 - E3 < 2. 7 eV
As E4 - E2 = 2. 7 eV
F
GR Ch I
H 2 JK 2.7
RhCh h
2
 2
4
R Ch F I
 G 1J 2.7
1
H4 K
h
4
L
E1 3
M O

4 4 NP 2.7
Q
2.7 x 16
 E1   14.4eV
3
 Ionisation energy  14.4eV
E1 E1 14.4
Emax  E4  E1  2
 2 =  14.4  135
. eV
4 1 6
E1 E1
Emin  E4  E3  2
  0.7eV
4 32

Problem 7 : Iodine moecule dissociates into atoms after absorbing light of 4500Å . If
one quantum of radiation is absorbed by each molecule,Calculate the kinetic
energy of iodine atoms (B.E of l 2 of 240 KJ/mole
hc
Solution : Energy given to l2 molecule =

6.625 x 10 34 x 3 x 108

 10
 4.417 x 10 19 Joule
4500 x 10
Energy used for breaking up of l2 molecule
240 x 103
 23
 3. 9 8 4 x 1 0  1 9 J o u le
6 .0 2 3 x 1 0
 Energy used in imparting kinetic energy of two l atoms
= 4. 417 x 10-19 - 3.984 x 10-19 =( 4.417 - 3.984) x 10-10 J
= 0.431 x 10-19 Joule
0.431
 K. E / atom = x 10 19  0.216 x 10 19 J
2
Problem 8 : Photo - electrons are liberated by ultraviolet light of wavelength 3000Å from
a metallic surface for which the photoelectric threshold is 4000Å. Calculate
de-Broglie wavelength of electrons emitted with maximum kinetic energy
o hc hc
Solution : As, h  h  KE   o  K. E
 
F
G1 1I
H   JK=
hc(   o )
 K.E  hc 0 
 x o
6.625 x 10 34 x 3 x 108 ( 4000 x 10 10  3000 x 10 10 )

 10
 16565
. x 10 19 Joule
3000 x 10 x 4000 x 10
1
Also  m v 2  1.6 2 6 5 x 1 0  1 9  m 2 v 2  2 x 1.6 5 6 5 x1 0  1 9 x m
2
 m2 v 2  2 x 16565
. x 10 19 x 9.109 x 1031  m  5.49 x 10 25
h 6.625 x 10 34
  25
. x 10 9 m
 12
mv 5.49 x 10
Problem 9 : A mixture contains atoms of fluorine and chlorine.The removal of an electron

from each atom of sample absorbs 284 kJ while the addition of an electron to
each atoms of mixture release 68.89 kJ. Determine the percentage composition
of the mixture given that the ionization energies of Fand Cl are 27.91 x 10 -22 and
20.77 x 10-22 kJ, respectively ,and electron affinities are 5.53 x 10-22 and 5.78 x 10-22
kJ respectively.
Solution : Let atoms of chlorine and fluorine in the mixture be x and y respectively
 Energy absorbed = 284 KJ = (x) x 20. 77 x 10-22 + Y x 27.91 x 10-22 ..... (i)
Energy released = 68.8 kJ = (x) x 5.78 x 10-22 + Y x 5.53 x 10-22..... (ii)

From solving equation (i) and (ii) we can get the values of x and y respectively.
% of Cl = 62. 19
% of F = 37. 81
Problem 10 : Two hydrogen atoms collide head on and end up with zero kinetic energy.Each
then emits a photon of wave length 121. 6 nm which transition leads to this
wavelength? How fast were the hydrogen atoms travelling before collision ?
RH = 1.09678 x 107 m-1
MH = 1.672 x 10-27 kg
Solution : As wavelength of emitted radiation is 121. 6 nm, which falls in UV region of spectrum
Therefore, n1 = 1
1 1L
M
1 O
For hydrogen atom
 1 N P
 RH 2  2
n Q
1 L1  1 O
 1.099678 x 10 M
1 n P
7

. x 10
1216 9
N2
Q
n=2
Energy released is due to collision and all the kinetic energy released in form of radiant
energy
1 hc
mv 2 
2 
1 6.625 x 10 34 x 3 x 108

