Unit 1

Atomic Structure

Daltons Theory of Matter

Dalton proposed that matter was made up of extremely small particles called atoms.
Main postulates of Daltons atomic theory :
1. Matter is made up of small invisible particles called atom.
2. Atom is the smallest particle of an element that takes part in a chemical reaction.
3. Atoms of same element are identical.
4. Atoms of different elements are different.
5. Atoms can neither be created nor can be destroyed.
A chemical reaction is just a rearrangement of atoms.
6. Atoms of different elements combine in a fixed ratio of small whole numbers to form compound
atoms, called molecules.
But later scientists established that atom was not the smallest indivisible particle but has a complex
structure of its own, and was made up of still smaller particles like electrons, protons, neutrons etc.
Electron, proton and neutron are regarded as fundamental particles.

Models of Atoms
Thomsons Model (Plum Pudding Model)
He suggested that atom is a positively charged sphere having electrons embedded uniformly giving an
overall view of plum pudding.

Rutherfords Model
He allowed a narrow beam of light to fall on a thin gold foil and determined the path of particles with the
help of ZnS fluorescent screen.
The ZnS gives off a visible flash of light when struck by an -particles.

Observation of Rutherford
1. Most of the -particles pass straight through the gold strips with little or no deflection.
2. Some -particles are deflected from their path and diverge.
3. Few -particles are deflected backwards through angles greater than 90.
2 Indian National Chemistry Olympiad

Atomic Model Proposed by Rutherford

Rutherford proposed atomic model as follows:
1. Atom consists of two parts (a) Nucleus and (b) Extra nuclear part
2. All the protons (positive charge) and the neutrons (neutral charge) i.e.,nearly the total mass of an
atom is present in very small region at the centre of the atom. The atoms central core is called
nucleus.
3. Diameter of nucleus is about 1013 cm. Atom has a diameter of order of 108 cm. Size of atom is
105 times more than that of nucleus.
4. Most of space outside nucleus is empty.
5. Electrons revolve around the nucleus with fast speed in various circular orbits.
6. The centrifugal force arising due to fast speed of an electron balances coulombic force of attraction
of the nucleus and electron remains stable in its path.

Defects in Rutherfords Model

1. The exact position of electrons from the nucleus are not mentioned.
2. Neils Bohr found Rutherfords model defective in respect of stability of atom. According to law of
electrodynamics the electron should therefore, continuously emit or use energy for moving and get
closer to the nucleus and after passing through a spiral path, ultimately fall into the nucleus.
Neils Bohr proposed an improved form of Rutherfords atomic model based on the quantum theory
of radiation put forth by Max Planck.

Few Important Terms

1. Atomic number Atomic number of an element is the number of protons contained in the
nucleus of the atom of that element. It is represented by Z.
2. Nucleons It is the number of neutrons and protons together present in a nucleus.
3. Mass number The total number of protons and neutrons present in the nucleus. It is
represented by A.
IUPAC notation of an atom (nuclide)
The element can be represented as Z X A
Where, X = chemical symbol of element.
4. Isotopes Atoms of the element with same atomic number but different mass number.
2
1H , 1 H , 1H
1 3
Example are three isotopes of hydrogen.
5. Isobars Atoms having same mass number but different atomic number.
32 32
Example 15 P and 16 S are isobar.
6. Isotones Atoms having same number of neutrons but different number of protons or
mass number.
14 16 15
Example 6C , 8 C , 7 N are isotones.
7. Isoelectronic Atoms, molecules or ions having same number of electrons.
Example N2, CO, CN
8. Atomic mass unit It is equal to 1/12 of the mass of 6 C12 atom. 1 u = 1.66 1027 kg
Atomic Structure 3

