CHAPTER 2

STRUCTURE OF ATOM
BASI C TERM S USED I N ATOM I C STRUCTURE
The fundamental particles present in atoms are Protons, Electrons and Neutrons. Their properties are
given below:

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

charge/C charge mass/u
Electron J.J. Thomson e –1.6022 × 10–19 –1 9.10939 × 10–31 0.00054 0
–19 –27
Proton Goldstein p +1.6022 × 10 +1 1.67262 × 10 1.00727 1
Neutron J. Chadwick n 0 0 1.67493 × 10–27 1.00867 1

Atomic Terms
(i) Atomic Number (Z)
The atomic number of an element is the number of protons contained in the nucleus of the
atom of that element.
(ii) Nucleons
Protons and neutrons are present in a nucleus. These fundamental particles are collectively
known as nucleons.
(iii) Mass Number (A)
The total number of protons and neutrons present in the nucleus is called the mass number of
the element.
A pn ; p  An ; n  A p

IUPAC notation of an atom

Let X be the chemical symbol of the element. It's atomic number be Z and mass number be A.
Then the element can be represented as Z X A .
(iv) Isotopes
Atoms of the element with same atomic number but different mass number are known as
isotopes.
e.g., 1H
1
, 1 H 2 , 1 H 3 are three isotopes of hydrogen.
(v) Isobars
Atoms having the same mass number, but different atomic numbers are known as isobars
e.g., 15 P 32 and 16 S 32 are isobars.
34 Structure of Atom

(vi) Isotones
Atoms having the same number of neutrons but different number of protons or mass number
e.g. 6C14, 8O16, 7N15 are called isotones.
(vii) Isoelectronic
Atoms, molecules or ions having same number of total electrons are called isoelectronic, e.g.,
N2, CO, CN  .
(viii) Atomic mass unit
Exactly equal to 1/12 of the mass of 6 C 12 atom.
1 amu = 1.66  10 27 kg = 931.5 MeV
Not in CBSE Syllabus 2020
Example 1

Calculate the total number of electrons present in one mole of methane.

1 molecule of CH4 contains = 6 + 4 = 10 electrons
23 24
 1 mole, i.e., 6.022 × 10 molecules will contain = 6.022 × 10 electrons
14
Find (a) the total number and (b) the total mass of neutrons in 7 mg of C (Assume
–27
that the mass of neutron = 1.675 × 10 kg)
14 23 23
(a) 1 g mole of C = 14 g = 6.022 × 10 atoms = (6.022 × 10 ) × 8 neutrons
14
(as each C atom has 14 – 6 = 8 neutrons)
Example 2

23
Thus, 14 g or 14000 mg have 8 × 6.022 × 10 neutrons.
8  6.022  1023
 7 mg will have neutrons =  7  10 3  2.4088  1021
14
27
(b) Mass of 1 neutrons = 1.675 × 10 kg.
21 21 –27
 Mass of 2.4088 × 10 neutrons = (2.4088 × 10 ) (1.675 × 10 )
–6
= 4.0347 × 10 kg
Find (a) the total number and (b) the total mass of protons in 34 mg of NH3 at S.T.P.
–27
(Assume the mass of proton = 1.6726 × 10 kg)
Will the answer change if temperature and pressure are changed?
23
(a) 1 mol of NH3 = 17 g = 6.022 × 10 molecules of NH3
23 24
= (6.022 × 10 ) × (7 + 3) protons = 6.022 × 10 protons
Example 3

6.022  1024 22
 34 mg, i.e. 0.034 g NH3 =  0.034 = 1.2044 × 10 protons.
17
–27
(b) Mass of one proton = 1.6726 × 10 kg
–27 22
Mass of 1.2044 × 1022 protons = (1.6726 × 10 ) × (1.2044 × 10 )kg
–5
= 2.014 × 10 kg
There is no effect of temperature and pressure.
Chemistry-XI 35

Example 4 An element has atomic number 30 and its mass number is 66, what will be the number
of protons and neutrons in this atom?
No. of protons = Atomic number = 30
No. of neutrons = Mass number – Atomic number = 66 – 30 = 36

Atomic numbers of two elements of same mass number A and B are respectively 18
and 20. If A has 22 neutrons in its nucleus, find out the number of neutrons in B.
Example 5

Mass no. = At. no. + n

 Mass no. of A = 18 + 22 = 40
Since, both A and B have same mass no., the mass no. of B will be 40
 No. of neutron in B = Mass no. – At. No. = 40 – 20 = 20

Mass numbers of isotones A, B and C are respectively 30, 31 and 32. If atomic
number of B is 15, find out the atomic numbers of A and C.
No. of n in B 31 = 31 – 15 = 16
Example 6

15

A, B and C are isotones (have same number of neutrons)

 At. No. of A = 30 – 16 = 14
and At. No. of C = 32 – 16 = 16

Mass numbers of two atoms X and Y having same atomic number are respectively
208 and 210. If X has 126 neutrons in its nucleus, find out the number of neutrons in
Y and its atomic number.
Example 7

No. of ‘n’ in X 208 = 126

 At. No. of X 208 = 208 – 126 = 82
 Atomic Number of X 208 and Y 210 is same
 Atomic no. of Y 210 = 82
No. of ‘n’ in Y 210 = 210 – 82 = 128

An element with mass number 81 contains 31.7% more neutrons as compared to

protons. Assign the atomic symbol.
Mass number = 81, i.e., p + n = 81
Example 8

31.7
If protons = x, then neutrons = x +  x = 1.317 x
100
81
x + 1.317 x = 81 or 2.317 x = 81 or x = = 35
2.317

Thus, Protons = 35, i.e. atomic no. = 35

Hence, the symbol is 81
35 Br
36 Structure of Atom

Symbols 35
79
Br and 79 Br can be written whereas symbols 35
79 Br and 35
Br are not
acceptable. Answer briefly.
Example 9

35
79 Br is not acceptable because atomic number should be written as subscript, while mass
number should be written as superscript. 35 Br is not acceptable because atomic number of
an element is fixed. However, mass number is not fixed as it depends upon the isotope
taken. Hence, it is essential to indicate mass number.

An atom of an element contains 29 electrons and 35 neutrons. Calculate mass number

Example 10

of the element.
For neutral atom, number of protons = number of electrons = 29
Thus, atomic number of the element = 29
Mass number = no. of protons + no. of neutrons = 29 + 35 = 64.

Try Yourself-1
1. (i) Calculate the number of electrons which will together weigh one gram.
[ 1.098 1027 ]
(ii) Calculate the mass and charge of one mole of electrons [ 5.486  104 g , 9.65 104 C ]
2. If the atomic numbers of Na, P and Cl are respectively 11, 15 and 17. Calculate the number
of electrons, protons and neutrons in each of the following:
(i) Na+ [ e  10, p  11, n  12 ]
(ii) P [ e  15, p  15, n  16 ]
(iii) Cl- [ e  18, p  17, n  18 ]
80
3. Calculate the number of protons, neutrons and electrons in 35 Br . [p = e = 35, n = 45]
4. The number of electrons, protons and neutrons in a species are equal to 18, 16 and 16
respectively. Assign the proper symbol to the species. [ 1632 S 2 ]
5. Nitrogen atom has atomic number 7 and oxygen has atomic number 8. Calculate total no. of
electrons in one nitrate ion. [32]
238
6. How many neutrons are present in a pentavalent cation of 92U ? [146]
7. An element has atomic number 11 and the mass number 23. How many numbers of neutrons,
protons and electrons does it have? [ n = 12, p = 11, e = 11 ]

8. The monovalent anion ( X ) of any non-metal contains 18 electrons. The mass number of
non-metal is 35. Find out the number of neutrons in the nucleus of non-metal. [18]
9. An ion with mass number 37 possess one unit of negative charge. If the ion contains 11.1%
more neutrons than the electrons, find the symbol of the ion. 37
[ 17 Cl  ]
10. An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons
than electrons. Assign the symbol to this ion. [ Fe3 ]

11. Which one of the following sets of ions represents the collection of isoelectronic species?
(a) K+, Ca2+, Sc3+, Cl (b) Na+, Ca2+, Sc3+, F
(c) K+, Cl, Mg2+, Sc3+ (d) Na+, Mg2+, Al3+, Cl
Chemistry-XI 37

(Atomic numbers: F = 9, Cl = 17, Na = 11, Mg = 12, Al = 13, K = 19, Ca = 20, Sc=21)

12. Of the following sets which one does not contain isoelectronic species?
(a) PO 34 , SO 24 , ClO 4 (b) CN  , N 2 , C 22
(c) SO 32 , CO 32 , NO 3 (d) BO 33 , CO 32 , NO 3
13. Which of the following are isoelectronic species i.e., those having the same number of
electrons?
Na+, K+, Mg2+, Ca2+, S2–, Ar.

CH ARACTERI STI CS O F W AV ES
A wave is a sort of disturbance which originates from some vibrating source and travels outward as a
continuous sequence of alternating crests and troughs. Every wave has some important
characteristics, namely, wavelength (), frequency (), velocity (c), wave number (  ) and
amplitude (A).
Crest 
Amplitude

Trough

(i) Wavelength ()

The distance between two neighbouring troughs or crests is known as wavelength. It is
denoted by  and is expressed in centimeter (cm), meter (m), nanometer(nm) and
Angstrom(Å).
1 nm = 10 9 m and 1 Å = 10 10 m
(ii) 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 (nu) and is expressed in cycles per second (cps)
or hertz (Hz).
1 Hz = 1 cps
The frequency of a wave is inversely proportional to its wave length ().
velocity 1
 or  
λ λ
(iii) Velocity
The distance travelled by the wave in one second is called its velocity.
velocity = 

The electron is revolving around the nucleus in a circular orbit. How many revolutions it
Example 11

can make in one second?

Let the velocity of electron be v m/sec. The distance it has to travel for one revolution 2r, (i.e.,
v
the circumference of the circle). Thus, the number of revolutions per second is =
2 r
38 Structure of Atom

(iv) Wave number (  )

It is defined as number of oscillations per unit length. It is denoted by  and is expressed in
cm 1 or m–1.
1 
 or 
 c
(v) Amplitude (A)
It is the height of the crest or depth of the trough of a wave and is denoted by A. It determines
the intensity or brightness of the beam of light.

RAD I AN T EN ERGY
James Maxwell showed that when electrically charged particle moves under acceleration, alternating
electrical and magnetic fields are produced and transmitted. These fields are transmitted in the forms
of waves called electromagnetic waves or electromagnetic radiation.
Radiant energy has wave nature and is associated with electric as well as magnetic field. Thus, these
radiations are called electromagnetic radiations.

Properties of electromagnetic Wave

(i) The oscillating electric and magnetic field produced by oscillating charged particles are
perpendicular to each other and both are perpendicular to the direction of propagation of the
wave.

The electric and magnetic field components of an electromagnetic wave. These components have the same
wavelength, frequency, speed and amplitude, but they vibrate in two mutually perpendicular planes.
(ii) Electromagnetic wave do not require medium and can move in vacuum.
(iii) The various forms of electromagnetic radiations are -rays, x-rays, ultraviolet waves, visible
rays, infra-red rays, microwaves, and radio waves such as TV, FM, AM rays. These waves
differ from one another in wavelength (or frequency).
(iv) Electromagnetic radiations arranged in the increasing order of wavelength (or frequency) and
energy is called electromagnetic spectrum.
Chemistry-XI 39

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 or a dispersion
grating, all the colours of white light get separated into violet, indigo, blue, green, yellow, orange
and red (VIBGYOR).