 . x 10 27 x V 2 
167
2 121.6 x 10 -9
 V  4.42 x 10 4 m / sec

Objectives
Problem 1 : If the total energy of an electron in a hydrogen like atom in excited state is - 3.4
eV , then the de Brglie wavelenth of the electron is
(A) 6 . 6 x 10-10 (B) 3 x 10-10
(C) 5 x 10 9
(D) 9 . 3 x 10-12
E1 13.6
Solution : Total energy (En )  2
 3.4eV 
n n2
13.6
 n2   4 n = 2
3.4
V1 2.18 x 106
The velocity of electron in 2nd orbit =  m / sec
2 2
h 6.625x10 34 x2
  31 6
 6.6x10 12 m
mv 9.1089 x 10 x 2.18 x 10
= 6 . 6 x 10-10 cm
( A )
Problem 2 : The highest excited state that an unexcited hydrogen atom can reach when
they are bombarded with 12. 2 eV electron is :
(A) n = 1 (B) n = 2
(C) n = 3 (D) n = 4
Solution : E1 = -13.6 eV . After absorption of 12. 2 eV, energy of electron = - 13. 6 + 12.2 =- 1.4
eV
E1 13.6
En   n2   9.71 n=3
n 2 1.4
 (C)
Problem 3 : If 10-7 J of light energy is needed by the interior of human eye to see an
object. The photons of green light (  = 550 nm ) needed to see the object are.
(A) 27 (B) 28
(C) 29 (D) 30
hc
Solution : Required energy = 10-17 J = n x

6.625 x 10 -34 x3 x108

nx J  10 17 J
550 x 10 9
 n = 28
 (B)
Problem 4: The wave number of the shrotest wave length transition in Balmer series of
atomic hydrogen will be
(A) 4215 Å (B) 1437 Å
(C) 3942 A (D) 3647 Å
1 F1  1 I
Solution :  shortest
 RZ 2 G
Hn n J
2
1 K 2
2

F
G 1 I
H2  JK
1
= 109678 x 12 x 
2 2
  3.647 x 105 cm
= 3647 Å
 (D)
Problem 5: Which have the same number of S electrons as the d- electrons in Fe 2+

(A) Li (B)na
(C) N (D) P
Solution : P has 6 electrons in s sub shell as in the d sub shell of Fe2+

 (D)
Problem 6 : Which orbital has two angular nodal planes

(A) s (B) p
(C) d (D) f
Solution : Angular node =  , For d - orbital  = 2

 (C)
Problem 7 : Which ions has the maximum magnetic moment

(A) Mn3+ (B) Cu2+
(C) Fe3+ (D) V3+
Solution : Magnetic moment = n(n  2

where n = number of unpaired electron.
 (C)
Problem 8 : Ionisation potential of hydrogen is 13.6 eV. Hydrogen atom in the ground state
are excited by monochromatic light of energy 121. eV. The spectral lines
emitted by hydrogen according to Bohr’s theory
(A) One (B) Two
(C) Three (D) Four
Solution : The electron in H atom is excited to IIl shell after absorbing 121. eV. The possible
tranition state = 
b g3 .
331
2
 (C)
Problem 9 : Predict the total spin in Ni2+ ion

(A) 5 / 2 (B) 3 / 2
(C) 1 / 2 (D) 1
Solution : No of unpaired electron = 2
 (D)
Problem :10 With increasing principal quantum number, the energy difference between
adjacent energy levels in atoms.
(A) decreases (B) increases
(C) Remains constant (D) decreases for low z and increases for high z

1
Solution : E
n2
(A)
Problem :11 The number of electrons in sulphur atom having n +  = 3 ?

(A) 2 (B) 4
(C) 6 (D) 8
Solution : The electronic configuration of sulphur atoms 1s2 2s22p63s23p4, the orbitals with
( n +  ) = 3 are 2p and 3s, therefore 8 electrons in sulphur atom have (n+  ) = 3
 (D)
Problem12 : Which atom contains an electron with quatum number n = 3 ,  -2, m = -1 s= -1/2
(A) Ne (B) Co
(C) Cl (D) K
Solution : Qauntum number n = 3,  = 2, m = -1 S = -1/2 represent 3d electron which is