Characteristics of Waves
A wave is a sort of disturbance which originates from some vibrating sources and travels outwards as a
continuous sequence of alternating crests and trough.
Every wave has five important characteristics, i.e.,wavelength ( ), frequency (), velocity (c ), wave number
( ) and amplitude (a).
1. Wavelength ( ) The distance between two neighbouring troughs and crests is known as
wavelength. It is expressed in cm, m , nm and .
2. Frequency () The frequency of a wave is the number of times a wave passes through a given
point in one second. It is denoted by . It is expressed in cycles per second (cps) or hertz. (Hz)
1Hz = 1 cps.
The frequency of a wave is inversely proportional to its wavelength ().
1


c
or =

3. Velocity The distance travelled by the wave in one second. It is denoted by c and is expressed
in cm/s.
c =
4. Wave number () It is defined as the number of wavelengths per cm. It is denoted by and is
expressed in cm 1 .
1
= , =
c
5. Amplitude (a) It is the height of the crest or depth of trough of a wave. It is denoted by a. It
determines the intensity or brightness of the beam of light.

Radiant Energy
It is the energy transmitted from one body to another in the form of radiation. Maxwell found that an
alternating current of high frequency radiates energy in the form of waves which travel in space with the
same speed as light. These waves were called as electromagnetic waves or electromagnetic radiations.
Radiant energy has wave nature and is associated with electric as well as magnetic field. These
radiations are called electromagnetic radiation.
Various forms of electromagnetic radiations are cosmic rays, -rays, X-rays, UV rays, visible rays,
infrared rays, microwaves, radar waves and radio waves such as TV, FM, AM rays.
Electromagnetic radiations arranged in the increasing order of wavelength or frequency, called
electromagnetic spectrum.
Thus, the spectrum of radiations means different radiations arranged according to their wavelength.
When a band of visible light is passed through a prism of glass, all the colours of white light get
separated into violet, indigo, blue, green, yellow, orange and red. It is known as spectrum and there is no
overlapping of colours.
hc
E = hv =

where, = Frequency, c = Velocity of radiations, = Wavelength, E = Energy of radiations
4 Indian National Chemistry Olympiad

Plancks Quantum Theory

When different solids are heated to same temperature they glow and emits different types of radiations.
1. Substances radiate or absorb energy discontinuously in the small packets or bundles of energy.
2. The smallest packet of energy is called quantum. In case of light the quantum is known as photon.
3. The energy of a quantum is directly proportional to the frequency of the radiation.
E
E = h
= Frequency of radiation
h = Plancks constant
h = 6.626 1027 erg s1 = 6.626 1034 J/ s
4. A body can radiate or absorb energy in whole number multiples of a quantum i.e., h, 2h, 3h, nh
where, n is the positive integer.

Atomic Spectrum
Spectrum is the impression produced on a photographic film when the radiation(s) or particular
wavelength(s) is (are) analysed through a prism or diffraction grating.

Types of Spectrum
(i) Emission spectrum
Spectrum produced by radiation emitted is known as emission spectrum. This spectrum corresponds to
the radiation emitted when an excited electron returns back to the ground state.

(ii) Absorption spectrum

Spectrum produced by the absorbed radiation.

Types of Emission Spectra

(i) Continuous spectrum
When white light from any source is analysed by passing through prism, it splits up into 7 different wide
bands of colour. These colours are so continuous that each of them merges into next without any gap or
break.

(ii) Line spectrum

When an electric discharge is passed through a gas at low pressure light is emitted. If this light is
resolved by a spectroscope, it is found that some isolated coloured lines are obtained on a photographic
plate separated from each other by dark spaces. Each line in the spectrum corresponds to a particular
wavelength each element gives its own characteristic spectrum.

(iii) Band spectrum

The spectrum which consists of bright bands each having sharp edge.

Atomic Spectra of Hydrogen Atom

If an electric discharge is passed through hydrogen gas in atomic state taken in a discharge tube under
low pressure and the emitted radiations is analysed with the help of spectrograph the spectrum does
not have radiations of all the wavelengths but radiations of only certain wavelengths. The spectrum of
hydrogen is found to consist of a series of sharp lines in the UV visible and IR regions.
Atomic Structure 5

The wavelength of all these series can be expressed as :

1 1 1
= = R 2 2
n
1 n 2

= Wave number
= Wavelength
R = Rydberg constant (10967 z cm 1 )
n1 ; n2 have integral values
Series n1 n2 Main spectral lines
Lyman 1 2,3,4 UV
Balmer 2 3,4,5 Visible
Paschen 3 4,5,6 IR
Brackett 4 5,6,7 IR
Pfund 5 6,7,8 IR

