Chemistry - Atomic Structure - Gaseous State - Complete Module

XI MODULE - III
ATOMIC STRUCTURE
&
GASEOUS STATE
Modus Operandi for Practice
(Suggested Ideal Approach)
Step – I CatalyseR 's Practice Sheets & NCERT

{while Chapter is running in Class-Room}
(Mandatory)
Step – II
CatalyseR 's Module
(Mandatory)
Step – III Previous Years’ JEE Subjective & Objective Questions,

R C Mukherjee solved and unsolved questions
(Mandatory)
Step – IV After Completion of Step – III, if time permits, students can

solve questions from previous year’s INCHO, NCHO, KVPY
(Optional) papers, Physical chemistry books by Atkins, Bruce H. Mahan
This Study Package is Prepared by

d`fr
o f Ca talyseR
t Wing
Conten
ATOMIC STRUCTURE
INDEX
 CONCEPTS IN BRIEF (ATOMIC STRUCTURE) 01 – 15

 SOLVED EXAMPLES 16 – 20
 EXERCISE # 01 OBJECTIVE EXERCISE # 01 21 – 25
 EXERCISE # 02 ADVANCED EXERCISE 26 – 37
 EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01) 38 – 40
 EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS 44 – 46
 EXERCISE # 06 JEE (MAIN) CORNER 47 – 48
 EXERCISE # 07 JEE (ADVANCED) CORNER 49 – 50
 ANSWER KEYS 51 – 54
WEIGHTAGE OF ‘ATOMIC STRUCTURE’ IN JEE (MAIN & ADVANCED) in Last Three Years
JEE (MAIN) Formely known as AIEEE
MARK /
YEAR No. Of Qs.
CHEMISTRY TOTAL MARKS
2015 1 4/120
2016 1 4/120
2017 1 4/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2015 1 4/168
2016 0 0/124
2017 3 9/122
ATOMIC STRUCTURE
IIT–JEE Syllabus
Atomic structure; Rutherford Model; Spectrum of hydrogen atom; Bohr model;
de Broglie relations, Uncertainty principle, Quantum model; Electronic configuration of
elements (upto atomic number 36) ; Aufbau principle, Pauli’s exclusion principle and
Hund’s rule, shapes of s, p, and d orbitals.
INTRODUCTION
Structure of Atom

Rutherford's Model Bohr's Model Wave mechanical model
Dalton’s concept of the indivisibility of the atom was completely discredited by a series of
experimental evidences obtained by scientists. A number of new phenomena were brought to
light and man’s idea about the natural world underwent a revolutionary change. the discovery of
electricity and spectral phenomena opened the door for radical changes in approaches to
experimentation. It was concluded that atoms are made of three particles : electrons, protons and
neutrons. These particles are called the fundamental particles of matter.
PROPERTIES OF CATHODE RAYS :

 They emanate normally from the surface of the cathode and travel in straight lines at a
high velocity.

 They are a beam of minute material particles.
 They consist of negatively charged particles.
 Like light rays, the cathode rays can affect a photographic plate.
 The nature of the cathdoe rays does not depend upon the nature of the gas in the
discharge tube and the nature of the cathode material.
 For each negatively charged particle of the cathode rays, the ratio of charge (e) to mass
(m) is constant.
Don’t ever get comfortable when you have the ability to achieve more.
2 ATOMIC STRUCTURE
PRODUCTION OF ANODE RAYS (DISCOVERY OF PROTONS) :
Goldstein (1886) repeated the experiment with a discharge tube filled with a perforated cathode
and found that new type of rays came out through the hole in the cathode.
When this experiment is conducted, a faint red glow is observed on the wall behind the cathode.
Since these rays originate from the anode, they are called anode rays.
PROPERTIES OF ANODE RAYS :
 Anode rays travel along straight paths and hence they cast shadows of object placed
in their path.
 They rotate a light paddle wheel placed in their path. This shows that anode rays are
made up of material particles.
 They are deflected towards the negative plate of an electric field. This shows that these
rays are positively charged.
 For different gases used in the discharge tube, the charge to mass ratio (e/m) of the
positive particles constituting the positive rays is different.
DISCOVERY OF NEUTRON :
Later, a need was felt for the presence of electrically neutral particles as one of the constituent of
atom. These particles were discovered by chadwick in 1932 by bombarding a thin sheet of
beryllium with -particles, when electrically neutral particles having a mass slightly greater than
that of the protons were emitted. He named these particles as neutrons.
9
4 Be  42 He 
 12 1
6 C  0n
ATOMIC MODELS
Thomson’s Model of the Atom :

An atom is electrically neutral. It contains positive charges (due
to the presence of protons ) as well as negative charges (due
to the presence of electrons). Hence, J J Thomson assumed
that an atom is a uniform sphere of positive charges with
electrons embedded in it.
CatalyseR Eduventures (India) Pvt. Ltd.