present in Co.
 (B)
Problem13 : The wavelength of a spectral line for an electronic transition is inversely

reltated to
(A) number of electrons undergoing transition
(B) the nuclear charge of the atom
(C) velocity an electron undergoing tranition
(D) the difference in the energy levels involved in the transition .
hc hc
Soluiton : E  
 E
(D)
Problem :14 If E1 ,E2 and E3 represent respectively the kinetic energies of an electon,
particle and a proton, each having same de Broglie’s wave length then
(A) E1 > E3 > E2 (B) E2 > E3 > E1
(C) E1 > E2 > E3 (D) E1 = E2 = E3
h
Solution : K.E  1 / 2mv 2 ,  
mv
h2 h2
 K.E  1 / 2m 
(m )2 2m2
( A )
Problem 15 : When the frequency of light incident on a metallic plate is doubled, the K.E of the
emitted photoelectrons will be
(A) doubled (B) halved
(C) increase but more than double of the previous K.E (D) unchanged
Solution : Upon doubling the frequency, energy of photon will be be doubled with work function
of metal will remain constant . So K.E of photo electron will be more than the double
of what it possessed previously .
(C)

Assigments
Sujbective
LEVEL-1
1. A single electron system has ionization energy 11180 kJ/mol.Find the number of protons
in the nucleus of the system.
2. Calculate the wavelenth of the photon, which excites the electron of hydrogen atom from
ground state to fourth energy level.Ionization energy of hydrogen atom is 1312 kJ /mol.
3. Calcualte the mass of photon of electromagnetic radiation with a wavelength of 5.89 x10 -7 M
4. Calculate the velocity of an electron placed in the third orbit of hydrogen atom. Also calcu
late the number of revolutions per second that this electron makes around the nucleus.
5. If the electron of hydrogen atom has been excited to energy level, difference corresponding
to 10.2 electron volts. What is the wavlength of light emitted when the atom returns to its
ground state ?
6. How much will the kinetic energy and total energy of an electron in H atom change if the
atom emits a photon of wavelength 4860 Å ?
7. With what velocity should an particle travel towards the nucleus of copper atom so as
to arrive at a distance 10-13 meter from the nucleus of the copper atom ?
8. Calculate the wavelength of radiations emitted producing a line in Lymann series , when
electron falls from fourth stationary state in hydrogen atom to ground state (RH= 1.1 x 107 m-1)
9. An electron beam can undergo diffraction by crystals. Through what potential should a
beam of electrons be accelerated . So that its wave length becomes equal to 1.54 Å.
10. The reaction between H2 and Br2 to form HBr in the presence of light is initiated by the
photo decomposition of Br2 into free bromine atoms (Free radicals ) by absorption of light.
The bond dissociation energy of Br2 is 192 kJ/mole. What is the longest wavelength of the
photon that would initiate the reaction ?
11. Calculate the energy emitted when electrons in 1 g atom of hydrogen undergo transition
giving spectral lines of lowest energy in the visible region of its atomic spectrum.
12. Calculate the de Broglie wavelength of the electron in the ground state of hydrogen atom,
given that its kinetic energy is 13.6 eV. ( 1eV = 1. 602 x 10-19J ).

LEVEL-ll
. x 10 12
217
1. The energy E for an electron in H atom is given as En  erg. Calculate the
n2
energy required to remove electron completely from n = 2 orbit. Also calculate the longest
wavelength of light that can be used to cause this transition
2. The dissociation energy of H2 is 430.53 kJ/mol. If H2 is exposed to radiation energy of wave

length 253.7 nm. What % of radient energy will be converted into kinetic energy ?
3. The kinetic energy of a subatomic particle is 4.55 x 10-25 J. Calculate the frequency of the
particle wave ( h = 6.625 x 10-34 J sec )
4. The minium energy required to overcome the attractive forces between electron and the
surface of Ag metal is 7.52 x 10-19 J. What will be the maximum kinetic energy of electron
ejected out from Ag metal surface which is being exposed to UV light of wavelength
360Å
5. Calculate the accelerating potential that must be imparted to a proton beam to give it an
effective wavelength of 0.005 nm.
6. Wavelength of high energy transition of H-atoms is 91.2 nm. Calculate the corresponding
wavelenth of He atoms.
7. The angular momentum of an electron in a Bohr orbit of H atom is 4.2178 x 10-34 Kg m2/sec.
Calculate the wavelength of spectral line emitted when electron falls from this level to next level.
8. What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition , n = 4 to n = 2 of He+ spectrum ?
9. A bulb emits light of wavelength 4500 Å. The bulb’s rated as 150 watt and 8 % of the energy is
emitted as light. How many photons are emitted by the bulb per second ?