Bohrs Model and Hydrogen Spectrum

Main postulates of Bohrs Model are as follows :
(i) An atom consists of positively charged nucleus.
(ii) The electrons revolve around the nucleus in certain permitted circular orbits of definite radii.
(iii) The permitted orbits are those for which the angular momentum of an electron is an integral
multiple of h/2.
h = Plancks constant
If m is the mass; v is the velocity of an electron in a permitted orbit of radius r then
L = mvr = nh/ 2p ; n = 1, 2, 3
L = Orbital angular momentum
n = Number of orbit
The integer n is called principal quantum. This equation is known as Bohr quantization postulate.
(iv) When electrons move in permitted discrete orbits they does not radiate or loose energy these are
stationary or non-radiating orbits. Greater the distance of energy level from the nucleus, the more is
the energy associated with it. The different energy levels were numbered as 1, 2, 3, 4 and called as
K, L, M, N, etc.
(v) Ordinarily an electron continues to move in a particular stationary state of orbit. Such a stable state,
of atom is ground state when energy is given to the electron it jumps to any higher energy level and is
said to be in excited state. When electrons jump from higher to lower energy state the energy is
radiated.

Hydrogen Spectrum
According to Bohr, the spectrum arises when, the electron and nucleus from any excited stationary orbit
of principal quantum number n2 jumps to the ground state or any lower stationary orbit of principal
quantum number n1 , so that the difference of the energy associated with these orbits is emitted as a
photon of frequency ().
2 2mZ 2e 4 K 2 2 2mZ 2e 2K 2
Accordingly, h = E 2 E1 =

n22h 2 n12h 2
2 2mZ 2e 4 K 2 1 1
Hence, = 3 2 2 (Z = 1 for H atom)
h n1 n2
6 Indian National Chemistry Olympiad

Since the wavelength, of the photon is related to by = c/

c 2 2me 4 K 2 1 1
Hence, = 2 2
h3 n
1 n 2

1 2 2me 4 K 2 1 1 1 1 1
= 2 2 or = = RH 2 2
3
hc n1 n2 n1 n2
where, R H is called the Rydberg constant of the hydrogen atom.
2 p2mK 2e4
RH = = 1.097 107 m 1
h3C
Above equations is called Rydberg equation.
Different types of series lie in hydrogen spectrum and their wave numbers of photons are as follows :

(i) Lyman series

The spectral lines correspond to the transition of the electron from higher energy state (n) to the lower
energy state corresponding to nf = 1
= R H 2 2 ; n = 2, 3, 4,
1 1
2 n
These lines are found in the ultraviolet region of the electromagnetic spectrum.

(ii) Balmer series

The spectral lines correspond to the transition of the electron from some higher energy corresponding
to nf = 2.
1 1
Thus, = R H 2 2 ; n = 3, 4, 5, .
2 n
These lines are found in the visible region.

(iii) Paschen series

Here, = RH 2 2 ; n = 4, 5, 6,
1 1
3 n
These lines are found near in the infrared region.

(iv) Brackett series

Here, = RH 2 2 ; n = 5, 6, 7
1 1
4 n
These lines are also found in the infrared region.

(v) Pfund series

Here, = RH 2 2 ; n = 6, 7, 8,
1 1
5 n
These lines are found in the far infrared region.

Merits of Bohrs Theory

(i) Value of radii and energies in hydrogen atom are in good agreement with that calculated on the
basis of Bohrs theory.
(ii) Bohrs concept of stationary state of electron explains the emission and absorption spectra of
hydrogen like atom.
(iii) The experimental values of the wavelength of the spectral lines in the hydrogen spectrum are in
close agreement with that calculated by Bohrs theory.
Atomic Structure 7

Limitations of Bohrs Theory

(i) It doesnt explain the spectra of atoms having more than one electron.
(ii) Bohrs atomic model failed to account for the effect of magnetic field (Zeeman effect) or electric
field (Starck effect ) on the spectra of atoms or ions.
(iii) Postulate of Bohr, that electrons revolve in well defined orbits around the nucleus with well
defined velocities is thus not valid.