R
O
Y
G
B
I
V

A certain radio station broadcast on a frequency of 900 kHz (kilohertz). What is the
wavelength of electromagnetic radiation broadcast by the radio station?
The frequency of the radiation emitted,
 = 900 kHz = 900 × 103 Hz = 900 × 103 s–1.
Example 12

c
We know that     c or 

Where c = 3.0 × 108 m s–1.
3.0  108 ms 1
 = 333.33m
900  103 s1
Thus, wavelength of radio wave broadcast by the station = 333.33 m.
Arrange the following types of radiations in increasing order of frequency:
Example 13

(a) radiation from microwave oven (b) Amber light from traffic signal
(c) radiation from FM radio (d) cosmic rays from outer space and
(e) X-rays
Cosmic rays < X-rays < Amber light < microwaves < Radiation from FM radio.
40 Structure of Atom

Try Yourself-2
1. The Vividh Bharati station of All India Radio, Delhi, broadcasts on a frequency of 1,368 kHz
(kilo hertz). Calculate the wavelength of the electromagnetic radiation emitted by transmitter.
Which part of the electromagnetic spectrum does it belong to? [ = 219.3m, radio wave]
2. The wavelength range of the visible spectrum extends from violet (400 nm) to red (750 nm).
Express these wavelengths in frequencies (Hz) (1nm = 10–9 m) [4.0 × 1014 to 7.5 × 1014 Hz]
3. Calculate (a) wave number and (b) frequency of yellow radiation having wavelength 5800 Å.
[(a) 1.724  104 cm 1 (b) 5.172  1014 s 1 ]
4. AIR service on Vividh Bharti is transmitted on 219 m band. What is its transmission
frequency in Hertz. [ 1.37  106 Hz ]
5. The frequency of the strong yellow line in the spectrum of sodium is 5.09 × 1014 s-1.
Calculate the wavelength of the light in nanometer. [589.39nm]
6. Calculate the range of frequencies of visible light from 3800 – 7600 Å .
[ 3.95  1014 to 7.89  1014 s 1 ]
7. How long would it take a radio wave of frequency, 6  103 sec 1 to travel from Mars to the
Earth, a distance of 8  107 km ? [4 min 26 sec.]
8. Calculate the wave number of radiations having a frequency of 4  10 Hz . [ 1.33 104 Cm 1 ]
14

9. A particular radio station broadcast at a frequency of 1120 kHz (kilohertz). Another radio
station broadcasts at a frequency of 98.7 MHz (megahertz). What are the wavelengths of the
radiations from each station? [267.85m,3.395m]
10. Yellow light emitted from a sodium lamp has a wavelength (  ) of 580 nm. Calculate the
frequency (  ) and the wave number  of the yellow light.
11. Calculate the wavelength, frequency and wave number of a light wave whose period is
2.0 × 10–10 s.

PLAN CK’S QUAN TUM TH EORY

Max Planck observed that when different solids are heated to same temperature they glow and emit
different type of radiations. Max Planck assigned this observation to the oscillation or vibration of
the atoms of that material with a different and definite frequency. To explain this, Max Planck put
forward a theory known as Planck’s quantum theory. The main points of this theory are:
(i) Substances radiate or absorb energy discontinuously in the form of small packets or bundles
of energy.
(ii) The smallest packet of energy is called quantum. In case of light energy, the quantum is
known as photon.
(iii) The energy of a quantum is directly proportional to the frequency of the radiation. E   (or)
E = h where  is the frequency of radiation and h is Planck’s constant having the value
6.626  10 27 erg-s or 6.626 1034 Js.
(iv) 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.
Neils Bohr used this theory to explain the structure of atom. However it is important to
understand some concepts related to atomic spectrum.
Chemistry-XI 41

Neon gas is generally used in the sign boards. If it emits strongly at 616 nm, calculate (a)
the frequency of the emission (b) distance travelled by this radiation in 30 s (c) energy of
quantum (d) number of quanta present if it produces 2 J of energy.
Given:
 = 616 nm = 616 × 10–9 m
Example 14

c 3.0  108 ms1

(a) Frequency,  = = = 4.87 × 1014 s–1
 616  10 9 m
(b) Velocity of the radiation = 3.0 × 108 ms–1
Distance travelled in 30 s = 30 × 3 × 108 m = 9.0 × 109 m
c (6.626  10 34 Js)  3.0  10 8 ms1
(c) E = h = h = = 32.27 × 10–20 J
 616  10 9 m
2
(d) No. of quanta in 2J of energy = = 0.06197 × 1020 = 6.2 × 1018.
32.27  1020
Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of
Example 15

photons emitted is 5.6 × 1024, calculate the power of this laser.

Power of laser = energy with which it emits photon.
c (5.6  1024 )(6.626  10 34 Js)(3.0  108 ms1 )
E = n hv = nh = = 3.3 × 106 J
 (337.1  10 9 m)

What is the ratio between the energies of two radiations one with a wavelength of 6000 Å
and the other with 2000 Å.
Example 16

1 = 6000 Å, 2 = 2000 Å
hc hc
E1  , E2 
1 2

E1 hc 2 2 2000 Å 1
Ratio      Or E2  3E1
E2 1 hc 1 6000 Å 3

A 25-watt bulb emits monochromatic yellow light of wavelength of 0.57 µm. Calculate
the rate of emission of quanta per second.
Given that
–1 –1
Energy emitted by the bulb = 25 watt = 25J s (1 watt = 1 J s )
and wave length = 0.57  m = 0.57 106 m
Example 17

c
Energy of one photon (E) = h = h

–6 –6
Here,  = 0.57 µm = 0.57 × 10 m (1 µ m = 10 m)
8 –1 –34
Putting c = 3 × 10 ms , h = 6.62 × 10 J s, we get
(6.62  10 Js)(3  10 ms )
 34 8 1
–19
E= = 3.48 × 10 J
0.57  10 m
6

25Js1 19
No. of photons emitted per sec = = 7.18 × 10 .
3.48  10 J
19
42 Structure of Atom

In astronomical observations, signals observed from the distant stars are generally weak.
If the photon detector receives a total of 3.15 × 10–18 J from the radiations of 600 nm,
calculate the number of photons received by the detector.
Hint:
Example 18

c (6.626  10 34 Js)(3  108 ms1 )

Energy of one photon = h = h = = 3.313×10–19J
 (600  10 9 m)

Total energy receive = 3.15 × 10–18 J

3.15  10 18
 No. of photons received = = 9.51  10
3.313  10 19

The longest wavelength doublet absorption transition is observed at 589 and 589.6 nm.
Calculate the frequency of each transition and the energy difference between the two
excited states.
Example 19

c 3.0  108 ms1

 1 = 589 nm = 589 × 10–9 m  v1 = = = 5.093 × 1014 s–1.
1 589  10 9 m

c 3.0  108 ms1

 2 = 589.6 nm = 589.6 × 10–9 m  v2 = = = 5.088 × 1014 s–1.
2 589.6  10 9 m

E = E2 – E1 = h (v2 – v1) = (6.626 × 10–34 J s) (5.093 – 5.088) × 1014 s–1 = 3.31 × 10–22 J

Try Yourself-3
1. Calculate the energy per quantum associated with light of wavelengths,
(a) 5890 Å (b) 250 × 10–9 m
(c) 4.0 × 10–8 cm (d) 600 nm
[(a) 3.37  10 J ,(b) 7.95  1019 J ,(c) 4.97  109 erg (d) 3.3  1019 J ]
19

2. Calculate energy of one mole of photons of radiation whose frequency is 5 × 1014 Hz.
[199.51 kJ mol–1]
3. Calculate the energy of a photon of radiation having wavelength 6000 Å.
[ 3.3125 1019 J ]
4. Find the energy of each of the photons which
15
(i) corresponds to light of frequency 3 × 10 Hz [ 19.88  1019 ]
(ii) have wavelength of 0.50 Å. [ 39.76  1016 J ]
5. What is the relationship between eV and the wavelength in metre of the energetically
equivalent photon? [ 12.40  107 m ]
6. Compare the energies of two radiations one with a wavelength of 800 nm and other with
wavelength of 400 nm. [ 1 : 2]
7. Lifetime of the molecules in the excited state are often measured by using pulsed radiation
source of duration nearly in the nano-second range. If the radiation source has the duration of
2 ns and the number of photons emitted during the pulse source is 2.5 × 1015, calculate the
energy of the source. [ 8.28 1010 J ]
8. A 100-watt bulb emits monochromatic light of wavelength 400 nm. Calculate the number of
photons emitted per second by the bulb. [2.012 × 1020 s–1]
9. Calculate the number of photons emitted in 10 hour by a 60 W sodium lamp if  photon  5893 Å
Chemistry-XI 43

[ 6.4  1024 ]
10. What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of
energy? [ 2  1016 ]
11. A bulb emits light of   4500Å . The bulb is rated as 150 watt and 8% of the energy is
emitted as light . How many photons are emitted by the bulb per second? [ 27.2  1018 ]
12. A photon of 300 nm is absorbed by a gas and then re-emits two photons. One re-emitted
photon has wavelength 496 nm. Calculate energy of other photon re-emitted.
[ 2.625  1019 Joule]

BOH R' S M OD EL AN D H YD ROGEN SPECTRUM

Bohr retained the essential features of the Rutherford model of the atom. However, in order to
account for the stability of the atom he introduced the concept of the stationary orbits. The Bohr
postulates are:
1. An atom consists of positively charged nucleus responsible for almost the entire mass of the
atom (This assumption is the retention of Rutherford’s model).
2. The electrons revolve around the nucleus in certain permitted circular orbits of definite radii
and energy.
3. The permitted orbits are those for which the angular momentum of an electron is an integral
multiple of h/2 where h is the Planck's constant. If m is the mass and v is the velocity of the
electron in a permitted orbit of radius r, then
nh
L = mvr = ; n = 1, 2, 3……..
2π
where L is the orbital angular momentum and n is the number of orbit. The integer n is
called the principal quantum number. This is known as the Bohr quantization postulate.
4. When electrons move in permitted discrete orbits they do not radiate or lose energy. Such
orbits are called stationary or non-radiating orbits. In this manner, Bohr overcame
Rutherford’s difficulty to account for the stability of the atom. 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… etc., and called as K, L, M, N, … etc., respectively.
5. Ordinarily an electron continues to move in a particular stationary state or orbit. Such a stable
state of atom is called ground state. When energy is given to the electron it jumps to any
higher energy level and is said to be in the excited state. When the electron jumps from
higher to lower energy state, the energy is radiated.
6. The frequency of radiation absorbed or emitted when transition occurs between two
stationary states that differ in energy by E, is given by
E E 2  E1
 
h h
Where El and E2 are the energies of the lower and higher allowed energy states respectively.
The radii of the stationary states are expressed as
rn  n 2 a 0

Where a 0  52.9 pm. Thus, the radius of the first stationary state, called the Bohr radius, is
52.9 pm.
44 Structure of Atom

Energy of nth stationary state

 1  2
E n   RH  2  × Z ; where n  1, 2,3,.....
n 
and RH  2.18  1018 J
Z2 Z2
 En = –2.18  1018  2
J per atom = –13.6  eV per atom
n n2

1 electron volt is defined as the amount of energy gained by an electron when it accelerates
through a electric potential of 1V.
 1 eV = 1.6  10 19 J
The negative sign in the above equations shows that the electron and nucleus form a bound
system, i.e., the electron is attracted towards the nucleus. Thus, if electron is to be taken away
from the nucleus, energy has to be supplied. The energy of the electron in n = 1 orbit is called
the ground state energy; that in the n = 2 orbit is called the first excited state energy, etc.
When n =  then E = 0 which corresponds to ionized atom, i.e., the electron and nucleus are
infinitely separated, e.g.,
H 
 H+ + e- (ionization).
Bohr’s theory can also be applied to the ions containing only one electron, similar to that
present in hydrogen atom. For example, H+, Li2+, Be3+. The energies of the stationary states
associated with these hydrogens like species are given by the expression.
 Z2 
E n  2.18  1018  2  J
n 
52.9(n 2 )
and radii by the expression rn  pm
Z

(i) The energy associated with the first orbit in the hydrogen atom is –2.18 × 10–18 J
atom–1. What is the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
Example 20

Hint:
2.18  1018 2.18  1018
(i) En =– J  E5 = = –8.72 × 10–20 J.
n2 52
(ii) For H-atom, rn = 0.529 × n2 Å
r5 = 0.529 × 52 = 13.225 Å = 1.3225 nm.
The energy of electron in the second and third Bohr orbit of the hydrogen atom is
5.42  1012 erg and 2.41  1012 erg respectively. Calculate the wavelength of emitted
radiation when the electron drops from the 3rd to 2nd orbit.
Example 21

hc
E3  E2  hv 

6.626  1027 erg  3  1010 cm
2.41  1012  (5.42  10 12 ) 

6.626  1027  3  1010
 = 6.604  105 cm
3.01  1012
Chemistry-XI 45

The electron of H atom in the ground state works out to be 2.18  1018 J per atom.
Calculate what will happen to the position of the electron in this atom if an energy of
1.938  1018 J is supplied to each H atom?
E1 ( H )  2.18  1018 J
Example 22

2.18  1018
Energy provided = 1.938  1018 J , En ( H )  
n2
Here, n is the orbit to which e gets excited on absorbing extra energy.
 En  2.18  1018  1.938  1018 = 0.242  1018 J
2.18  1018
or n2   9.0 or n=3.
0.242  1018
According to Bohr’s theory the electronic energy of hydrogen atom in the nth Bohr orbit
21.76  1019
is given by E n   J per atom
n2
Calculate the longest wavelength of light that will be needed to remove an electron from
the third orbit of He+ ion.
For hydrogen like ion, i.e., He+, the relation is:
21.76  1019  z 2
Example 23