10. The dissociation l2  h  2l utilizes one photon per iodine molecule dissociated . The maxi
mum  for this is 4995 Å . Calculate number of moles of l2 dissociated per kJ of photon
energy.
11. A particle of charge equal to that of an electron and mass 208 times the mass of electron
( i. e., mu- meson ) moves in a circular orbit around a nucleus of charge + 3e. (Take the
mass of the nucleus to be infinite ) . Assuming that the Bohr model of the atom is applicable
to this system . (RH = 1. 097 x 107 m-1)
(i) Derive an expression for the radius of Bohr orbit
(ii) Find the value of n for which the radius of the orbital is approximately the same as that
of the first Bohr orbit for H-atom .
(iii) Find the wavelength of the radiation emitted when the mu- meson jumps from the third
orbit to the first orbit.
12. Estimate the difference in energy between 1st and 2nd Bohr’s orbit for a H atom. At what
minimum at no. a transition from n = 2 to n = 1 energy level would result in the emission
of X- rays with   3.0 x 10 8 m ? Which hydrogen atom like species does this atomic no.
corresponds to ?

LEVEL- III
1. A certain laser transition emits 6.37 x 1015 quanta per second per square metre.Calculate
the power output in joule per square metre per second.
Given = 632.8 nm
2. Compare the energy of n = 5 to n = 4 transition of an electron plus nucleus with z = 3

with the energy of n = 2 to n = 1 transition for an electron plus nucleus with z = 2
3. Which hydrogen like ion has the wavelength difference between the first line of Balmer
and Lyman series equal to 59.3 nm ? RH = 109678 cm-1
4. Calcualate the wavelength of the radiation that would be emitted when an electron in the
fourth orbit of He+ ions falls to the second Bohr orbit. To what transition does this light
radiation would correspond in the hydrogen atom ?
5. Energy required to stop the ejection of electrons form Cu plate is 0.24 eV. Calculate the
work function when radiaitons of = 253.7 nm strikes the plate.
6. In a photoelectric effect experiment, irradiation of a metal with light of frequency 2.00 x

1016 Hz yields electrons with maximum kinetic energy 7.5 x 10-18 J. Calcualate  o for the
metal .
7. Photoelectric emission requires a threshold frequency of  o . For a certain metal 

=2200 Å and =1900 Å produce electrons with maximum kinetic energy KE1and KE2 . If
KE2 = 2KE1 calculate the corresponding wave length.
8. The velocity of electron in a certain Bohr orbit of H atom bears the ratio 1:275 to the velocity
of light.
(A) What is the quantum number (n) of orbit ?
(B) Calculate the wave number of radiations emitted when electron jumps from (n+1) state
to ground state.
9. Consider the hydrogen atom to be a proton embedded in a cavity of radius a0 (Bohr radius )
whose charge is neutralized by the addition of an electron to the cavity in vacuum, infinitely
slowly, Estimate the average total energy of an electron in its ground state in a hydrogen atom
as the work done in the above neutralization process .Also if the magnitude of the average
kinetic energy is half the magnitude of the average potential energy, find the average potential
energy.
10. O2 undergoes photochemical dissociation into one one normal oxygen atom and one oxygen
atom, 1.967 eV more energetic than normal . The dissociation of O2 into two normal atoms of
oxygen requires 498 kJ mole-1 .What is the maximum wavelength effective for photochemi
cal dissociation of O2?
11. The Characteristics X - ray wavelength for the line of the K series in elements X and Y are
9 .87 Å and 2.29 Å respectively. If Moseley’s equation v = 4. 9 x 10 ( z - 0.75) is followed,
7
what are atomic number of X and Y ?
12. 1 gm of Mg atoms ( atomic mass 24. 0 a. m. u ) in the vapour phase absorb 50.0 KJ of energy
.Find the composition of the final mixture, if the first and second ionization energies of Mg are
740 and 1450 kJ mol-1 respectively.