Dual Nature of Electron

Einstein suggested dual character of light wave and particle to explain the phenomenon of diffraction
and interference by taking light as waves and phenomenon of black body radiation and photoelectric
effect on the basis of its particle nature.
de-Broglie said that matter can also have a dual character. He gave an expression between wavelength
of particle and its mass m moving with velocity i.e., = h / m .

de-Broglie Equation
The wavelength of the wave of a particle is calculated by analogy with photon.
Case I Photon having wave character energy,
E = h (according to Plancks quantum theory) (i)
Case II Photon having particle character energy,
E = mc 2 (ii)
By Einstein equation, here m is the mass of photon and c is the velocity of light.
By Eqs. (i) and (ii)
h = cm 2
If the m and c of photon are replaced by the m and n of particle then
h h
= =
m P
As m = P the momentum of the particle

Heisenbergs Uncertainty Principle

It is impossible to measure simultaneously the position and momentum of a small microscopic moving
particle with absolute accuracy or certainly.
If an attempt is made to measure any one of these two quantities with higher accuracy, the other
becomes less accurate.
Its mathematical expression is x P h/ 4.

Quantum or Wave Mechanical Model of Atom

This model of atom is based on de-Broglies principle, Heisenbergs uncertainty principle and dual
nature of matter. According to this model motion of electron in three dimensional space is represented
by Schrodinger wave equation as follows
2 2 2 8 2m
2
+ 2
+ 2
+ (E v ) = 0
x y z h
8 Indian National Chemistry Olympiad

where x, y and z are coordinates.

m = Mass of electron
E = Total energy
= Potential energy
= Wave function of electron wave
2 = Probability of finding electron in atom.

Features of Quantum, Mechanical Model

1. The energy of electron in atom is quantised.
2. Solution of Schrondinger equation gives the energy values of quantised levels.
3. It doesnt specify the exact position and momentum of electron but focuses on most probable
regions Orbitals.
4. Electron in each orbital has definite amount of energy.
5. Whenever an electron is described by a wave function it means electron occupies an orbital.
6. 2 is probability density and always has positive value.
7. The solution of Schrodinger wave equation gives values of n, l and m.
Probability distribution curve (graph) is a plot prepared by plotting probability (2 ) against the distance
from nucleus (r ). Radial probability distribution curve gives probability of finding electron in a given
volume.

4r 22

For 1s-orbital

Node

4r22 4r22

r r
For 2s-orbital For 2 p-orbital

At mode probability of finding electron is zero.

Atomic Structure 9

Shape of Orbitals

s-orbital
2px 2py 2pz
z z z

x x x

y y y

p-orbital
dxy dxz
z z

x x
y
y
(a) (b)

dyz dx2 y2
z z

x y x
y
(c) (d)
d z2
z

y
x

(e)
d-orbital

Photoelectric Effect
Sir JJ Thomson, observed the photoelectric effect. When a light of certain frequency strikes the surface
of a metal, electrons are ejected from the metal, and the ejected electrons are called photoelectrons.
Only cesium shows this effect in visible light as it has low ionization energy but others show it under
more high UV rays.

Experimental Findings of Photoelectric Effect

(i) When light of required energy strikes the surface of metal, electrons come out.
(ii) The light of minimum frequency, i.e., threshold frequency is require to eject the electrons.
10 Indian National Chemistry Olympiad

(iii) Photoelectric current is directly proportional to the intensity of light of same frequency is more will
be the current if the intensity is greater.
Let, the threshold frequency = 0
If a photon of frequency 0 strikes the metal it give its energy to the electron = (h 0 )
By getting h0 energy electron can break away from the atom by overcoming the attraction force of
nucleus. But if the frequency < 0 then no effect will take place
The more of frequency than 0 gives more energy to the electron
Given a certain velocity (i.e., kinetic energy ) to the electron
h = h 0 + KE
1 1
h h 0 = m 2 m 2 = h ( 0 )
2 2
Now, h0 is the work function denoted by and it is constant for a particular metal.
The KE of photoelectron and frequency of induct light is linear i.e., a straight line whose slope is equal to
Planck's constant h and intercept is h 0 . Quantum n0 and atomic orbitals. There are 4 quantum
numbers which describe the location energy, orbital, its shape and orientation etc. of the electron.