En   J per atom
n2
where Z is atomic number. For He+, Z = 2
21.76  1019  4
Energy of He+ ion in third orbit (n = 3), E3   J
32
Energy required to remove an electron from third Bohr orbit of He+ ion is:
 21.76  1019  4  19
E  E   E 3 = 0  J = 9.67  10 J
 9 
hc hc 6.626  1034  3.0  108
Now, E  or   = 2.055  107 m  205.5nm
 E 9.67  1019 J
Calculate the energy required to remove an electron completely from n = 2 orbit. What is
the longest wavelength (in cm) of light that can be used to cause this transition?
Electron energy in H atom
2.17  1011
En   erg
n2
Example 24

2.17  1011
E2   erg = 0.5425  1011 erg
4
E  E  E2  5.425  1012 erg
hc
E

6.626  1027  3  1010 6.626  1027  3  1010
5.425  1012  or   cm = 3.66  105 cm
 5.425  1012

Try Yourself-4

1. Calculate the frequency of radiation emitted when the e falls from n  4 to n  1 in an H

atom. (Ionization energy of H  2.18  1018 J atom 1 and h  6.626  1034 Js ) [ 3.08 1015 s 1 ]
2. What are the frequency and wavelength of a photon emitted during a transition from n = 5
state to the n = 2 state in the hydrogen atom? [ = 6.9 × 1014 Hz,  = 434 nm]
46 Structure of Atom

3. Calculate the energy associated with the first orbit of He+ . What is the radius of this orbit?
[E = 8.72 × 10-18 J, r = 0.02645nm ]
4. The ionization energy of H-atom (in ground state) is x kJ. Find the energy required for an
electron to jump from 2nd to 3rd energy level. [5x/36]
5. Calculate the longest wavelength which can remove the electron from Ist Bohr’s orbit of H
atom. ( Given E1 = 13.6 eV) [9.09 × 10-8m]
Transition giving the spectral lines of lowest energy in the visible region of its atomic
spectra.
(Given : RH = 1.1 × 107m–1, c = 3 × 108 m sec–1 and h = 6.62 × 10–34 J sec. )
[182.2kJmol–1]

ATOM I C SPECTRUM
Spectrum is the impression produced on a photographic film when the radiation is analysed through
a prism or diffraction grating with respect to wavelength or frequency present in it.
Types of Spectrum
(1) Emission spectrum
When the radiation emitted from some source, (by passing electric discharge through a gas at
low pressure or by heating some substance to high temperature, etc.), is passed directly
through the prism and then received on the photographic plate, the spectrum obtained is
called ‘Emission spectrum’.
(2) Absorption spectrum
When white light from any source is first passed through the solution or vapours of a
chemical substance and then analysed by the spectroscope it is observed that some dark lines
are obtained in the otherwise continuous [Link] these spectra can be of two types
(i) Continuous Spectrum
When white light from any source such as sun or bulb is analyzed by passing through
a prism, it splits up into seven different wide bands of colour from violet to red (like
rainbow). These colours are so continuous that each of them merges into the next
without any gap or break. Hence the spectrum is called continuous spectrum.
e.g., Carbon arc in vacuum and electric glow lamp give continuous spectrum.
(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 coloured lines are
obtained on a photographic plate separated from each other by dark spaces. This
spectrum is called line spectrum. Each line in the spectrum corresponds to a particular
wavelength. Each element gives its own characteristic spectrum.

H YD ROGEN SPECTRUM
If an electric discharge is passed through hydrogen gas in atomic state taken in a discharge tube
under low pressure and the emitted radiation 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.
This series of lines is known as line or atomic spectrum of hydrogen. The lines in the visible region
can be directly seen on the photographic film.
Chemistry-XI 47

According to Bohr, the spectrum arises when the electron 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 .

Explanation of Line Spectra

hc
E = h = E2  E1 or  E2  E1


 1   1   1 
 E n   RH  2   E1   RH  2  and E2   RH  2 
n   n1   n2 
hc  RH    RH 
 E     
  n22   n12 
1 1 hc 1 1
 E  RH  2  2    RH  2  2
 n1 n2    n1 n2 
1 R 1 1
  H  2  2
 hc  n1 n2 

 RH  1 1 3.29  1015 s 1  1 1 1 1
   2  2 
= 1  2
 2   1.09677  107  2  2  m1
c hc  n1 n2  3  10 ms  n1 n2 
8
 n1 n2 
1 1 1
or    RH  2  2
  n1 n2 
where RH is called the Rydberg constant of the hydrogen atom.
RH = 1.097 107 m–1
Note that n2  n1 and the term in the parenthesis is positive.
In case of absorption spectrum photon (light) of the calculated wave number is absorbed whereas in
case of emission spectrum, photon (light) of calculated wave number is released.
Above equation is called the Rydberg equation. Using this equation, the wave numbers of photons
of the various spectral series are calculated as follows:

1. Lyman Series
In this series, the spectral lines correspond to the transition of the electron from some higher
energy state (n) to the lower energy state corresponding to n1 = 1.
1 1 
  R H  2  2  ; n = 2, 3, 4, …
1 n 
These lines are found in the ultraviolet region of the electromagnetic spectrum.
2. Balmer Series
In this series, the spectral lines correspond to the transition of the electron from some higher
energy state (n) to the lower energy state corresponding to n1 = 2.
 1 1 
  R H  2  2  ; n = 3, 4, 5, …
2 n 
These lines are found in the visible region.
48 Structure of Atom

3. Paschen Series
In this series, the spectral lines correspond to the transition of the electron from some higher
energy state (n) to the lower energy state corresponding to n1 = 3.
1 1 
  R H  2  2  ; n = 4, 5, 6, …
3 n 
These lines are found in the near infrared region.
4. Brackett Series
In this series, the spectral lines correspond to the transition of the electron from some higher
energy state (n) to the lower energy state corresponding to n1 = 4.
 1 1 
  R H  2  2  ; n = 5, 6, 7, …
4 n 

These lines are also found in the near infrared region.

5. Pfund Series
In this series, the spectral lines correspond to the transition of the electron from some higher
energy state (n) to the lower energy state corresponding to n1 = 5.
1 1
ν  R H  2  2  ; n = 6, 7, 8, …
5 n 
These lines are found in the far infrared region.
The Bohr’s theory successfully accounts for the spectra of hydrogen atom and hydrogen-like
(Hydrogenic) ions such as He+, Li2+, Be3+, B4+, etc.

n=8
n=7
n=6

n=5
Pfund Series

n=4
Brackett Series

n=3
Paschen Series

n=2
Balmer Series

n=1
Lyman Series

Transition of the electron in hydrogen atom

Determination of the spectral lines emitted by atomic hydrogen sample excited to nth energy level?
Chemistry-XI 49

Number of spectral lines that appear in hydrogen spectrum when an electron de-excites from nth
n n  1
energy level = (n  1) 
2
Merits of Bohr’s Theory
(i) The experimental value of radii and energies in hydrogen atom are in good agreement with
that calculated on the basis of Bohr’s theory.
(ii) Bohr’s concept of stationary state of electron explains the emission and absorption spectra of
hydrogen like atoms (i.e., one electron species).
(iii) The experimental values of the wavelength of the spectral lines in the hydrogen spectrum are
in close agreement with that calculated by Bohr’s theory.

Limitations of Bohr’s Theory

(i) It does not explain the spectra of atoms having more than one electron.
(ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman effect) or
electric field (Stark effect) on the spectra of atoms or ions.
(iii) de Broglie suggested that electrons like light has dual character. It has particle nature as well
as wave nature. Bohr treated the electron only as a particle.
(iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty Principle.

What is the wavelength of the light emitted when the electron in a hydrogen atom
undergoes transition from an energy level with n = 4 to an energy level with n = 2?
What is the colour corresponding to this wavelength? (Rydberg constant = 109, 677
–1
cm )
Example 25

 1 1   1 1  –1 –1
 = R  2  2  = 109677  2  2  cm = 20564.4 cm .
 n1 n 2  2 4 

1 1 –7 –9
= = = 486 × 10 cm = 486 × 10 m = 486 nm
 20564.4 cm 1

The colour corresponding to this wavelength is blue.

50 Structure of Atom

How much energy is required to ionise a hydrogen atom if the electron occupies
n = 5th orbit? Compare your answer with the ionisation energy of hydrogen atom
(energy required to remove the electron from n = 1st orbit).
Hint:
21.8  1019 –1
 En = – 2
J atom
n
For ionization from 5th orbit, n1 = 5, n2 = 
–19  1 1  –19  1 1 
Example 26

 E = E2 – E1 = –21.8 × 10  2  2  = 21.8 × 10  2  2
 n 2 n1   n1 n 2 
–19  1 1 20
= 21.8 × 10  2   = 8.72  10 J
5 
For ionization from 1st orbit, n1 = 1, n2 = 
–19 1 1 –19
E  = 21.8 × 10  2   = 21.8 × 10 J
1  
E ' 21.8  1019
= = 25
E 8.72  1020
Thus, the energy required to remove electron from 1st orbit is 25 times than that required to
remove electron from 5th orbit.
What is the maximum number of emission lines obtained when the excited electron of a
H atom in n = 6 drops to the ground state?
No. of lines produced when electron from nth shell drops to ground state
(n 2  n1 )  (6  1)  5  5  4  3  2  1  15
[These are produced due to following transitions:
Example 27

6 
5 5 
4 4 
3 3 
2 2 
1
6 
4 5 
3 4 
2 3 
1
6 
3 5 
2 4 
1
6 
2 5 
1
6 
1
[ (5 lines) (4 lines) (3 lines) (2 lines) (1 line)]
Chemistry-XI 51

Calculate the frequency, energy and wavelength of the radiation corresponding to the
spectral line of lowest frequency in Lyman series in the spectra of H atom. Also
calculate the energy for the corresponding line in the spectra of Li 2  .
( RH  1.09678  107 m 1 , c  3  108 ms 1 , h  6.625  10 34 Js )

1 1 1 1 1  1 1  3
 RH  2  2  = RH  2  2   RH  1  4   4 RH
  n1 n2  1 2   
Example 28

4 4 1
or    = 1.216  107 m
3RH 3 1.09678  107 m1

c 3  108 ms 1
v  = 2.47  1015 s 1
 1.216  10 m
7

E  hv = 6.625  1034 Js  2.47  1015 s 1

= 16.36  1019 J
ELi 2  Z 2  EH  32  16.36  1019 J = 147.24  1019 J

Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and
can be represented as v = 3.29 × 1015 Hz [1/32 – 1/n2]
Calculate the value of n if the transition is observed at 1285 nm. Find the region of the
spectrum.
Example 29

3.0  108 ms1

= 3.29 ×1015 
c 1 1 
v= =  
 1285  10 9 m 3
2
n2 

1 1 3.0  108 ms1 1 1

or = –  = 0.111 – 0.071 = 0.04 = or n2 = 25 or n = 5
n 2
9 1285  10 9 m 3.29  1015 25

The radiation corresponding to 1285 nm lies in the infrared region.

Calculate the wavelength for the emission transition if it starts from the orbit having
radius 1.3225 nm and ends at 211.6 pm. Name the series to which this transition belongs
and the region of the spectrum.
0.529n 2 52.9n 2
Radius of nth orbit of H-like particles = Å= pm
Z Z
25.9n12  r2 = 52.9n22
r1 = 1.3225 nm = 1322.5 pm = pm 211.6 pm =
Example 30

Z Z
 r1 1322.5 n 21 n 21 n1
= = 2
or = 6.25 or = 2.5
r2 211.6 n 2 n 22 n2

If n2 = 2, n1 = 5. Thus, the transition is from 5th orbit to 2nd orbit. It belongs to Balmer
series.
= 1.097 × 107 m–1 
1 1  21
   = 1.097 × × 107 m–1.
2 52 
2
100
1 100
or  = = m = 434 × 10–9 m = 434 nm
 1.097  21  10 7
52 Structure of Atom

Example 31 Of the following transitions in hydrogen atom, the one which gives an absorption line of
lowest frequency is
(a) n =1 to n = 2 (b) n= 3 to n = 8
(c) n = 2 to n = 1 (d) n = 8 to n = 3
Absorption line in the spectra arise when energy is absorbed, i.e., electron shifts from lower to
higher orbit, out of a & b, b will have the lowest frequency as this falls in the Paschen’s series.
 (b)

Try Yourself-5

1. Find the wavelength of the radiation emitted, when in a hydrogen atom electron falls from
infinity to stationary state 1(Rydberg constant = 1.097  107 m1). [91nm]
-1
2. Calculate the longest wavelength in H spectrum of Lyman series. RH = 109678 cm
[82,258 cm–1]
3. Calculate the wave number for the longest wavelength transition in the Balmer series of
atomic hydrogen. [ 1.523 106 m1 ]

4. Calculate the wavelength of radiations emitted producing a line in Lyman series, when an
electron falls from fourth stationary state to ground state in hydrogen atom.
(RH = 1.1 × 107m–1) [9.6 × 10–8 m]
5. In spectrum of Hydrogen atom, a spectral line corresponds to n1 = 3 and n2 = 5
(i) calculate the wavelength and frequency of this spectral line
[1.28 × 10-6m, 2.34 × 1014 Hz]