OBJECTIVES
LEVEL-l
1. How many electrons with  = 3 are there in an atom having atomic number 54.
(A) 3 (B) 10
(C) 14 (D) None
2. The maximum number of electrons possible in sublevel is equal to

(A) 2  + 1 (B) 2n2
(C) 2  2 (D) 4  + 2
3. Rutherford’s experiment ,which established the nuclear model of the atom, used a beam of
(A) - particles which impigned on a metal foil and got absorbed
(B)  -rays, which impigned on a metal foil and ejected electrons.
(C) helium atoms, which impigned on a metal foil and got scattered.
(D) helium nuclei, which impigned on a metal foil and got scattered.
4. The correct set of quantum number for the unpaired electron of chlorine atom is
(A) n  2,   1, m  0 (B) n  2,   1, m  1
(C) n  3,   1, m  1 (D) n  3,   0, m  0
5. If the energy of an electrol in the first Bohr orbit of H -atom is - 313.6 Kcal/mol; then energy
of electron in the second orbit will be
(A) - 34.84 Kcal/mol (B) -12.5 Kcal/mol.
(C) -78.4 Kcal/mol (D) 313.6 Kcal/mol
6. The wavelength associated with a golf ball weighing 200 g and moving at a speed of 5m/h is
of the order.
(A) 10-10 m (B) 10-20 m
(C) 10-30 m (D) 10-40 m
7. The statements whichis/are correct

(A) Number of total nodes in an orbital = (n -1 )
(B) Number of radial nodes in an orbita = n -  -1
(C) Number of angular nodes in an orbital = 
(D) All
8. Which represent an impossible arrangement ?

n  m s
(A) 3 2 -2 1/2
(B) 4 0 0 1/2
(C) 3 2 -3 1/2
(D) 5 3 0 1/2
9. Which set of quantum number is not consistent with theory ?

(A) n  2,   1, m  0, s  1 / 2 (B) n  4,   3, m  2, S  1 / 2
(C) n  3,   2, m  3, S  1 / 2 (D) n  4,   3, m  3, S  1 / 2
10. Which set of quantum number represent the electron of lowest energy ?
(A) n  2,   0, m  0, S  1 / 2 (B) n  2,   1, m  0, S  1 / 2
(C) n  4,   0, m  0, S  1 / 2 (D) n  4,   0, m  0, S  1 / 2

11. The nucleus of an atom is located at x = y = z = 0. If the probability of finding an s-
orbital electron in a tiny volume assumed x = a, y = z= 0, is 1 x 10 -5, what is the probability
of finding of the electron in the same sized volume around x = z = 0, y = a ?
(A) 1 x 10-5 (B) 1 x 10-5 a
(C) 4 x 10 a
-5 2
(D) 1 x 10-5 x a-1
12. Which orbital has two angular nodal planes

(A) s (b) p
(C) d (D) f
13. If wavelength is equal to distance travelled by the electron in one second , then
h h
(a)   (B)  
p m
h h
(C)   (D)  
p m
14. Number of photon of light of wavelength 4000 Å required to provide 1.00J of energy is
(A) 2. 01 x 1018 (B) 12. 01 x 1031
(C) 1. 31 x 10 17
(D) None is correct
15. As electron moves away from nucleus its K.E