Principal Quantum Number

(a) It is denoted by letter n and can have +ve value e.g.,1, 2, 3,
(b) It gives angular distance between electrons and nucleus.
(c) It tells the energy of that electron.
(d) The maximum number of electrons present in any principal shell is given by2n 2.
Shell Maximum no. of electrons
n
K 1 2
L 2 8
M 3 18
N 4 32

Azimuthal or Angular Quantum Number

(a) Denoted by l and represent the subshells present in the main shell.
(b) It can have any integral value 0 to n 1.
(c) It tells the shape of the shell.
(d) Through it angular momentum can be calculated as, = l (l + 1) h / 2 or l (l + 1) h

Magnetic Quantum Number

Angular motion of an electron produces an electric field around the nucleus which give rise to magnetic
field. Due to which electrons can orient themselves in certain preferred regions of spaces around the
nucleus called orbitals. The magnetic quantum number determine the number of preferred orientation
of the electron present in the sub-shell.
m has value between l to +l including 0.

Spin Quantum Number

Electron revolves around the nucleus as well as spins about its own axis either clockwise or
anti-clockwise.
1 1
It can have two value + or . This helps us to explain magnetic properties of the substances.
2 2
Atomic Structure 11

Shapes and Size of Orbital

Space around nucleus where probability of finding an electron is maximum is known as orbital.
s-orbitals (l = 0), the shape of s-orbit symmetrical about the p-orbitals ( l = 1).
The probability of finding the p-electron is maximum in
two lobes on the opposite sides of the nucleus. This give
rise to a dumb-bell shape for the p- orbital for p-orbital 1s
2p
l = 1. Hence, m = 1, 0, +1 thus p-orbital have three 2s 3d
different orientations. These are designated as p x ,p y , and 3p
4d
4f
3s
p z depending upon whether the density of electron is 4p
maximum along the x, y and z-axis respectively. They are 4s 5d
5p
symmetrical but have directional characters. The two 5s
lobes of p-orbitals are separated by a nodal plane, where 6p
the probability of finding electron is zero the three 6s
p-orbitals belonging to a particular energy shell have 7s
equal energies and are called degenerate orbitals
d-orbitals (l = 2).
Aufbau principle
For d-orbitals, l = 2 Hence, m = 2, 1, 0, +1, +2 thus
5d-orbitals they have different geometrical shape orbitals
are (d xy , d yz , d zx ) are lie in between the axis and the other two d and d lie along the axis.
z2 x2 y 2

Aufbau Principle
This principle states that the electrons are added in orbitals one by one in the various orbitals in order of
their increasing energy starting with the orbital of lowest energy.
(n + l ) Rule The energy of an orbital depends upon the sum of the values of the principal quantum
number (n) and the azimuthal quantum number (l ), this is called (n + l ) rule. According to this rule, In
neutral isolated atom the lower the value of (n + l ) for an orbital, lower is its energy.

Paulis Exclusion Principle

According to this principle No two electrons in an atom will have the same value of all the four
quantum numbers.

Hunds Rule of Maximum Multiplicity

Electron pairing in p, d and f orbitals cannot occur until each orbital of a given sub-shell contains one
electron each or is singly occupied.
Factors responsible for the extra stability of half-filled and completely filled sub-shells :
(i) Symmetrical distribution It is well known fact that symmetry leads to stability. Thus the
electronic configuration in which all the orbitals of the same sub-shell are either completely filled
or are exactly half-filled are more stable because of symmetrical disturbance of the electrons.