(ii) To which spectral series does this line belong to [Paschen series]
(iii) In which region of electromagnetic spectrum, will this line fall? [IR]
6. What is maximum number of emission lines when the excited electron of a H atom in n = 7
drops to ground state. [21]
7. To what series does the spectral lines of atomic hydrogen belong if its wave number is equal
to the difference between the wave numbers of the following two lines of the Balmer series,
486.1 and 410.2 nm? What is the wavelength of that line? [Pfund series, 2,627nm]
8. What is the energy in joules required to shift the electron of the hydrogen atom from the first
Bohr orbit to the fifth Bohr orbit and what is the wavelength of the light emitted when the
electron returns to the ground state? The ground state electron energy is –2.18 × 10–11 ergs.
[ 951Å ]
–11 2
9. The electron energy in hydrogen atom is given by En = (–2.18 × 10 )/n erg. Calculate the
energy required to remove the electron completely from n = 2 orbit. What is the longest
wavelength of light in cm that can be used to cause this transition? [ 3.647 105 cm ]
10. The wavelength of the first line in the Balmer series is 656 nm. Calculate the wavelength of
the second line and the limiting line in Balmer series.
Chemistry-XI 53

PARTI CLE N ATURE OF ELECTROM AGN ETI C RAD I ATI ON

Black Body Radiation and Explanation by Planck’s Quantum Theory
An ideal black body may be defined as
A perfect absorber and a perfect emitter of radiations which means that it emits and absorbs
radiations of all frequencies which fall on its surface.
A black body absorbs all the radiations that are incident or falling on it. However, when such a body
is heated, it emits energy in the form of radiations. When a black body such as an iron rod is heated
in a furnace, it undergoes a series of changes in colour.
With rise in temperature, it initially becomes dull red in colour and then becomes more and more red
as temperature increases. The red colour changes to yellow and then to white and finally it becomes
blue at very high temperature. These observations are not in agreement with the wave theory of
radiations since according to the theory, 'the heat energy supplied must increase the intensity of the
same colour, i.e., Red and black body is not expected to undergo change in colour.

The explanation for the changes in colour which

a black body undergoes upon heating is provided
by Planck's Quantum theory. According to the
theory, there is a direct relation between energy
of the radiations and frequency (E   ). Thus,
when a black body is heated, it undergoes a
change in energy, i.e., energy increases and so is
frequency of the striking radiations. It is quite
obvious that the frequency of the radiations
emitted will also change. Since there is a co-
relation between the frequency and colour, the
changes in colour which we notice on heating a
black body can be justified.

According to wave theory, the wavelength (  ) of the radiations varies inversely as the frequency.
This means that at a given temperature, the intensity of the radiations emitted increases with increase
in wavelength. It reaches a certain maximum value at some wavelength and then starts decreasing as
shown graphically. The intensity of the radiations also increases with rise in temperature.' Thus for a
given wavelength, the intensity of the radiations is more at T2 than at T1 (T2 > T1).

Photo Electric Effect

In 1887, H. Hertz performed a very interesting experiment and observed that when a beam of light of
certain frequency strikes the surface of a metal (for example, potassium, rubidium, caesium, etc.,),
electrons are ejected from the metal. This phenomenon is known as photoelectric effect and the
ejected electrons are called photoelectrons.
A few metals like Cesium, which are having low ionisation energy show this effect under the action
of visible light but many more show it under the action of more energetic ultraviolet light.
54 Structure of Atom

Light
radiation Ejected
E = hv electron

Metal plate

When a radiation of sufficient energy is made to fall on the metal plate the following observations
are noted.
(i) Electrons come out as soon as the light (of sufficient energy) strikes the metal surface, i.e.,
there is no time lag between the ejection of electrons from the metal surface.
(ii) The light of just any frequency will not be able to cause ejection of electrons from the metal
surface. There is a minimum frequency called the threshold (or critical) frequency (o),
which can just cause the ejection. This frequency varies with the nature of the metal. The
higher the frequency of the light, the more energy the photoelectrons will have.
(iii) Photoelectric current is increased with increase in intensity of light of same frequency, if
emission is permitted, i.e., a bright light yields more photoelectrons than a dim one of the
same frequency, but the electron energies remain the same.
Let, the threshold frequency of light required to eject electrons from a metal is o. When a
photon of light of this frequency strikes a metal it imparts its entire energy (hvo) to the
electron.
E = hvo E > hvo

[Link] = hv – hvo
K. E = 0

Metal

This energy enables the electron to break away from the atom by overcoming the attractive influence
of the nucleus. Thus, each photon can eject one electron. If the frequency of light is less than o there
is no ejection of electron. If the frequency of light is higher than o (let it be ), the photon of this
light having higher energy (h), will impart some energy to the electron that is needed to remove it
away from the atom and the excess energy would give a certain velocity (i.e, kinetic energy) to the
electron.
h = ho + K.E
h = ho + ½ mv2 where,  = frequency of the incident light
o = threshold frequency, v = velocity of electron.
½ mv2 = h –ho
y = mx + c
Chemistry-XI 55

ho is called the threshold energy, or the work function denoted by  = ho (minimum energy of the
photon to liberate electron). It is constant for a particular metal.
The kinetic energy of the photoelectrons increases linearly with the frequency of incident light.
Thus, if the kinetic energy of the ejected electrons is plotted as a function of frequency, it results in a
straight line whose slope is equal to Planck’s constant h and intercept is hvo.

K.E
slope (m) = h
of
Photoelectrons

o
c = ho 

Calculate the kinetic energy of the electron ejected when yellow light of frequency
5.2  1014 sec 1 falls on the surface of potassium metal. Threshold frequency of potassium
Example 32

is 5  1014 sec 1 .
1
K.E. of the ejected electron is given by mv2  h  h 0  h(   0 )
2
= 6.625  1034 (5.2  1014  5.0  1014 )  6.625 1034  0.2  1014 joules = 1.325  1020 joules .
Irradiation of a metal with light of frequency 5.2  1014 s 1 yields electrons with maximum
K.E. 1.3  1019 J . Calculate threshold energy (v0 ) for the metal.
Example 33

Given :v  5.2 1014 s 1

K .E.  1.3 1019 J
K .E. 1.3  1019 J
hv  hv0  K .E. or v0  v   (5.2  1014 s 1 ) 
h 6.626  1034 Js
= 5.2  1014 s 1  1.962  1014 s 1 = 3.238  1014 s 1
–7
A photon of wavelength 4 × 10 m strikes on metal surface, the work function of the
metal being 2.13 eV. Calculate
(i) the energy of the photon (eV)
(ii) the kinetic energy of the emission and
–19
(iii) the velocity of the photoelectron. (1 eV = 1.602 × 10 J)
hc (6.626  10 Js)  (3  108 ms 1 )
34
–19
(i) Energy of the photon (E) = h = = = 4.97 ×10 J
Example 34

 4  10 m
7

4.97  1019
= eV = 3.10 eV
1.602  1019
  1
(ii) Kinetic energy of emission =  mv 2  = h  h 0 = 3.10 – 2.13 = 0.97 eV
2 
1 –19
(iii) mv 2 = 0.97 eV= 0.97 × 1.602 × 10 J
2
1 –31 2 –19
i.e. × (9.11 × 10 kg) × v = 0.97 × 1.602 × 10 J
2
or v 2  0.341 1012  34.1 1010 or v  5.84  105 ms 1
56 Structure of Atom

Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 6800 Å. Calculate the threshold frequency ( 0 ) and work
function (W0) of the metal.
Example 35

We are given the velocity of electron = 0

–10
Threshold wavelength ( 0 ) = 6800 Å = 6800 × 10 m

3.0  108 ms1 14 –1

As c    0 = = 4.41 × 10 s .
6800  10 10

–34 14 –1 –19
Work function (W0) = h  0 = (6.626 × 10 Js) (4.41 × 10 s ) = 2.92 × 10 J

If proton of the wavelength 150 pm strikes an atom and one of its inner bound electrons
is ejected out with a velocity of 1.5 × 107 ms–1, calculate the energy with which it is
bound to the nucleus.
(6.626  1034 J )(3.0 108 ms 1 )
= 13.25 × 10–16 J
hc
Energy of the incident photon = =
Example 36

 (150  1012 m)

mv2 = (9.11 × 10–31 kg) (1.5 × 107 ms–1)2 = 1.025 ×

1 1
Energy of the electron ejected =
2 2
10–16 J
Energy with which the electron was bound to the nucleus = 13.25  1016 J – 1.025  1016 J
12.225 1016
= 12.225 × 10–16 J = eV = 7.63 × 103 eV
19
1.602 10

Try Yourself-6
1. When electromagnetic radiation of wavelength 300 nm falls on the surface of sodium,
electrons are emitted with a kinetic energy of 1.68 × 105 J mol–1. What is the minimum
energy needed to remove an electron from sodium? What is the maximum wavelength that
will cause a photoelectron to be emitted? [ 3.84  1019 J, 517 nm]
2. The threshold frequency  0 for a metal is 7.0  1014 s 1 . Calculate the kinetic energy of an
electron emitted when radiation of frequency   1.0  1015 s 1 hits the metal. [ 1.988  1019 J ]
3. The dissociation energy of H 2 is 430.53kJ mol 1 . If H 2 is exposed to radiation energy of
wavelength 253.7 nm, what % of radiant energy will be converted into kinetic energy?
[8.68%]
4. Iodine molecule 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. (Bond
energy of I 2  240kJ mol 1 ) [ 0.216  1019 J ]
5. The work function for caesium atom is 1.9 eV. Calculate (a) the threshold wavelength and (b)
the threshold frequency of the radiation. If the caesium element is irradiated with a
wavelength 500 nm, calculate the kinetic energy and the velocity of the ejected
photoelectron.
[(a)654nm, (b) 4.59  1014 s 1 , K.E. = 9.36  1020 J , V  4.53  105 ms 1 ]
Chemistry-XI 57

6. Following results were observed when sodium metal is irradiated with different wavelengths.
Calculate (a) threshold wavelength and (b) Planck’s constant
 (nm) 500 450 400
–6 –1
v × 10 (ms ) 2.55 4.35 5.20
[ 0  531nm ; h  6.66  1034 Js ]
7. The ejection of the photoelectron from the silver metal in the photoelectric effect experiment
can be stopped by applying a voltage of 0.35 V when the radiation 256.7 nm is used.
Calculate the work function for silver metal. [ 4.48ev]
8. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the sodium atom.
–1
Calculate the ionization energy of sodium in kJ mol . [ 494.5kJ mol 1 ]

D UAL CH ARACTER OF ELECTRON

Einstein suggested dual character of light, i.e., light behave as wave as well as particle. The
phenomenon of diffraction and interference only could be explained by taking light as waves and the
phenomenon like black body radiation and photoelectric effect could be explained only on the basis
of its particle nature.
de-Broglie proposed that matter can also have a dual character, i.e., wave and particle. He derived an
expression for calculating the wave length  of a particle of mass m moving with velocity v.
h h
i.e.,   
mv p

This equation is popularly known as de-Broglie equation.

1 2
We know K.E. = mv
2
 mv  2m K .E.