(A) Decreases (B) Increases
(C) Remains constant (D) None

LEVEL - II
1. The work function of a photelectric material is 3.3 eV .Its threshold frequency will be
(A) 8.87 x 1015 Hz (B) 15 x 1033 Hz
(C) 8 x 10 Hz
10
(D) 4 x 1011 Hz
2. The threshold frequency of a metal is 4 x 1014 s-1. The minium energy of photon to cause
photoelectric effect is
(A) 3.06 x 10-12 J (B) 1.4 x 10-48 J
(C) 3.4 x 10-19 J (D) 2.64 x 10 -19 J
3. Ultra violet light of 6.2 eV falls on aluminium surface (work function = 4.2 eV). The kinetic
(in Joule ) of the fastest electron emitted is approximately.
(A) 3. 10-21 (B) 3 x 1019
(C) 3 x 10 -17
(D) 3 x 10-15
4. In the emission line spectra of hydrogen atom,how many lines can be accounted for by all
possible electronic transition form 5th energy levels within the atom.
(A) 4 (B) 5
(C) 10 (D) 20
5. The potential energy of an electron in hydrogen atom is - 3.02 eV, its kinetic energy will be
(A) 1.51 eV (B) 15. 10 eV
(C) 13.6 eV (D) 1.36 eV
6. An electron in a hydrogen atom in its ground state absrobs twice its ionisation energy
what is the wavelength of the emitted electron ?
(A) 3.32 x 10-10 m (B) 33.2 x 10-10 m
(C) 0.33 x 10 m
-4
(D) 0.33 x 10-6 m
7. The quantum numbers +1/2 and -1/2 for the electron spin represent
(A) rotation of the electron in clockwise and anticlockwise direction respectively.
(B) rotation of the electron in anticlockwise and clockwise direction respectively.
(C) magnetic moment of the electron pointing up and down respectively.
(D) two quantum mechanical spin states which have no classical analogue.
8. The energy of an electron in the first Borh orbit of H- atom is -13.6 eV. The possible energy
value (s) of the excited stae (s) for electron in Bohr orbit of hydrogen is (are )
(A) -3.4 eV (B) - 4.2 eV
(C) - 6. 8 eV (D) + 6.8 eV
9. The electron identified by quantum number n and l (i) n = 4 ,  = 1, (ii) n = 4  = 0, (iii) n =

3, l = 0, (iv) n = 3,  =1 can be placed in order of increasing energy from lowest to highest .
(A) (iii) < (iv) < (ii) < (i) (B) (iii) < (iv) < (i) < (ii)
(C) (i) < (iii) < (ii) < (iv) (D) (iii) < (i) < (iv) < (ii)
10. Which of the the following represent (s) the correct set of four quantum numbers of a 4d
electron?
(A) 4, 3, 2 +1 /2 (B) 4, 2 , 1 + 1/2
(C) 4, 3, -2, +1/2 (D) None.

11. Wave function vs distance from nucleus graph of an orbital is given below:
+

r 
The number of nodal sphere of this orbital is

(A) 1 (B) 2
(C) 3 (D) 4
r
12. For an electron in a hydrogen atom the wave function , y is proportional to , where ao
a0
e
is the Bohr’s radius . What is the ratio of probability of finding the electron at nucleus
to the probability of finding the electron at the nucleus to the probability of inding it a 0.
(A) e (B) e2
1
(C) (D) Zero
e2
13. If each orbital can hold a maximum of 3- electrons. The number of elements in 4 th period
of periodic table is :
(A) 48 (B) 57
(C) 27 (D) 36
14. The no. of orbital is a subshell is equal to

(A) n2 (B) 2
(C) 2 + 1 (D) m
15. Which of the following statements (s) is (are ) correct

(A) The electronic configuration of Cr is[Ar ]3d5 4s1
(B) The magnetic quantum number may have negative value
(C) In silver atom 23 electrons have spin of one type adn 24 of the opposite type (atomic
number of Ag= 47 )
(D) All

ANSWERS
SUBJECTIVE
LEVEL -I
1. z=3
2. 97.45 X 10-9 m
3. 3.752 x 10-36 Kg
4. V3 = 7.275 x 105 m /sec ; rps = 2.432 x 1014
5. = 1219 Å
6. KE = 2.553 eV( increases ); E= 2. 553 eV(decreases )
7. 8.97 x 106 m/ s
8. = 9.67 x 10-8 m
9. 63.5 V
10. 6235 Å
11. 182.5 kJ
12. 0.3328 nm
LEVEL - II
1. E = 5.425 X 10-12 erg, 366. 4 nm