ATOMIC STRUCTURE 3
Rutherford’s Experiment :
 Most of the -particles passed straight through the gold foil without suffering any
deflection from their original path.
 A few of them were deflected through small angles, while a very few were deflected to a
large extent.
 A very small percentage (1 in 100000) was deflected through angles ranging from 90° to
180°.
Rutherford’s nuclear concept of the atom.
 The atom of an element consists of a small positively charged ‘nucleus’ which is situated
at the centre of the atom and which carries almost the entire mass of the atom.
 The electrons are distributed in the empty space of the atom around the nucleus in
different concentric circular paths, called orbits.
 The number of electrons in orbits is equal to the number of positive charges (protons) in
the nucleus. Hence, the atom is electrically neutral.
 The volume of the nucleus is negligibly small as compared to the volume of the atom.
 Most of the space in the atom is empty.
DRAWBACKS OF RUTHERFORD MODEL :

1. This was not according to the classical theory of electromagnetism proposed by maxwell.
According to this theory, every accelerated charged particle must emit radiations in the form
of electromagnetic waves and loses its total energy.
since energy of electrons keep on decreasing, so radius of the circular orbits should also
decrease and ultimately the electron should fall in nucleus.
2. It could not explain the line spectrum of H-atom.
4 ATOMIC STRUCTURE
THE NUCLEUS
Electrons, protons & neutrons are the fundamental particles present in all atoms, (Except
hydrogen)
Particles Symbol Mass Charge Discoverer
Electron 0 9.1096 x 10-31 kg – 1.602 x l0–19

–1e or  J.J. Thompson
Coulombs Stoney Lorentz 1887
0.000548 amu – 4.803 × 10–10 esu
Proton 1 1.6726 x 10–27 kg + 1.602 x 10–19

1H Goldstein
Coulombs Rutherford1907
1.00757 amu + 4.803 x 10–10 esu
Neutron 1 1.6749 x 10–27 kg

0n neutral James Chadwick
1.00893 amu 0 1932
1 amu  1.66 × 10–27 kg
 Atomic number of an element

= Total number of protons present in the nucleus
= Total number of electrons present in the atom
 Atomic number is also known as proton number because the charge on the nucleus
depends upon the number of protons.
 Since the electrons have negligible mass, the entire mass of the atom is mainly due to
protons and neutrons only. Since these particles are present in the nucleus, therefore
they are collectively called nucleons.
 As each of these particles has one unit mass on the atomic mass scale, therefore the
sum of the number of protons and neutrons will be nearly equal to the mass of the atom.
 Mass number of an element = No. of protons + No. of neutrons.

 The mass number of an element is nearly equal to the atomic mass of that element.
However, the main difference between the two is that mass number is always a whole
number whereas atomic mass is usually not a whole number.
 The atomic number (Z) and mass number (A) of an element ‘X’ are usually represented
alongwith the symbol of the element as
23 35
e.g. 11 Na, 17 Cl and so no.