Where
p = momentum of the particle
m = mass of particles
 is called de Broglie wavelength?
Distinction between the wave- particle nature of a photon and the wave-particle nature of a
Sub-atomic particle

[Link] Photon Sub - Atomic Particle

.
1. Energy = h 1
Energy = m 2
2
2. c h
Wavelength = Wavelength =
 m
[Note: We should never interchange any of the above]
58 Structure of Atom

Bujho is now in class 11. He is weighing 70 kg was jogging at 15 km/hr. Calculate the
wavelength at which he was jogging.
Example 37

15  1000
Velocity u  15km / hr   4.167 ms 1
60  60
h 6.626  1034
  = 2.27  1036 m
mv 70  4.167

How fast is an electron moving if it has wavelength equal to the distance it travels in one
second?
Example 38

h h h
  v  v or V 2 
mv mv m
1/2 1/2
h  6.626  1034 
Or v  = 31 
= 2.697  102 ms 1
m  9.108  10 

Two particles A and B are in motion. If the wavelength associated with particle A in
motion is 5  108 m, calculate the wavelength associated with particle B if its momentum is
half than that of A.
Example 39

h h
A  ; B 
p p/2

B
Or 2
A

Or B  2   A = 2  5  108  107 m

The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 ×
Example 40

105 m s–1. If the hockey ball of mass 0.1 kg is moving with this velocity, calculate the
wavelength associated with this velocity?
6.626  1034 kg m 2 s 1
=15.16 × 10–39 m
h
 = =
mv (0.1 kg )(4.37 105 ms 1 )
Show that the circumference of the Bohr orbit for hydrogen atom is an integral multiple
of the de Broglie wavelength associated with the electron moving around the orbit.
h h
According to Bohr postulate of angular momentum, mvr = n or 2  r = n ...(i)
Example 41

2 mv
h
According to de Broglie equation,  = ...(ii)
mv

Substituting this value in eqn. (i) , we get 2  r = n 

Thus, the circumference (2  r) of the Bohr orbit for hydrogen atom is an integral multiple of
de Broglie wavelength.
Chemistry-XI 59

Try Yourself-7

1. Calculate the wavelength of an electron moving with velocity of 2.05 × 107 ms–1.
[ 3.55 10 11 m ]
2. The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its wavelength.
[ 8967 Å ]
25
3. The kinetic energy of an electron is 4.55  10 J . Calculate the wavelength.
(h  6.6  1034 Js, m  9.1 1031 kg )
4. Similar to electron diffraction, neutron diffraction microscope is also used for the
determination of the structure of this molecule. If the wavelength used here is 800 pm,
calculate the characteristic velocity associated with the neutron.
5. What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s–1 ?
[ 6.6261034 m( J  kgm 2 s 2 ) ]
6. Calculate the kinetic energy of moving electron which has a wavelength of 4.8 pm. (mass of
electron = 9.11 × 10–31 kg, h = 6.63 × 10–34 J s) [ 1.05 1014 J ]
7. Calculate the mass of a photon with wavelength 3.6 Å. [ 6.135  1033 kg ]
8. Dual behaviour of matter proposed by de Broglie led to the discovery of electron microscope
often used for the highly-magnified images of biological molecules and other types of
material. If the velocity of the electron in this microscope is 1.6 × 106 m s–1, calculate de
Broglie wavelength associated with this electron. [455pm]
6 –1
9. If the velocity of the electron in Bohr’s first orbit is 2.19 × 10 m s , calculate the de Broglie
wave length associated with it. [ 332pm]

H EI SEN BERG’S UN CERTAI N TY PRI N CI PLE

This principle states that "It is impossible to measure simultaneously the position and
momentum of a small microscopic moving particle with absolute accuracy or certainty", i.e., if
an attempt is made to measure any one of these two quantities with higher accuracy, the other
becomes less accurate.
The product of the uncertainty in position (x) and the uncertainty in the momentum (p ) (p =
mv where m is the mass of the particle and v is the uncertainty in velocity) is equal to or greater
than h/4 where h is the Planck’s constant.
Thus, the mathematical expression for the Heisenberg’s uncertainty principle is simply written as
h
x.p 
4

h h
or x  mv  or x  v 
4 4 m

Note that if m is large enough, the uncertainties x and v can be quite small and still satisfy the
uncertainty principle. For objects large enough to be seen, the uncertainties are small, and we can
easily describe their orbits. Thus, the orbit of a baseball and the orbit of the earth have meaning. But
when the mass is that of an electron, the uncertainties become significant.
60 Structure of Atom

Significance of Heisenberg’s uncertainty principle

Like de Broglie equation, although Heisenberg’s uncertainty principle holds good for all objects, but
it is of significance only for microscopic particles. The reason for this is quite obvious. The energy of
the photon is insufficient to change the position and velocity of bigger bodies when it collides with
them. For example, the light from a torch falling on a running rat in a dark room neither changes the
speed of the rat nor its direction, i.e., position.
This may be further illustrated with the following examples:
For a particle of mass 1 mg, we have
h 6.626  1034 kg m 2 s 1
x.  =  1028 m 2 s 1
4m 4  3.1416  (106 kg )
Thus, the product of x and v is extremely small. For particles of mass greater than 1 mg, the
product will be still smaller. Hence, these values are negligible.
For a microscopic particle like an electron, we have
h 6.626  1034 kgm2 s 1
x.    104 m 2 s 1
4m 4  3.1416  (9.11  1031 kg )
Thus, if uncertainty in position is 10–4 m, uncertainty in velocity will be = 1.0 m s–1 which is quite
significant. It is for this reason that Bohr’s concept of fixed circular path with definite position and
momentum of the electron have been replaced by stating that the electron has the probability of
having a given position and momentum. Thus, forms the basis of quantum or wave mechanical
model of atom.
Since in everyday life, we come across big objects only, the position and velocity of which can be
measured accurately, Heisenberg’s uncertainty principle has no significance in everyday life.
Reasons for the Failure of The Bohr Model
One can now understand the reasons for the failure of the Bohr model. In Bohr model, an electron is
regarded as a charged particle moving in well-defined circular orbits about the nucleus. The wave
character of the electron is not considered in Bohr model.
Further, an orbit is a clearly defined path and this path can completely be defined only if both the
position and the velocity of the electron are known exactly at the same time. This is not possible
according to the Heisenberg uncertainty principle.
Bohr model of the hydrogen atom, therefore, not only ignores dual behaviour of matter but also
contradicts Heisenberg uncertainty principle. In view of these inherent weaknesses in the Bohr
model, there was no point in extending Bohr model to other atoms.
In fact an insight into the structure of the atom was needed which could account for wave-particle
duality of matter and be consistent with Heisenberg uncertainty principle. This came with the advent
of quantum mechanics.
With the help of the uncertainty principle, explain why an electron is not present in the
nucleus.
Electron to remain in nucleus, in it, then the uncertainty in its velocity (v) must be less than
that of velocity of light, i.e., 3 × 108 ms–1. Let us calculate the actual value of v . In case the
electron is to be a part of the nucleus, then the uncertainty in its position (x) cannot be more
Example 42

than the diameter of the nucleus i.e., 10–15 m. Taking the mass of the electron as 9.1 × 10–31
kg, the value of v can be calculated
h h
x  p = or x  mv 
4 4

v 
h
=
 6.626  1034 kg m 2 s 1 
= 5.79 × 1010 ms–1.
4mx 4  3.143  (9.1  1031 kg)  (1015 m)
Since the value comes out to be more than the velocity of light (3.0 × 108 ms–1), this means
that the electron cannot exist in the nucleus of atom and is a part of extra nuclear portion.
Chemistry-XI 61

Calculate the uncertainty in the position of an electron if uncertainty in its velocity is

(i) 0.001% (ii) zero
(The mass of electron = 9.1 × 10–31 kg, velocity of electron = 300 ms–1)
Mass of electron = 9.1 × 10–31 kg,
h = 6.6 × 10–34 Js
(i) When v = 0.001% of velocity of electron
0.001 300
=  3.0  103 ms1
Example 43

100
h
Now, x  mv 
4
h 6.6  1034 kgm 2s 1
 x  = = 1.92  102 m
4 mv 4  3.142  (9.1  1031 kg)  (3.0  103 )
(ii) When v  0
h
x 
4 mv
If v is zero, then denominator in the above expression becomes zero and therefore,
uncertainty in position is infinity.
An electron has a speed of 500 ms–1 with uncertainty of 0.02%. What is the uncertainty in
locating its position?
Velocity of electron = 500 ms–1.
500  0.02
Uncertainty in velocity, v  500  0.02% = = 0.1ms1
100
Mass of electron, m  9.1  1031 kg
Example 44

h  6.6  1034 kgm 2 s1

h
According to uncertainty principle, x  p 
4
h
or x  mv 
4
h 6.6  1034 kgm 2s 1
or x    5.77  104 m
4 mv 22
4   9.1  1031  0.1
7
 Uncertainty in position = 5.77 × 10–4 m.
Show that Heisenberg uncertainty principle is of negligible significance for an object of
 h 
106 kg mass.   0.528  1034 kg m 2 s 1 
 4 
Example 45

h 0.528  1034 kg m 2 s 1
x  v  = = 0.528  1028 m 2 s 1
4 m 106 kg

It is an extremely small value and so, uncertainty principle is of negligible significance for an
object of mass 106 kg .
On the basis of uncertainty principle show that the e (mass = 9  1031 kg ) cannot exist
Example 46

within an atomic nucleus of radius 1015 m .

h 0.528  1034
v  = = 5.87  1010 ms 1
4 m  x 9  1031  1015
Since, the uncertainty in velocity is much higher than the velocity of light (3  108 ms 1 ) , which
is not possible. Hence, and e cannot exist within an atomic nucleus.
62 Structure of Atom

If the position of the electron is measured within an accuracy of 2  103 nm, calculate the
uncertainty in the momentum of the electron. Suppose the momentum of the electron is h/(4  ×
0.05) nm, is there any problem in defining this value?
x = 0.002 nm = 2 × 10–3 nm = 2 × 10–12 m
Example 47

h
x × p =
4
h 6.626  1034 kg m 2 s1
 p = = = 2.638 × 10–23 kg m s–1.
4 x 4  3.14  (2  1012 m)
h h 6.626  10 34 kg m 2 s1
Actual momentum = = = = 1.055 × 10–24 kg m s–1.
4  0.05nm 11
4  5  10 m 4  3.14  5  10 11 m
It cannot be defined as the actual magnitude of the momentum is smaller than the uncertainty.

Try Yourself-8

1. In what way Heisenberg’s uncertainty principle differs from the Bohr’s concept of stationary
states?
2. Is Heisenberg’s uncertainty principle applicable to a stationary electron? Give reason for your
answer.
3. Why is it not possible to determine exact position and momentum of fast moving sub atomic
particles llike electrons simultaneously?
4. A microscope using suitable photons is employed to locate an electron in an atom within a
distance of 0.1 Å. What is the uncertainty involved in the measurement of its velocity?
[ 5.79  106 ms 1 ]
5. A golf ball has a mass of 40g, and a speed of 45 m/s. If the speed can be measured within
accuracy of 2%, calculate the uncertainty in the position. [1.46×10–33m]
6. If the position of the electron is measured within an accuracy of nm, calculate the uncertainty
in the momentum of the electron. Suppose the momentum of the electron is h/(4  × 0.05)
nm, is there any problem in defining this value? [ 1.055×10–24kgms–1.]
7. The uncertainty in position and velocity of a particle are 1010 m and 5.27  1024 ms 1
respectively. Calculate the mass of the particle. ( h  6.625  1034 Js ). [0.10kg]

QUAN TUM M ECH AN I CAL M OD EL OF ATOM

In the discussion of de Broglie relationship, we have studied that an electron has a dual nature, i.e.,
wave as well as particle nature. Heisenberg has stated that it is not possible to measure
simultaneously the position and momentum (velocity) of the electron with absolute accuracy. In
1926, Erwin Schrodinger developed an atomic model taking into account both the wave and particle
nature of the electron. This is known as quantum (or wave) mechanical model of atom. The wave
mechanics is also called Quantum Mechanics. It describes the electron as a three-dimensional wave
in the electronic field of the positively charged nucleus. The wave motion of the electron in this field
is described with the help of an equation known as Schrodinger wave equation which is a differential
equation and is expressed as :
 2   2   2  8 2 m
   [E  V]   0
x 2 y 2 z 2 h2
Here x, y, z are the space (or cartesian) co-ordinates.
m = Mass of the electron ; E = Total energy of the electron
Chemistry-XI 63

V = Total potential energy of the electron

(Psi) = Wave function of the electron
2
= Second differential of  with respect to x axis and so on.
x 2
For an electron with charge = – e; and nuclear charge +e (in case of H-atom), potential energy may
be given as ;
e2
V
r
:. In the light of this, the Schrodinger wave equation may be written as :
 2   2   2  8 2 m  e2 
    E    0
x 2 y 2 z 2 h2  r 

Important Features of Quantum Mechanical Model of Atom

Schrodinger wave equation gives a better picture of the atom than the Bohr’s Model. This model of
atom popularly known as Quantum Mechanical Model of Atom has the following important
consequences.
 The energy of electrons in an atom is quantized, i.e., it can have only certain specific values.
 The quantized energy levels in which electrons can be present are obtained from the solution
of the Schrodinger wave equation.
 As pointed by Heisenberg’s uncertainty principle, both the exact position and the exact
velocity (or momentum) of an electron cannot be determined simultaneously. The path of the
electron is only probable and not exact. This has ultimately led to the concept of atomic
orbitals.
 The atomic orbital is represented by the wave function. Since a number of such wave
functions are possible for an electron, the corresponding atomic orbitals are also possible. In
each orbital, the electron has a definite energy and it cannot have more than two electrons.
 The probability of finding an electron at a point within an atom is proportional to square of
the wave function, i.e., []2 at different points within an atom, one can predict the region
around the nucleus where the electron will be most probably found or closed.