2. 8.53 %
3. v = 1. 366 x 109 Hz
4. 47.868 x 10-19 J
5. 32.85 v
6. He= 22.8 nm
7. 1.8 x 10-6 m
8. n2 = 2 to n1 = 1
9. 27.2 x 1018
10. 4.175 x 10-3 moles of l2
(i) r  n2
L
M
2
h x4  0
O
P 2
 n x 8.4 x 10 14
m
11.
M
N4 m' Ze
2 2
P
Q
(ii) n = 25
15. 10.2 eV, 2, He+
LEVEL -III
1. 2 X 10-3 Jm-2 sec-1
2. E1/E2 = 0.0675
3. Z = 3 , Li2+ ion
4. 1212 Å ; n = 2 to n = 1
5. 4.65 eV
6. 8.7 x 1015 Hz
7. o = 2612 Å; vo = 1.1483 x 1015 Hz
8. (a) n = 2 , (b)   9.75 x 104 cm 1
9. P.E = -e2/4  0 a 0
T. E = - e2/ 8  0 a0
10. 1741.3 Å
11, x = 12 , y = 24
12. % of Mg+ = 68. 3, % of Mg2+ = 31.7

OBJECTIVE
LEVEl - I
1. D 2. D 3. D 4. C 5. C
6. C 7. D 8. C 9. C 10. A
11. A 12. C 13. D 14. A 15. A
LEVEl - lI
1. A 2. D 3. B 4. C 5. A
6. A 7. D 8. A 9. A 10. B
11. A 12. D 13. C 14. C 15. D

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Electron Proton Neutron

Approximate relative 1/1836 of mass of 1 1

Mass in Kg 9.109534x 10-31 1.6726485 x 10-27 1.6749543 x 10-27

Mass in amu 5.4858026 x 10-4 1.007276471 1.008665012

Actual charge /C 1.6021892 x 10-19 1.6021892 x 10-19 0

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Nucleons : Sub-atomic particles in the nucleus of an atom , i. e protons and neutrons.

Isoelectronic : Atoms molecules or ions having the same number of electrons, e. g N 2,

Rutherford’s -rays scattering experimet : A beam of alpha particles, (dipositive helium

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Typical atomic structures may be represented as follows :

Line Spectrum of Hydrogen Atom

The spectrum of hydrogen consists of lines corresponding to widely different frequencies.

Where  is the wavelength , v is frequency, c is the velocity of light, R  a constant known as

Series n m Position in solar Spectrum

Lyman 1 2,3, 4 etc ultra-violet

Balmer 2 3,4, 5 etc Visible

Paschen 3 4, 5, 6 etc infra-red

Brackett 4 5, 6, 7 etc infra-red

Pfund 5 6, 7, 8 etc infra-red

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The Bohr Atom

Bohr’s model of an atom can be described as follows

Radius & Energy Levels of Hydrogen Atom

Coulombic force = Centrifugal force

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N KJ/mole. Ergs/ molecules

4 -82 -1.36 x 10-12

2 -328 -5.42 x 10-12

1 -1312 -21.8 x 10-12

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i) Find the wavelength of radiation required to excite the electron in

Excitation energy = E  E3  E1  13.6 x 3

= + 13.6 x 9 [ 1 - 1/9 ] = 13. 6 x 9 x 8/9 = 108.8 ev .

Illustration 2 : Ionisation energy of hydrogen atom is 13.6 eV.Calculate the ionisation

Solution : Ionization energy of hydrogen = - E1 ( Energy of first Bohr orbit )

Ionization energy of Li2+

Ionization energy of Be3+

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Illustration 3 : Calcualate the energy emitted when electrons of 1.0 gm atom of

Solution : Visible region of H- spectrum correspond to Balmer series n1 = 2, n2 = 3 (

i) A series of lines in the spectrum of atomic hydrogen lies at wavelengths 656.46 ,

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Shortcomings of Bohr’s theory

4. Another objection to Bohr’s theory came from Heisenberg’s uncertainty principle .

Particle and Wave Character (Dual Character ) of Electrons

Derivation of de Broglie’s equation .

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Pauli’s Exclusion Principle

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Shapes and Sizes of Orbitals

s- orbitals (  = 0 ) : The orbitals are spherical and Y

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1. The major energy shell , 1, 2, 3, 4 etc., is written first.

2. The subshell , Viz, s, p, d and f is written next.

3. The number of electrons in the particular subshell is shown by a superscript placed to

The increasing order of energy of various orbitals is ;

Electronic Configurations of Elements