ATOMIC STRUCTURE 5
1. sotopes : Such atoms of the same element having same atomic number but different
mass numbers are called isotopes.
1
1 H, 12H and 3
1 H and named as protium, deuterium (D) and tritium (T) respectively.
Ordinary hydrogen is protium.
2. Isobars : Such atoms of different elements which have same mass numbers (and of
course different atomic numbers) are called isobars
40 40 40
e.g. 18 Ar, 19 K, 20 Ca.
3. Isotones : Such atoms of different elements which contain the same numer of neutrons
are called isotones
14
e.g. 6 C, 15 16
7 K, 8 O.
4. Isoelectronics : The species (atoms or ions) containing the same number of electrons
are called isoelectronic.
For example, O2–, F–, Na+, Mg2+, Al3+, Ne all contain 10 electrons each and hence they
are isoelectronic.
SOME IMPORTANT CHARACTERISTICS OF A WAVE
 Wavelength of a wave is defined as the distance between any two consecutive crests or
troughs. It is represented by  (lambda) and is expressed in Å or m or cm or nm
(nanometer) or pm (picometer).
1 Å = 10– 8 cm = 10–10 m
1 nm = 10– 9 m, 1 pm = 10–12 m
 Frequency of a wave is defined as the number of waves passing through a point in one
second. It is represented by  (nu) and is expressed in Hertz (Hz) or cycles/sec or simply
sec–1 or s–1.
1 Hz = 1 cycle/sec
 Velocity of a wave is defined as the linear distance travelled by the wave in one second.
It is represented by v and is expressed in cm/sec or m/sec (ms–1).
6 ATOMIC STRUCTURE
 Amplitude of a wave is the height of the crest or the depth of the trough. It is represented
by ‘a’ and is expressed in the units of length.
 Wave number is defined as the number of waves present in 1 cm length. Evidently, it will
be equal to the reciprocal of the wavelength. It is represented by  (read as nu bar).
1


If  is expressed in cm,  will have the units cm–1.
Relationship between velocity, wavelength and frequency of a wave. As frequency is the
number of waves passing through a point per second and  is the length of each wave,
hence their product will give the velocity of the wave. Thus
v=×
Cosmic rays <  – rays < X-rays < Ultraviolet rays < Visible < Infrared < Micro waves <
Radio waves.
QUANTUM THEORY OF LIGHT

The light energy from any source is always an integral multiple of a smallers energy value called
quantum of light.
Quantum of light is called as photon.
Energy of one photon = h
h = plank’s constant = 6.625 × 10–34 Js
   = frequency of light
c hc
=  – wavelength E=
 
PHOTOELECTRIC EFFECT :
When certain metals (for example Potassium, Rubidium, Caesium etc.) were exposed to a beam
of light electrons were ejected as shown in Fig.
The phenomenon is called Photoelectric effect.
(i) The number of electrons ejected is proportional to the intensity or brightness of light.

ATOMIC STRUCTURE 7
(ii) For each metal, there is a characteristic minimum frequency, 0 (also known as threshold
frequency) below which photoelectric effect is not observed. At a frequency  > 0, the ejected
electrons come out with certain kinetic energy.
1
h = h0 + me2
2
where me is the mass of the electron and v is the velocity associated with the ejected electron.
SOME IMPORTANT FORMULA

1. A = Z + N (Number of neutrons)
2. dynamic mass of particle m = m0 / [1 – (v/c)2]1/2
3. Radius of nucleus R = R0 (A)1/3, R0 = 1.2 x 10–15 m
4. c = 
5. wave number  = l / 
6. E = h  = hc /  = hc 
q1 q2 1
7. F=K ;K= = 9.0 × 109 Nm2/C2
r2 40
8. E = h = E2 – E1
1 Z.2e
9. m v 2  K ; r = distance of closest approach,
2 r
v = initial v elocity of a   particle
1
10. ET  E0  KE; h   h 0  m v 2
2
BOHR’S ATOMIC MODEL
It is based on quantum theory of light.
Assumptions of Bohr’s model :
 There are certain orbits around the nucleus such that if electron will be revolving in these
orbit, then it need not emit any electromagenetic radiation. These are called stationary
orbit. The neccessary centripetal force is produced by attraction forces of nucleus.
mv 2 Ke2 Z
=
r r2
 Angular momentum of the electron in these stationary orbit is always an integral multiple
h nh
of mvr =
2 2
 Electron can make jump from one stationary orbit to another stationary orbit by absorbing
or emitting a photon of energy equal to difference in the energies of the stationary orbit.
hc
= E E – difference in the energy of orbit

8 ATOMIC STRUCTURE
BOHR’S MODEL FOR HYDROGEN LIKE ATOMS

h
1. mvr = n
2
2 2
E1 2 –18 Z J/atom = -13.6 Z eV 22 me4K 2
2. En = Z = -2.178 × 10 ; E1 =
n2 n2 n2 h2
n2 h2 0.529  n2
3. rn = × = Å
Z 42 e2mK Z
2 Ze2K 2.18  106  Z