QUAN TUM N UM BERS AN D ATOM I C ORBI TALS

Each electron in an atom is described by four different quantum numbers, three of which
(n, l, m) specify the wave function that gives the probability of finding the electron at various points
in space. A wave function for an electron in an atom is called an atomic orbital. An atomic orbital is
pictured qualitatively by describing the region of space where the probability of finding the electrons
is maximum.
Quantum numbers may be defined as a set of four numbers with the help of which we can get
complete information about all the electrons in an atom, i.e., location, energy, the type of orbital
occupied, shape and orientation of that orbital, etc.,

Principal Quantum Number (n)

It tells us about the shell in which the electron resides and is denoted by the letter 'n'. It can have any
positive value 1, 2, 3 and so on. It gives the following information:
(i) It gives the average distance of the electron from the nucleus.
(ii) It determines the energy of the electron in hydrogen atom and hydrogen like species.
64 Structure of Atom

(iii) The maximum numbers of electron present in any principal shell is given by 2n2 where n is
the number of the principal shell.

Shell K L M N
Principal quantum number (n) 1 2 3 4
Maximum number of electrons 2 8 18 32

Azimuthal or Angular Momentum Quantum Number (  )

This represents the number of subshells present in the main shell and is denoted by  . It can have any
integral value ranging from 0 to (n  1). This quantum number gives the following information:
(i) The number of subshells present in the main shell.
For a given value of n, l can have n values ranging from 0 to n – 1, that is, for a given value
of n, the possible value of l are : l = 0, 1, 2, .......... (n – l)
For example, when n = 1, value of l is only 0. For n = 2, the possible value of l can be 0 and
1. For n = 3, the possible l values are 0, 1 and 2.
Each shell consists of one or more subshells or sub-levels. The number of subshells in a
principal shell is equal to the value of n. For example in the first shell (n = 1), there is only
one sub-shell which corresponds to l = 0. There are two sub-shells (l = 0, 1) in the second
shell (n = 2), three (l = 0, 1, 2) in third shell (n = 3) and so on.
Each sub-shell is assigned an azimuthal quantum number (l). Sub-shells corresponding to
different values of l are represented by the following symbols.
Value for l : 0 1 2 3 4 5 ............
notation for s p d f g h ............
sub-shell
(ii) The shape of the subshells.
(iii) The orbital angular momentum of the electron in any subshell, L =   1 h 2

h
or L =   1  (for a particular value of n) [Where   ]
2
Magnetic Quantum Number (m)
An electron due to its angular motion around the nucleus generates an electric field. This electric
field is expected to produce a magnetic field. Under the influence of external magnetic field, the
electrons of a subshell can orient themselves in certain preferred regions of space around the nucleus
called orbitals. The magnetic quantum number gives information about the spatial orientation of the
orbital with respect to standard set of co-ordinate axis.
For any sub-shell (defined by ‘l’ value) the possible value of m is (2  1) and these values are
given by :
ml = – l, – (l –1), – (l – 2)... 0,1... (l – 2), ( l – 1), l = 2l + 1
Thus for l = 0, the only permitted value of ml = 0, [2(0) + 1 = 1, one s orbital]. For l = 1, ml can be –
1, 0 and +1 [2(1) + 1 = 3, three p orbitals]. For l = 2, ml = –2, –1, 0, +1 and +2, [2(2) + 1 = 5, five d
orbitals]. It should be noted that the values of ml are derived from l and that the value of l are derived
from n.
 Chemistry-XI 65

Spin Quantum Number (s)

Just like earth which not only revolves around the sun but also spins about its own axis, an electron
in an atom not only revolves around the nucleus but also spins about its own axis. Since an electron
can spin either in clockwise direction or in anticlockwise direction, therefore for any particular value
of magnetic quantum number, spin quantum number can have two values, i.e., +1/2 and –1/2 and
these are represented by two arrows pointing in the opposite directions, i.e., and . When an
electron goes to a vacant orbital, it can have a clockwise or anticlockwise spin, i.e., +1/2 or –1/2.
This quantum number helps us to explain the magnetic properties of the substances.
Quantum Number Symbol Restrictions Range of values Significance
Principal quantum number n Positive integers 1,2,3……. Identities shell, determines size and
energy of orbital, number of orbital in
the nth shell = n2.
Azimuthal quantum number l Positive integers 0,1,2….(n–1) Identifies subshell; determines shape
or Angular momentum less than n Total possible of the orbital, energy of orbital in a
quantum number values = n multi electron atom along with n and
orbital angular momentum i.e.
l (l  1)h / 2

Magnetic quantum number ml integers –l to +l including determines orientation of the orbital

between 0 Total possible
–l and +l values = (2l + 1)

Spin quantum number ms Half integers +1/2 or –1/2 determines orientation of the spin.
+1/2 or –1/2
Table: Permissible Values of Quantum Numbers for Atomic Orbitals

Number of orbitals in
n  m Subshell Notation
the subshell
1 0 0 1s 1
0 0 2s 1
2
1 1, 0, +1 2p 3

0 0 3s 1
3 1 1, 0, +1 3p 3
2 2, 1, 0, +1, +2 3d 5
0 0 4s 1
1 1, 0, +1 4p 3
4 2 2, 1, 0, +1, +2 4d 5
3 3, 2, 1, 0, 4f 7
+1, +2, +3
66 Structure of Atom

Which set of quantum number is not consistent with the quantum mechanical theory
Example 48
(a) n = 2,  = 1, m = 1, 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
There is a well defined co-relation between n,  , m and s quantum numbers in an atom.
If n = n then  = (n  1), m will be   and s will always be ½. For n = 3 there cannot be
m = 3. Highest value m will be 2.
Which of the following sets of quantum numbers is correct for an electron in 4 f
orbital?
Example 49

(a) n = 4, l = 3, m = +4, s = +½ (b) n = 4, l = 4, m = 4, s = ½

(c) n = 4, l = 3, m = +1, s = +½ (d) n = 3, l = 2, m = 2, s = +½
For an electron present in 4f orbital possible values of the set of quantum numbers are
n l ml ms
4 3 3…..0….+3 ±½
An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for this
Example 50

electron.
For 3d orbital, n = 3, l = 2. For l = 2, ml = – 2, – 1, 0, +1, +2.

(i) an atomic orbital has n = 3. What are the possible values of l and ml?
When n = 3, l = 0, 1, 2.
When l = 0, ml = 0. When l = 1, ml = –1, 0, +1. when l = 2, m = –2, –1, 0, +1, +2
(ii) List the quantum numbers (ml and l) of electrons for 3d - orbital.
Example 51

For 3d-orbital, n = 3, l = 2, For l = 2, ml = –2, –1, 0, +1, +2

(iii) Which of the following orbitals are possible?
1p, 2s, 2p and 3f.
1p is not possible because when n = 1, l = 0 only (for p, l = 1)
2s is possible because when n = 2, l = 0, 1 (for s, l = 0)
2p is possible because when n = 2, l = 0, 1 (for p, l = 1)
3f is not possible because when n = 3, l = 0, 1, 2 (for f, l = 3)

Explain, giving reasons, which of the following sets of quantum numbers are not possible.
(a) n = 0, l = 0, ml = 0, l  1 ms = 1/2 (b) n = 1, l = 0, ml = 0, ms = –1/2
Example 52

(c) n = 1, l = 1, ml = – 0, ms = +1/2 (d) n = 2, l = 1, ml = 0, ms = –1/2

(e) n = 3, l = 3, ml = –3, ms = +1/2 (f) n = 3, l = 1, ml = 0, ms = +1/2
(a) Not possible because n  0 (b) possible
(c) Not possible because when n = 1, l  1 (d) Possible
(e) Not possible because when n = 3, l  3 (f) possible
Chemistry-XI 67

How many electrons in an atom have the following quantum numbers?

1
(i) n = 4, ms = –
Example 53
2
Total electrons in n = 4 are 2n2, i.e. 2 × 42 = 32. Half of them, i.e., 16 electrons have
1
ms = –
2
(ii) n = 3, l = 0
n = 3, l = 0 means 3s orbital which can have 2 electrons

Try Yourself-9

1. What is the total number of orbitals associated with the principal quantum number n = 3 ?[9]
2. Using s, p, d, f notations, describe the orbital with the following quantum numbers
(a) n = 2, l = 1, (b) n = 4, l = 0,
(c) n = 5, l = 3, (d) n = 3, l = 2 [2p, 4s, 5f, 3d]
3. What is the maximum number of orbitals which can have each of the following set of
quantum numbers?
(a) n = 4, l = 2
(b) n = 3, l = 0 [(a) 5, (b) 1]
4. In which shell, the g orbitals will appear first.
5. Which of the following subshells cannot exist 2d, 9s, 3f, 2p

SH APES OF O RBI TALS

An orbital is the region of space around the nucleus within which the probability of finding an
electron of a given energy is maximum (90–95%). The shape of this region (electron cloud) gives
the shape of the orbital. It is basically determined by the azimuthal quantum number (  ), while the
orientation of orbital depends on the magnetic quantum number (m).
As already explained, for the coordinates (x, y, z) of the electron with respect to the nucleus,
Schrodinger wave equation can be solved to get the value of the orbital wave function  . But  has
not physical significance. Instead, the square of its absolute value, i.e., |  |2 has the significance as it
gives the electron probability density of the electron at that point.
The variation of  and |  |2 at different distance (r) from the nucleus for 1s and 2s orbitals are
shown in fig.
These probability density variations can be visualized in terms of electron cloud diagrams .

(a)
68 Structure of Atom

(b)
Variation of (a) orbital wave function  (b) probability density  2 with distance of the electron from the nucleus for
1s and 2s orbitals
Thus, we observe that the probability of 1s electron is found to be maximum near the nucleus and
decreases as the distance from the nucleus increases. In case of 2s electrons, the probability is again
maximum near the nucleus and then decreases to zero and increases again and then decreases as the
distance from the nucleus increases. The intermediate region (a spherical shell) where the probability
is zero is called a nodal surface or simply node. Alternatively, the point where the wave function, 
changes sign from + to – represents a node. Thus, 2s orbital differs from 1s orbital in having one
node within it. Similarly, 3s has two nodes. In general, any ns orbital has (n – 1 ) nodes. i.e., sum
of l angular momentum nodes and (n – l – 1) radial notes.
Let us now see the shapes of orbitals in the various subshells.

s-orbitals (  = 0)
These orbitals are spherical and symmetrical about the nucleus. The probability of finding the
electron is zero near the nucleus and keep on increasing as the distance from the nucleus increases,
becomes maximum and thereafter decreases. There is vacant space between two successive s–
orbitals known as radial node or nodal surface. But there is no radial node for 1s orbital since it is
starting from the nucleus.
The size of the orbital depends upon the value of principal quantum number(n). Greater the value of
n, larger is the size of the orbital. Therefore, 2s orbital is larger than 1s orbital but both of them are
non-directional and spherically symmetrical in shape.

p–orbitals (  =1)
The probability of finding the p–electron is maximum in two lobes on the opposite sides of the
nucleus. This gives rise to a dumb–bell shape for the p–orbital. For p–orbital  = 1. Hence m = –1,
0, +1. Thus, p–orbital have three different orientations. These are designated as px, py & pz
depending upon whether the density of electron is maximum along the x, y and z axis, respectively.
They are symmetrical but have directional characters. The two lobes of p–orbitals are separated by a
nodal plane, where the probability of finding electron is zero.
Chemistry-XI 69

y y y
z . .
. .. . .. z z
. . .. .
. . . . .. . . .. . .
.. .
. . .. . . .. .. . ....
.
. .. . ... .. . .. ... .
.. . . . .. .
. .. . . .. . ..
. ... ..
. x . . . .
. .. . ... .. . . .
.. . .. .
.
.. .
. .
.. .
.
. . . . .. . . . . . .
. .
. .. . . .
. x . .. . . .. . . .. . . .. . x
.. . . ... ... ... .. . ... ... ... ..
. .
. . . . .. . . . .
. . . .. . .. .
. .. . . . . . . ..
.
.. . . . . .. . .
. .. . . .. ... ....
. ... .. ... .
. . .. .
. ... ..
.

pz py px

The three p orbitals belonging to a particular energy shell have equal energies and are called
degenerate orbitals.
d–orbitals (  =2)
For d–orbitals,  =2. Hence m = –2, –1, 0, +1, +2. Thus there are five dorbitals. They have
relatively complex geometry. Out of the five orbitals, the three (dxy, dyz,dzx) project in between the
axis and the other two d z and dx 2  y 2 lie along the axis.
2

dz2 dx2 – y2
X X Y

.
. .. . .. .
. .. . ..
.
. .. . ..
.. . . . . ... . . . .. .... . ... . . . .. . . . . ... . . .
. .. . . ... . . . .. . . ... . . .. . . ... .
. .. . .. . ..
. ..
. . .. . . Y . .. Z . . .. . . .
Z
. . .
. .. . . .
. .. . . . ..
... .. . . .. . . . . ... .. . . .. . . . . ... .. . . .. . . . .
. ... . ... . . ... . . .. . . ... . ... .
. . .. . . . . . .. . dyz
. . .. . . .
dxy . . .. . . . .. . dxz . . .. . . .