(ii) Exchange energy The electrons with the parallel spins present in the degenerate orbitals tend
to exchange their position. The energy released during this exchange is called exchange energy. The
number of exchanges that can take place in maximum when the degenerate orbitals (orbitals of
same sub-shell having equal energy) are exactly half-filled or completely filled. As a result, the
exchange energy is maximum and so is the stability.
12 Indian National Chemistry Olympiad

Some Important Points

1. Some uncommon fundamental particles
Positron +1e 0 (Anderson, 1932)
Neutrino and antineutrino (Jumi, 1934)
Mesons ( + , 0 , and ) (Yukawa, 1935, Kemma).
2. General symbol for an atom of element X is AZ X where, A = mass number, Z = atomic number.
A=Z +n
m0
3. Mass of e at high speed m =
2
1
u
c
where, m0 = rest mass, u is velocity of e and c is velocity of light. If u = c, then m
A 1
4. Radius of nucleus =
Avogadro no. 4 r 3
3
1
Frequency = c/ ; wave number =

hc
Energy of photon E = h = = hc (Energy is inversely proportional to wavelength).

5. E = En 2 En1 = h if n2 > n1; emission spectra if n2 < n1 absorption spectra
h
6. Angular momentum of e = n = mr
2
h
7. Orbital angular momentum of e = l (l + 1)
2
h
8. Spin angular momentum of e = s (s + 1)
2
2 e 2 Z 6Z uZ
9. Velocity of e in an orbit un = = 2.178 10 m per = 1
h n n n
10. Energy of an e in a shell (En )
2 2me 4 Z2 1 E Ze 2
En = 2 = 1 ; En =
h2 n 4 0 n2 2rn
Z2 Z2 Z2
En = 21.79 1019 2
J-atm = 13.6 2
eV = 313.5208 kcal mol 1
n n n2
1
11. In CGS =1
4 0
1
12. In MKS = 9 109 Nm2 C2 , 4 0 = permittivity factor of medium
4 0
1 1
E = 1312 2 2 kJ mol 1
n2 n1
E = energy required to jump from e or emitted when e drops from n2 to n1 level.
13. Separation energy En En (given)
hc 1 1 1
14. = , = = RH 2 2
En 2 En 1 1
n n 2

15. RH = Rydberg constant = 109677 cm1 for H atom

2 2mZ 2e 4K 2
16. RH = ;
h 3c
Atomic Structure 13

1
17. K= = 9 109 Nm2 C2
4 0
18. Number of fine lines of a line in atomic spectrum of H = n1 n2
19. The possible number of given out = n = (n2 n1)
h h
20. = = , de-Broglie equation
mV p
h h
21. Heisenbergs uncertainty principle x p or
4 2
n (n 1)
22. Maximum number of lines =
2
1
23. Einstein photoelectric equation mv 2 = h h0
2
circumferences
24. 2 r = n number of waves in any orbit = = n
wavelength
Ze 2
25. PE =
rn
1 Ze 2 2 Ze 2
26. KE = mv =
2 rn r
27. = a (Z b) ; (Moseley) a,b are constants Z = atomic number
28. Para-magnetic momentum = n (n + 2)
29. Isorlirs Molecules having same number of atoms and same number of e for example N2O and CO2
(3 atoms and 22 e ).
30. Isodiaphers Same difference of neutrons and protons .
31. Isoelectronic Same number of e .
32. Diamagnetic Doubly occupied (no unpaired e ).
33. Paramagnetic Atoms which consist of at least one of the orbitals singly occupied.
34. Kernel Part remained after H e moving the outermost shell.
Core charge Number of e in outer most orbit.
35. Number of orbitals in any sub-shell = (2l + 1)
36. Maximum number of e in main energy shell = 2n 2
37. Number of sub-shells in main energy shell = n
38. Number of orbitals in a main energy shell = n 2

Illustrative Solved Examples

Example 1. 1.8 g H2 atoms are excited to radiations. The study of spectra indicates that 27% of the atoms
are in 3rd energy level and 15% of atoms in second energy level the rest in ground state. IP of H is 13.6 eV.
Calculate
(a) number of atoms present in third and second energy level.
(b) total energy evolved when all the atoms return to ground state.
Solution 1g H contains = H atoms
1.8 g H contains = N 1.8 atoms = 6.023 1023 1.8 = 10.84 1023 atoms
14 Indian National Chemistry Olympiad