4. v= = m/s
nh n
0.657  Z 2  1016
5. revolutions per sec = v / 2r =
n3
1.52  1016  n3
6. Time for one revolution = 2r / v =
Z2
7. En = K.E + P.E (P.E. = – 2KE)
1 Ze2
8. K.E = 1/2 mv2, P.E = –
40 r
9. Ionisation energy = En  – Eelectron = – Eelectron
ENERGY LEVEL DIAGRAM :
(i) Orbit of lowest energy is placed at the bottom, and all other orbits are placed above this.
(ii) The gap between two orbits is proportional to the energy difference of the orbits.
0 eV n= 
-0.85 eV n=4
-1.51eV n=3
-3.4eV n=2
12.1eV
10.2eV
-13.6eV n=1
Energy level diagram of H-atom
DEFINITION VALID FOR SINGLE ELECTRON SYSTEM
 Ground State :
lowest energy state of any atom or ion is called ground state of the atom.
Ground state energy of H–atom = – 13.6 ev
Ground state energy of He+ on = – 54.4 ev
 Excited State :
States of atom other than the ground state are called excited states :
n=2 first excited state
n=3 second excited state
n=4 third excited state
n=n+1 nth excited state

ATOMIC STRUCTURE 9
 Ionisation energy (E) :

Minimum energy required to move an electron from ground state to
n =  is called ionisation energy of the atom or ion.
 onisation energy of H–atom = 13.6 ev
 onisation energy of He+ ion = 54.4 ev
 onisation energy of Li+2 ion = 122.4 ev
 Ionisation Potential (.P.) :

Potential difference through which a free electron must be accelerated from rest, such
that its kinetic energy becomes equal to ionisation energy of the atom is called ionisation
potential of the atom.
  .P. of H atom = 13.6 v
  .P. of He+ on= 54.4 v

  Excitation Energy :
Energy required to move an electron from ground state of the atom to any other state of
the atom is called excitation energy of that state.
excitation energy of 2nd state = excitation energy of 1st excited state = 1st excitation
energy = 10.2 ev.

  Excitation Potential :
Potential difference through which an electron must be accelerated from rest to so that its
kinetic energy become equal to excitation energy of any state is called excitation potential
of that state.
excitation potential of third state = excitation potential of second excited state = second
excitation potential = 12.09 v.
  Binding Energy ‘or’ Seperation Energy :

Energy required to move an electron from any state to n =  is called binding energy of
that state.
Binding energy of ground state = .E. of atom or on.
HYDROGEN SPECTRUM
Study of Emission and Absorption Spectra :
An instrument used to separate the radiation of different wavelengths (or frequencies) is

called spectroscope or a spectrograph. Photograph (or the pattern) of the emergent
radiation recorded on the film is called a spectrogram or simply a spectrum of the given
radiation The branch or science dealing with the study of spectra is called spectroscopy.
10 ATOMIC STRUCTURE
Emission spectra :
When the radiation emitted from some source e.g. from the sun or 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’.
Depending upon the source of radiation, the emission spectra are mainly of two type :
  Continuous spectra :
When white light from any source such as
sun, a bulb or any hot glowing body is
analysed by passing through a prism it is
observed that it splits up into seven different
wide band of colours from violet to red. These
colours are so continuous that each of them merges into the next. Hence the spectrum is
called continuous spectrum.
  Line spectra :
When some volatile salt

(e.g., sodium chloride) is
placed in the Bunsen
flame or an electric
discharge is passed
through a gas at low pressure light emitted depends upon the nature of substance.
It is found that no continuous spectrum is obtained but some isolated coloured lines are
obtained on the photographic plate separated from each other by dark spaces. This
spectrum is called ‘Line emission spectrum’ or simply Line spectrum.
  Absorption spectra :
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 spectrum. These dark lines are
supposed to result from the fact that when
white light (contanining radiations of many wavelengths) is passed throught the chemical
substance, radiations. of certain wavelengths are absorbed, depending upon the nature
of the element.