EN ERGI ES OF ORBI TALS

The energy of an electron in a hydrogen atom is determined solely by the principal quantum number.
Thus, the energy of the orbitals in hydrogen atom increases as follows:
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d = 4f
Although the shapes of 2s and 2p orbitals are different, an electron in H atom has the same energy
when it is in the 2s orbital as when it is present in 2p orbital. The orbitals having the same energy are
called degenerate. The 1s orbital in a hydrogen atom, corresponds to the most stable condition and is
called the ground state and an electron residing in this orbital is most strongly held by the nucleus.
An electron in the 2s, 2p or higher orbitals in a hydrogen atom is in excited state.
The stability of an electron in multi-electron atom is because total attractive interactions are more
than the repulsive interactions. The attractive interactions of an electron increase with increase of
positive charge (Ze) on the nucleus. Due to the presence of electrons in the inner shells, the electron
in the outer shell will not experience the full positive charge of the nucleus (Ze).
The effect will be lowered due to the partial screening of positive charge on the nucleus by the inner
shell electrons. This is known as the shielding of the outer shell electrons from the nucleus by the
70 Structure of Atom

inner shell electrons, and the net positive charge experienced by the outer electrons is known as
effective nuclear charge (Zeff e). Despite the shielding of the outer electrons from the nucleus by the
inner shell electrons, the attractive force experienced by the outer shell electrons increases with
increase of nuclear charge. In other words, the energy of interaction between, the nucleus and
electron (that is orbital energy) decreases (that is more negative) with the increase of atomic number
(Z).
Both the attractive and repulsive interactions depend upon the shell and shape of the orbital in which
the electron is present. For example, electrons present in spherical shaped, s orbital shields the outer
electrons from the nucleus more effectively as compared to electrons present in p orbital. Similarly
electrons present in p orbitals shield the outer electrons from the nucleus more than the electrons
present in d orbitals, even though all these orbitals are present in the same shell.
Further within a shell, due to spherical shape of s orbital, the s orbital electron spends more time
close to the nucleus in comparison to p orbital electron which spends more time in the vicinity of
nucleus in comparison to d orbital electron. In other words, for a given shell (principal quantum
number), the Zeff experienced by the electron decreases with increase of azimuthal quantum number
(l), that is, the s orbital electron will be more tightly bound to the nucleus than p orbital electron
which in turn will be better tightly bound than the d orbital electron.
The energy of electrons in s orbital will be lower (more negative) than that of p orbital electron
which will have less energy than that of d orbital electron and so on. Since the extent of shielding
from the nucleus is different for electrons in different orbitals, it leads to the splitting of energy
levels within the same shell (or same principal quantum number), that is, energy of electron in an
orbital, as mentioned earlier, depends upon the values of n and l. Lastly it may be mentioned here
that energies of the orbitals in the same subshell decrease with increase in the atomic number (Zeff).
For example, energy of 2s orbital of hydrogen atom is greater than that of 2s orbital of lithium and
that of lithium is greater than that of sodium and so on, that is,
E2s(H) > E2s(Li) > E2s(Na) > E2s(K).

Energy level diagrams for the few electronic shells of (a) hydrogen atom and (b) multi-electronic atoms.
Chemistry-XI 71

Which Statement are true

(i) orbitals for the same value of principal quantum number, have the same
Example 54

energies even for different azimuthal quantum number for hydrogen atom.
(ii) In case of multi-electron atoms, orbitals with same principal quantum number
possess different energies for different azimuthal quantum numbers.
(i) True (ii) True

RULES FOR FI LLI N G OF ELECTRON S I N VARI OUS ORBI TALS

The atom is built up by filling electrons in various orbitals according to the following rules.
Aufbau Principle
This principle states that the electrons are added one by one to the various orbitals in order of their
increasing energy starting with the orbital of lowest 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,7p……………………
How to remember such a big sequence?
To make it simple we are giving you the method to write the increasing energy order of the orbitals.
Starting from the top, the direction of the arrows gives the order of filling of orbitals.

1s

2s
2p

3s
3p
3d
4s
4p
4d
4f
5s
5p 5d
6s
6p

7s

(n +  ) Rule
Alternatively, the order of increasing energy of the various orbitals can be calculated on the basis of
(n +  ) rule.
The energy of an orbital depends upon the sum of values of the principal quantum number (n) and
the azimuthal quantum number (  ). This is called (n +  ) rule. According to this rule,
“In neutral isolated atom, the lower the value of (n+  ) for an orbital, lower will be its energy.
However, if the two different types of orbitals have the same value of (n +  ), the orbitals with lower
value of n has lower energy’’.
72 Structure of Atom

Illustration of (n +  ) rule

Type of
Value of n Values of  Values of (n +  ) Relative energy
orbitals

1s 1 0 1+0=1 Lowest energy

2s 2 0 2+0=2 Higher energy than 1s

orbital

2p 2 1 2+1=3 2p orbital (n = 2) have

lower energy than 3s
3s 3 0 3+0=3 orbital (n = 3)

Pauli’s Exclusion Principle

According to this principle "no two electrons in an atom will have same value of all the four
quantum numbers".
If one electron in an atom has the quantum numbers n = 1,  = 0, m = 0 and s = +1/2, no other
electron can have the same four quantum numbers. In other words, we cannot place two electrons
with the same value of spin quantum number (s) in a 1s orbital.
The orbital diagram does not represent a possible arrangement of electrons.
1s

Because in this case the four quantum numbers of the two electrons are becoming same.
Therefore, the correct representation should be
Hund’s Rule of Maximum Spin Multiplicity
This rule deals with the filling of electrons in the orbitals having equal energy (degenerate orbitals).
According to this rule,
“Same energy orbital (degenerate orbitals) should be singly occupied first, then and only then spin
pairing will occur.
This is due to the fact that electrons being identical in charge, repel each other when present in the
same orbital. This repulsion can however be minimised if two electrons move as far apart as possible
by occupying different degenerate orbitals. All the unpaired electrons in a degenerate set of orbitals
will have same spin.
As we now know the Hund’s rule, let us see how the three electrons are arranged in p orbitals.
The important point to be remembered is that all the singly occupied orbitals should have electrons
with parallel spins, i.e., in the same direction either-clockwise or anticlockwise.
2px 2py 2pz 2px 2py 2pz
or
Chemistry-XI 73

ELECTRON I C CON FI GURATI ON OF ELEM EN TS

Electronic configuration is the distribution of electrons into different shells, subshells and orbitals of
an atom.
Keeping in view the above mentioned rules, electronic configuration of any orbital can be simply
represented by the notation.
Number of electrons in the
subshell
nx
Principal quantum number Symbol of subshell or
orbitals (s,p,d,f)

Alternatively
To write the electronic configuration, we need to know (i) the atomic number (ii) the order in which
orbitals are to be filled (iii) maximum number of electrons that can be occupied in a shell, sub–shell
or orbital.
(a) Each orbital can accommodate two electrons.
(b) The number of electrons to be accommodated in a subshell is 2  number of degenerate
orbitals.

Subshell Maximum number of electrons

s 2

p 6

d 10

f 14
(c) The maximum number of electrons in each shell (K,L,M,N…) is given by 2n 2 where n is the
principal quantum number.

SOM E UN EXPECTED ELECTRON I C CON FI GURATI ON S

The rule that you have learned for predicting electronic configurations work for most of the cases but
not always. Some exceptions to the rules are reported. Fortunately, most of these exceptions are of
little consequence to us because the elements involved are relatively rare and their chemistry will not
be important to us in this course. Some of the exceptions are important though, because they occur
with common elements, notably chromium and copper.
Cu has 29 electrons. Its excepted electronic configuration is 1s22s22p63s23p64s23d9 but in reality, the
configuration is 1s22s22p63s23p64s13d10 as this configuration is more stable. Similarly, Cr has the
configuration of 1s22s22p63s23p64s13d5 instead of 1s22s22p63s23p64s23d4.
74 Structure of Atom

FACTORS RESPONSI BLE FOR TH E EXTRA STABI LI TY OF H ALFFI LLED

AN D COM PLETELY FI LLED SUBSH ELLS
(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 subshell are either completely filled or are exactly half
filled are more stable because of symmetrical distribution of electrons.
(ii) Exchange energy
The electrons with 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 is maximum when the degenerate orbital (orbitals of same
subshell having equal energy) are exactly halffilled or completely filled. As a result, the
exchange energy is maximum and so is the stability.

Ground state electronic configuration of nitrogen atom can be represented by

Example 55

(a) (b)
(c) (d)
Only the configuration (a) and (d) follow Hund's rule.

Consider the ground state of Cr atom (Z = 24). The numbers of electrons with the
azimuthal quantum numbers, l = 1 and 2 are, respectively:
(a) 12 and 4 (b) 12 and 5
Example 56

(c) 16 and 4 (d) 16 and 5

Electronic configuration of chromium in ground state is 1s22s22p63s23p64s13d5.
Azimuthal quantum number, l = 1 stands for psubshell while l = 2 refers to dsubshell.
Therefore, the number of electrons with l = 1 is 6 + 6 i.e. 12.
The number of electrons with l = 2 is 5
 (b)
Which of the following statements in relation to the hydrogen atom is correct?
(a) 3s orbital is lower in energy than 3p orbital
(b) 3p orbital is lower in energy than 3d orbital
Example 57

(c) 3s and 3p orbitals are of lower energy than 3d orbital

(d) 3s, 3p and 3d orbitals all have the same energy
For hydrogen the energy order of orbital is
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
 (d)
Chemistry-XI 75

What atoms are indicated by the following electronic configuration?

(i) 1s 2 2s 2 2 p1 (ii) [ Ar ]4 s 2 3d 1
Example 58

(i) Total number of electrons in 1s 2 2s 2 2 p1  2  2  1  5  Atomic number of the element =

5
Hence, the element is Boron (B)
(ii) total number of electrons in [Ar] 4s 2 3d 1  18  2  1  21  Atomic number of the
element = 21
Hence the element is Scandium (Sc).
Discuss the possibility of the atom for existing in the following electronic configuration:
(i) 1s 2 2s 2 2 p1x (ii) 1s 2 2s1 2 p1x 2 p1y 2 p1z
(iii) 1s 2 2s1 2 px2 2 p1y (iv) 1s 2 2s 2 3s 2
(i) This electronic configuration is correct since it is in accordance with the rules for
Example 59

filling up of various orbitals.

(ii) This electronic configuration is wrong because it violates aufbau principle which states
that an orbital with lower energy, i.e., 2s in the present case should be completely filled
before the electrons go to higher energy subshell, i.e., 2p in the present case.
(iii) This electronic configuration is not correct since it violates Hund’s rule. According to
this rule, all the three 2p orbitals must have one electron each before the pairing
occurs. But in the present case 2px orbital has two electrons while 2pz orbitals is empty.
(iv) This electronic configuration is wrong since after filling 2s-orbital, the electrons should
go to 2p – orbital rather than 3s-orbital.
Give the value of four quantum numbers of the last electron of sodium. (At. No. = 11)
11 Na  1s , 2 s , 2 p , 3s
2 2 6 1

Last e   3s1
Example 60

n3 ( e  is in 3rd shell)

l 0 ( e  is in s sub-shell)
m0 ( l  0 )
1
s  
2
What information regarding quantum numbers is given by 3d7?
Example 61

3d7 tells that d-sub-shell of the atom contains 7e  for which n  3 and l  2

3
3 unpaired electrons. Total spin of unpaired electrons =
2
What will be the value of ml for ninth electron of d-orbital if l  2 ?
Example 62

ml  2  1 0  1  2

d9 =
m = +1 for 9th electron
 76 Structure of Atom

Example 63 What are the atomic numbers of elements whose outermost electrons are represented by
(a) 3s1 (b) 2p3 and (c) 3 d6 ?
(a) 1s2 2s2 2p6 3s1 ( Z = 11)
(b) 1s2 2s2 2p3 (Z = 7)
(c) 1s2 2s2 2p6 3s2 3p6 (Z = 26)

Give the number of electrons in the species H 2 , H 2 and O2 .

Example 64

H 2  1 H  1 H = 2 electrons

 H2 has = 2 – 1 = 1 electron

O2 = 8O + 8O = 16 electron

 O2 has = 16 – 1 = 15 electron

The quantum numbers of six electrons are given below. Arrange them in order of
increasing energies. List of any of these combination (s) has/have the same energy:
Example 65

(i) n = 4, l = 2, ml = –2, ms = 1/2 (ii) n = 3, l = 2, ml = 1, ms = +1/2

(iii) n = 4, l = 1, ml = 0, ms = +1/2 (iv) n = 3, l = 2, ml = –2, ms = – 1/2
(v) n = 3, l = 1, ml = –1, ms = +1/2 (vi) n = 4, l =1, ml = 0, ms = +1/2
The orbitals occupied by the electrons are (i) 4d (ii) 3d (iii) 4p (iv) 3d (v) 3p (vi) 4p
Their energies will be in the order : (v) < (ii) = (iv) < (vi) = (iii) < (i)
The bromine atoms possess 35 electrons. It contains 6 electrons in 2p orbitals, 6 electrons
Example 66

in 3p orbitals and 5 electrons in 4p orbitals. Which of these electrons experiences the

lowest effective nuclear charge?
4p electrons being farthest from the nucleus, experience the lowest effective nuclear charge.