10.84 1023 27
(a) Number of atoms in third shell = atoms = 292.68 1021
100
10.84 1023 15
Number of atoms in second shell = = 162.6 1021 atoms
100
10.84 1023 58
Number of atoms in first shell = = 628.72 1021 atoms
100
(b) When all the atoms return to first shell, then

E = (E3 E1 ) 292.68 1021 = + 13.6 1.602 1019 292.68 1021

13.6
9

= 5.668 105 J

E = (E 2 E1 ) 162.6 1021 = + 13.6 1.602 1019 162.6 1021

13.6
4

= 2.657 105 J
E = E + E = 5.668 105 + 2.657 105J = 832.50 kJ

Example 2. A hydrogen like atom (at. no. Z) is in a higher excited state of quantum number n. This excited
atom can make a transition to the first excited state by successively emitting 2 photons of energies
10.200 eV and 17.00 eV respectively. Alternatively, the atom from the same excited state can make a
transition to the second excited state by successively emitting 2 photons of energy 4.25 eV and 5.95 eV
respectively. Determine the value of n and Z.
Solution Total energy liberated during transition of electron from nth shell to first excited state
= 10.20 + 17 = 27.20 eV
= 27.20 1.602 1012 erg

= RH Z 2 h c 2 2
hc 1 1
(i)
2 n
Similarly, total energy liberated during transition of electron fromnth shell to second excited state
= 4.25 + 5.95 = 10.20 eV.
Dividing Eqs. (i) by (ii)
n=6
On substituting value of n in Eqs. (i) and (ii)
Z =3

Example 3. A gas identical H like 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 to a higher energy level by absorbing monochromatic light of photon energy 2.7 eV.
Subsequently the atoms emit radiations of only six different photons energies. Some of the emitted
photons have energy 2.7 eV. Some have more and some have less than 2.7 eV.
(a) Find principal quantum number of initially excited level B.
(b) Find the ionization energy for the gas atoms.
(c) Find the maximum and minimum energies of the emitted photons.
Solution The electrons being present in first shell and another shell n1, There are excited to higher level
n2 by absorbing 2.7 eV and on deexcitation emits six lines and thus excited state n2 comes to be 4.
[b = n = (n2 1) n2 = 4]
Atomic Structure 15

Rn ch Rn ch
Now, E1 = ; En = ; En = Rn ch
12 1
n12
Since deexcitation leads to different having photon energy 2.7 eV and this absorption of 2.7 eV
energy causing excitation to fourth shell and then reemitting photons of 2.7 eV is possible only when
n1 = 2.
The deexcitation from 4th shell occurs in first, second and third shell.
E 4 E 2 = 2.7 eV
E 4 E3 > 2.7 eV
E 4 E1 > 2.7 eV
R ch E
En = En = n 2 = 12
1 2
2 2
Since n1 = 2
E1 E1
Also E 4 E 2 = 2.7 eV + = 27
. eV
42 22
E1 = 14.4 eV IP = 14.4 eV
E E 14.4
E max = E 4 E3 = 21 + 12 = + 14.4 = 13.5 eV
4 1 16
E E
E min = E 4 E3 = 12 + 31 = 0.7 eV
4 3

Example 4. Balmers empirical formula is 1 = RH 12 12 ; n = 3, 4, 5

2 n
4
mee
Here, RH = = 109678/cm
820h3c
RH = Rydberg constant
me = mass of an electron
(a) Calculate longest wavelength in in the Balmer series of singly ionised He + . (Ignore nuclear motion).
(b) Write the formula analogous to Balmer's formula applies to the series of spectral lines which arise from
transition from higher energy level to lowest energy level of H atom. And also use it to determine the
ground state energy of H atoms in eV.
0h 2
(c) a 0 = = 0.53
mee 2
Determine the lowest energy and radius of first Bohr orbit of muonic hydrogen atom.
In muonic hydrogen atom electron is replaced by 207 times heavier particle, muon. But the charge is
same.
(d) Onsider a spherical shell of radius a 0 and thickness 0.001a. Estimate the probability of finding the
electrons in this shell.
Volume of spherical shell of inner radius r and thickness r is given by V = 4 r 2r .
(e) (i) H2 H + H (ii) H2 H+ + H
Put appropriate channel labels (i) and (ii) in the boxes.
(f) Calculate the energy change in H H + e system. Assuming that the Bohr energy formula is valid
for each electron with nuclear charge Z replaced by Zeff , calculate Zeff for H .
(g) H has a 2 electron, atomic.
16 Indian National Chemistry Olympiad