ATOMIC STRUCTURE 11
EMISSION SPECTRUM OF HYDROGEN

When hydrogen gas at low pressure is taken in the
discharge tube and the light emitted on passing electric
discharge is examined with a spectroscope, the spectrum
obtained is called the emission spectrum of hydrogen.
SPECTRA LINES OF HYDROGEN ATOM
Series n1 n2 > n1 Region of Spectrum
Lyman 1 2,3,..... Ultraviolet

Balmer 2 3,4,..... Visible
Paschen 3 4,5...... Infrared
Brackett 4 5,6,..... Infrared
Pfund 5 6,7,..... Infrared
n(n  1)
 = Max. no of spectral lines when an electron returns to ground state from nth
2
orbit.
1 1 1


=   RH  2  2   Z 2
 n1 n2 
R H  109678 cm 1  1.1 107 m 1 
 For First line of a series n2  n1  1

 Limiting spectral line (series limit) means n2  
 H line means n2  n1  1; also known as line of longest  , shortest  , least E
 Similarly H  line means n2  n1  2
12 ATOMIC STRUCTURE
DE-BROGILE RELATIONS
h h
    
mc p
De–Broglie pointed out that the same equation might be applied to material particle by using m for the mass
of the particle instead of the mass of photon and replacing c, the velocity of the photon, by v, the velocity of
the particle.
h h
  
mv 2m  KE 
,
 From the de–Broglie equation it follows that wavelength of a particle decrease

with increase in velocity of the particle. Moreover, lighter particles would have
longer wavelengths than heavier particles, provided the velocity is equal.
 If a charged particle Q is accelerated through potential difference V from rest

then de–broglie wavelength is
h

2mQV
 de–Broglie concept is more significant for microscopic or sub–micrscopic

particles whose wavelength can be measured.
 The circumference of the nth orbit is equal to n times the wavelength of the
electron.
2 rn  n .
 Wavelength of electron is always calculated using De–broglie calculation.
HEISENBERG’S UNCERTAINTY PRINCIPLE
It is impossible to measure simultaneously both the position and velocity (or momentum) of a
microscopic particle with absolute accuracy or certainty.
h h h
x.p > or m x.v  or x.v 
4 4 4m
where, x = uncertainty in position p = uncertaintly in momentum
h = Planck’s constant m = mass of the particle
v = uncertaily in velocity
 In terms of uncertainty in energy E, and uncertainty in time t, this principle is written as,
h
E.t  .
4
 Heisenberg replaced the concept of definite orbits by the concept of probability.

ATOMIC STRUCTURE 13
QUANTUM NUMBERS
The set of four integers required to define an electron completely in an atom are called quantum
numbers. The first three have been derived from Schrodinger wave equation.
(i) Principal Quantum Number (n) :
It describes the size of the electron wave and the total energy of the electron. It has
integral values 1, 2, 3, 4 ...., etc., and is denoted by K, L, M, N. ..., etc.
The maximum number of electrons which can be present in a principal energy
shell is equal to 2n2. No energy shell in the atoms of known elements possesses more
than 32 electrons.
(ii) Azimuthal Quantum Number () :
It describes the shape of electron cloud and the number of subshells in a shell. It can
have values from 0 to (n – 1), i.e.,  = 0 (s-subshell),  = 1 (p-subshell),  = 2 (d-subshell),
 = 3 (f-subshell).
(iii) Magnetic Quantum Number (m) :
It describes the orientations of the subshells. It can have values from – to +  including
zero, i.e., total (2 + 1) values. Each value corresponds to an orbital. s-subshell has one
orbital, p-subshell three orbitals (px, py and pz), d-subshell five orbitals
(dxy ,dyz ,dzx ,dx2  y2 ,dz2 ) and f-subshell has seven orbitals. The total number of orbitals
present in a main energy level is ‘n2’.
(iv) Spin Quantum Number (s) :
It describes the spin of the electron. It has values +1/2 and –1/2. (+) signifies clockwise
spinning and (–) signifies anticlockwise spinning.
Pauli’s Exclusion Principle :
No two electrons in an atom can have the same set of all the four quantum numbers, i.e.,
an orbital cannot have more than 2 electrons because three quantum numbers (principal,
azimuthal and magnetic) at the most may be same but the fourth must be different, i.e.,
spins must be in opposite directions.
14 ATOMIC STRUCTURE
Aufbau Principle :
Aufbau is a German word meaning builiding up. The electrons are filled in various orbitals
in order of their increasing energies. An orbital of lowest energy is filled first. The
sequence of orbitals in order of their increasing energy is :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ....
The energy of the orbitals is governed by (n + ) rule.
Hund’s Rule :
No electron pairing takes place in the orbitals in a sub energy shell until each orbital is
occupied by one electron with parallel spin. Exactly half filled and fully filled orbitals make
the atoms more stable, i.e., p3, p6, d5, d10, f 7 and f 14 configuration are most stable.
 Total no. of e– in main energy shell = 2n2