Among the following pairs of orbitals which orbital will experience the larger effective
nuclear charge?
Example 67

(a) 2s and 3s, (b) 4d and 4f, (c) 3d and 3p

(a) 2s is closer to the nucleus than 3s. Hence, 2s will experience larger effective nuclear
charge.
(b) 4d
(c) 3p (for same reasons)
Example 68

The unpaired electrons in Al and Si are present in 3p orbital. Which electron will
experience more effective charge from the nucleus?
Silicon has greater nuclear charge (+14) than aluminium (+13). Hence, the unpaired 3p electron
in case of silicon will experience more effective nuclear charge.

Indicate the number of unpaired electron in (a) P (b) Si (c) Cr (d) Fe, and (e) Kr
a) P = 1s2 2s2 2p6 3s2 3px1 3py1 3 pz1, No. of unpaired electron = 3
Example 69

15

(b) 14
Si = 1s 2s 2p 3s 3px 3py 3 py ,
2 2 6 2 1 1 1
No. of unpaired electron = 2
(c) 24
Cr = 1s2 2s2 2p6 3s2 3p6 3d5 4 s1, No. of unpaired electron = 6
(d) 26
Fe = 1s 2s 2p 3s 3p 3d 4 s ,
2 2 6 2 6 5 2
No. of unpaired electron = 4 (in 3d)
(e) 36
Kr = Noble gas. All orbitals are filled. Unpaired electrons = 0
Chemistry-XI 77

Try Yourself-10
1. Why can the 2p subshell of an atom hold more electrons than a 2s subshell?
2. Electronic Configuration of Fe3+ is more stable than Fe2+. Why?
3. What is the maximum number of electrons in an atom that can have n  l  4 .
4. Find the number of radial nodes and angular nodes in the following orbitals: 6f, 3p, 4d
5. (a) How many sub-shells are associated with n = 4?
(b) How many electrons will be present in the sub-shells having ms value of –1/2 for n = 4?
6. A neutral atom of element has 2K, 8L and 5M electrons. Find out the following: (a) Atomic
no. of the element (b) Total No. of s electrons (c) Total No. of p-electrons (d) No. of protons
in the nucleus and (e) Valency of the element.
7. Give the values of other quantum numbers of n = 3. Prove that the maximum number of electrons in
M-shell is 18
8. Write electronic configuration of the following ions:
(i) Mg 2  and O 2 (Mg = 12, O = 8)

(ii) Ca 2 and Cl  (Ca = 20, Cl = 17)

(iii) Al 3 and Cl  (Al = 13, Cl = 17)
(iv) Ti 2 (Ti = 22)
78 Structure of Atom

W ORKSH EET
BOHR’S MODEL

1. Calculate the wavelength of radiation emitted, producing a line in Lyman series, when an
electron falls from fourth stationary state in hydrogen atom. [9.7 × 10–8 m]
2. Calculate energy of electron which is moving in the orbit that has its radius. sixteen times the
radius of first Bohr orbit for H–atom. [–1.36×10–19Joules]
3. The wavelength of a certain line in the Paschen series in 1093.6 nm. What is the value of high
for this line. [RH = 1.0973 × 107 m1] [6]
4. Wavelength of the Balmer line is 6565 Å. Calculate the wavelength of H , line of same
hydrogen like atom. [4863Å]
5. Calculate the Rydberg constant R if He+ ions are known to have the wavelength difference
between the first (of the longest wavelength) lines of Balmer and Lyman series equal to
133.7nm. [1.096 × 107 m–1]
6. What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition, n=4 to n=2 of He+ spectrum. [n1=1,n2 = 2]
7. Calculate the total energy emitted when electrons of 1.0 g atom of hydrogen undergo
transition giving the spectral line of lowest energy in the visible region of its atomic
spectrum. [1.827×105 J/mol]
8. A photon having  = 854 Å causes the ionization of a nitrogen atom. Give the I.E. per mole
of nitrogen in kJ. [1403 KJ/mol]
9. H- atom is exposed to electromagnetic radiation of 1028 Å and gives out induced radiations
(radiations emitted when e– returns to ground state). Calculate  of induced radiations.
[6563 Å ; 1216 Å ; 1026 Å]
21.7  1012
10. The electron energy in hydrogen atom is given by En  n2
ergs. Calculate the energy

required to remove an e completely from n = 2 orbit. What is the largest wavelength in cm of

light that can be used to cause this transition. [5.425×10–12ergs,3.7×10–5cm]
11. Calculate the wavelength in angstrom of photon that is emitted when an e in Bohr orbit n=2
returns to the orbit n=1. The ionization potential of the ground state of hydrogen atom is
2.17×1011 erg/atom. [1220 Å]
12. The radius of an orbit of hydrogen atom is 0.85 nm. Calculate the velocity of electron in this
orbit. [5.44 × 105 m/s]
13. The velocity of e in a certain Bohr orbit of the hydrogen atom bears the ratio 1:275 to the
velocity of light. What is the quantum no. "n" of the orbit and the wave no. of the radiation
emitted for the transition from the quantum state (n+1) to the ground state?[2;9.75×104cm–1]
14. A doubly ionised lithium atom is hydrogen like with atomic number z = 3. Find the
wavelength of the radiation required to excite the electron in Li2+ from the first to the third
Bohr orbit. [113.74 Å]
15. Estimate the difference in energy between I and II Bohr Orbit for a hydrogen atom. At what
minimum atomic number a transition from n=2 to n=1 energy level would result in the
emission of Xrays with = 3.0 × 108 m? Which hydrogen like species does this atomic
number correspond to. [10.2 eV, z = 2]
Chemistry-XI 79

16. Calculate the wave no. for the shortest wavelength transition in the Balmer series of atomic
hydrogen. [27419.25 cm –1]
17. 1.8 g hydrogen 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 2nd energy level and the rest in ground
state. If I.P. of H is 21.7 × 1012 erg. Calculate 
(i) No. of atoms present in III & II energy level.
(ii) Total energy evolved when all the atoms return to ground state.
[292.68×1021 atoms, 162.60×1021 atoms, 832.50 KJ]
18. The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e– in the given
orbit. [h/]
19. The vapours of Hg absorb some electrons accelerated by a potential diff. of 4.5 volt as a
result of which light is emitted. If the full energy of single incident e is supposed to be
converted into light emitted by single Hg atom, find the wave no. of the light.[3.63×106m–1]
20. If the average life time of an excited state of H atom is of order 10–8 sec, estimate how many
orbits an e– makes when it is in the state n = 2 and before it suffers a transition to n =1 state.
[8×106]
21. Calculate the frequency of e– in the first Bohr orbit in a H-atom. [6530×1012Hz]
22. A single electron orbits around a stationary nucleus of charge +Ze where Z is atomic number
and ‘e’ is the magnitude of the electric charge. The hydrogen like species required 47.2 eV to
excite the electron from the second Bohr orbit to the third Bohr orbit. Find
(i) the value of Z and give the hydrogen like species formed.
(ii) the kinetic energy and potential energy of the electron in the first Bohr orbit.
[340 ev , – 680 eV]
23. A stationary He+ ion emitted a photon corresponding to a first line of the Lyman series. The
photon liberated a photoelectron from a stationary H atom in ground state. What is the
velocity of photoelectron. [3.09 × 108 cm/sec]
24. To what series does the spectral lines of atomic hydrogen belong if its wave number is equal
to the difference between the wave numbers of the following two lines of the Balmer series
486.1 and 410.2 nm. What is the wavelength of this. [Brackett;2.63×10–4cm]
25. In a hypothetical H-atom the mass of electron & it charge is double of what we consider then
calculate the total energy of electron in the Ist orbit of such a hypothetical H-atom?
[Assuming all other concepts and parameter to be same as we considered in Bohr's
model.] [– 13.6 × 32 eV]

PHOTOELECTRIC EFFECT
26. Calculate the threshold frequency of metal if the binding energy is 180.69 KJ mol1 of
electron. [4.5 ×1014 s–1]
27. Calculate the binding energy per mole when threshold wavelength of photon is 240 nm.
[497 KJ/mol]
80 Structure of Atom

28. A metal was irradiated by light of frequency 3.2 × 1015 S1. The photoelectron produced had
its KE, 2 times the KE of the photoelectron which was produced when the same metal was
irradiated with a light of frequency 2.0 ×1015 S1. What is work function. [319.2 KJ/mol]
29. U.V. light of wavelength 800 Å & 700 Å falls on hydrogen atoms in their ground state &
liberates electrons with kinetic energy 1.8 eV and 4 eV respectively. Calculate Planck’s
constant. [6.57 ×10–34 Js]
30. A potential difference of 20 KV is applied across an X-ray tube. Find the minimum
wavelength of X-ray generated. [0.62Å]
31. The K.E. of an electron emitted from tungsten surface is 3.06 eV. What voltage would be
required to bring the electron to rest. [3.06 V]
32. The eyes of certain member of the reptile family pass a single visual signal to the brain
when the visual receptors are struck by photons of wavelength 850 nm . If a total energy of
3.15  1014 J is required to trip the signal, what is the minimum number of photons that must
strike the receptor. [1.35×105]
33. Find the number of photons of radiation of frequency 5 × 1013 s–1 that must be absorbed in
order to melt one gm ice when the latent heat of fusion of ice is 330 J/g. [1022]
34. Suppose 1017 J of light energy is needed by the interior of the human eye to see an object.
How many photons of green light ( = 550 nm) are needed to generate this minimum amount
of energy. [28 photons]
GENERAL
35. What is de-Broglie wavelength of a He-atom in a container at 300 K.(Use Uavg) [0.79 Å]
36. Through what potential difference must an electron pass to have a wavelength of 500 Å.
[6.03×10–4volt]
37. A proton is accelerated to one- tenth of the velocity of light. If its velocity can be measured
with a precision + 1%. What must be its uncertainty in position? [1.05×10–13m]
38. To what effective potential a proton beam be subjected to give its protons a wavelength of
1 ×1010 m. [0.0826 volts]
–
39. Calculate magnitude of orbital angular momentum of an e that occupies 1s, 2s , 2p , 3d , 3p.
h h h
[0 ; 0 ; 2 ; 6 ; 2 ]
2 2 2
40. He atom can be excited to 1s1 2p1 by  = 58.44 nm. If lowest excited state for He lies
4857cm–1 below the above. Calculate the energy for the lower excitation state. [3.3×10–18J]
41. A certain dye absorbs 4530 Å and fluoresces at 5080 Å these being wavelengths of maximum
absorption that under given conditions 47% of the absorbed energy is emitted. Calculate the
ratio of the no. of quanta emitted to the number absorbed. [0.527]
42. The reaction between H2 and Br2 to form HBr in presence of light is initiated by the photo
decomposition of Br2 into free Br 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. [6235 Å]
43. The quantum yield for decomposition of HI is 0.2. In an experiment 0.01 moles of HI are
decomposed. Find the number of photons absorbed. [3×1022]
44. Calculate the wavelength of the radiation that would cause photo dissociation of chlorine
molecule if the Cl- Cl bond energy is 243 kJ/mol. [4.9 × 10–7m]
Chemistry-XI 81

45. The dissociation energy of H2 is 430.53 kJ/mol. If H2 is exposed to radiant energy of

wavelength 253.7 nm, what % of radiant energy will be converted into K.E. [8.68 %]
46. X-rays emitted from a copper target and a molybdenum target are found to contain a line of
wavelength 22.85 nm attributed to the K line of an impurity element. The K lines of
copper (Z = 29) and molybdenum (Z = 42) have wavelength 15.42 nm and 7.12 nm
respectively. Using Moseley’s law, 1/2 = a (Z – b) calculate the atomic number of the
impurity element. [24]
47. What is de Broglie wavelength associated with an e– accelerated through potential difference
= 100 KV. [3.88 pm]
48. Calculate the de-Broglie wavelength associated with motion of earth (mass 6 × 1024 Kg)
orbiting around the sun at a speed of 3 × 106 m/s. [3.68 × 10–65 m]
49. A baseball of mass 200 g is moving with velocity 30 × 102 cm/s. If we can locate the baseball
with an error equal in magnitude to the  of the light used (5000 Å), how will the uncertainty
in momentum be compared with the total momentum of baseball. [1.75 × 10–29]
50. An electron has a speed of 40 m/s, accurate up to 99.99%. What is the uncertainty in locating
its position. [0.0144 m]
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82 Structure of Atom

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