Solution (a) Longest wavelength , corresponds to n = 3

= 4RH 2 2 ; L = 1641.1
1 1 1
For He + ,
2 n

= RH 2 2 ; n = 2, 3, 4, ...
1 1 1
(b)
1 n
E = hcRH = 13.6 eV
(c) Lowest energy = 207 13.6 = 282 keV
0.53
Radius of the first Bohr orbit = = 2.6 10 3
207
(d) Probability = [ (a 0 )]2 4 a 02 0.001a 0 = 0.004e 2 = 5.41 104
(f) Channel (i) = 4.7 eV; channel (ii) = 17.6 eV
(g) Electron affinity = 13.6 ( 14.3) = 0.7 eV
2
13.6 + 27.2Zeff = 0.7; Zeff = 0.7

Example 5. Oxalic acid in presence of

2+ +
UO2+
2 + hv (UO2 )

[UO2+ 2+
2 ] + H 2C2O4 UO2 + CO + CO2 + H 2O

By absorbing light of 250 nm. 450 nm.

The reaction is used in estimating the amount of decomposed acid and quantum efficiency of the process.
Here the quantum efficiency is given to be 50%. 1.0 L of 0.005 M oxalic acid solution was irradiated with
light of = 310 nm in presence of UO22 + ion. 20 mL of irradiated solution on titration required 25 mL of
0.005 N KMnO4 solution. How many photons are absorbed per second if the solution was irradiated for
10.5 nm?
Solution Equivalents of KMnO4 that reached with excesss
0.005 25
H2C2O4 = = 1.25 104
1000
Equivalents of excess H2C2O4 in 20 mL = 1.25 104
Equivalents of excess H2C2O4 in 20 mL = 1.25 104 50 = 6.25 103
Moles of excess H2C2O4 in 1 L = 3.125 103
Initial moles of oxalic acid = 0.005
Moles of oxalic acid consumed by (UO22 + ) = 1.875 103
Moles of (UO22 + ) = 1.875 103
Moles of photons = 1.875 103
1.875 103 6.023 1023
Number of photons absorbed/sec = 100 = 3.58 1018
50 10.5 60

Example 6. The second ionization potential of Be is 17.98 eV. If the electron is Be+ is assumed to move in a
spherical orbit with a central field effective nuclear charge (Zeff ) consisting of the nucleus units of charge
is the nucleus sheilded by other electrons? The energy of electron in first Bohr orbit of H is 13.6 eV. If the
extent of shielding the K electrons of Li atom is the same as you have calculated above, find the ionization
potential of Li.
Atomic Structure 17

2
Solution IE = 13.62Z = 17.98 Zeff = 2.3
n
Shielding extent = Z Zeff = 4 2.3 = 1.7
Zeff for lithium = 3 1.7 = 1.3
13.6 (1.3)2
IE of lithium = = 5.746 eV
(2)2

Example 7. A mixture of atoms of ordinary hydrogen 11 H and tritium, 31 H excited and its spectrum is
observed. How far apart in wavelength will be the H2 lines of the 2 kinds of hydrogen ? Rydberg constant
for ordinary H2 atom is 1.096 >> .58 107 m 1, proton mass = 1.002276 u, mass of atomic 31 H = 3.016049 u,
electron mass = 0.000549 u.
R
Solution For hydrogen, 1 = R R1 12 12 = 36 1 1
2 3 5R R1 2
R
But 1 = 1 , the ratio of the reduced masses
R2 2
M1m M 2m
1 = and 2 =
M1 + m M2 + m
where, m = Electron mass
1 M1 M 2 + m
=
2 M 2 M1 + m
We know that M1 = 100 > 2 > 6 u, M 2 = 3.016049 u and n = 0.000549 u
1 36
= 0.999637 = 3.63 104
2 5R
107
where, R = 1.0967758
m
= 2.385