Total no. of e– in a subshell = 2 (2 + 1)
Maximum no. of e– in an orbital = 2

Total no. of orbitals in a subshell = (2 + 1)
No. of subshells in main energy shell = n

No. of orbitals in a main energy shell = n2
h
 Orbital angular momentum L =  (  1)
2
h 1
 Spin angular momentum S = S(S  1) ; S =
2 2
eh
 Spin magnetic moment s = s(s  1)
2 mc
or  = n(n  2) B.M. (n = no. of unpaired electrons)

eh
 Orbital magnetic moment s = s(s  1)
4 mc
THE SCHRODINGER EQUATION

The de Broglie wave relation is the basis for predicting the behavior of freely moving particles.
Shortly after it was proposed, Erwin Schrodinger demonstrated that the de Broglie expression
could be generalized so as to apply to bound particles such as electrons in atoms. The heart of
Schrodinger's theory is that the allowed energies of physical systems can be found by solving an
equation which so resembles the equations of classical wave theory that it is called the wave
equation. For the motion of one particle in one (the x) direction, the Schrodinger wave equation is
h2 d2 
– + V = E .
82m dx2

ATOMIC STRUCTURE 15
The "knowns" in this equation are m, the mass of the particle, and V, its potential energy
expressed as a function of x. The "unknowns" to be found by solving the equation are E, the
quantized or allowed energies of the particle, and , which is called the wave function. The
quantity d2/dx2 represents the rate of change of d/dx, the rate of change of . When this
equation is applied to real systems such as the hydrogen atom, it is found that it cannot be solved
unless E takes on certain values which are related by integers. Thus quantized energy and
quantum numbers are an automatic consequence of the Schrodinger theory, and do not have to
be tacked on to Newtonian mechanics as was done by Bohr.
What is ? By itself, it has no physical meaning. However, the square of the absolute value of ,
2, does have an important physical interpretation. It is a mathematical expression of how the
probability of finding a particle varies from place to place. Thus the exact trajectories of
Newtonian mechanics and the Bohr theory do not appear in the results of the Schrodinger
quantum mechanics; this, according to the Uncertainty Principle, is as it should be.
A similar analysis is possible for the other 2p-functions. The px function has the yz-plane as an
angular node, since the function is proportional sin  cos  and cos  = 0 everywhere in the yz-
plane. The maximum values of 1 for sin  and cos  occur along the positive x-axis. The py
function, proportional to the sin  sin , vanishes in the xz-plane, where sin  = 0, and has a
maximum along the positive y-axis, where both sin  and sin  are unity.
FIG. The 2p-orbitals of the hydrogen atom. (Adapted from K. B. Harvey and G. B. Porter, An Introduction to
Physical Inorganic Chemistry. Reading, Mass.: Addison-Wesley, 1963.)
The 3d-orbitals of the hydrogen atom. Note the relation between the labeling of the d-orbitals and their
orientations in space. (Adapted from K. B. Harvey and G. B. Porter, An Introduction to Physical Inorganic Chemistry.
Reading, Mass.: Addison-Wesley, 1963.)

16 ATOMIC STRUCTURE
SOLVED EXAMPLES
Example: 1 Atomic weight of Ne is 20.2. Ne is a mixutre of Ne20 and Ne22 . Calculat relative
abundance of heavier isotope.
Solution: Average atomic weight/ The average isotopic weight
% of 1st isotope  relative mass of 1st isotope  % of 2nd isotope  relative mass of 2nd isotope

100
a  20  (100  a)  22
 20.2  ;
100
 a  90 ; per cent of heavier isotope  100  90  10
Example: 2 Assuming a spherical shape for fluorine nucleus, calculate the radius and the nuclear
density of fluorine nucleus of mass number 19.
Solution: Weknow that,
r  (1.4  1013 )A1/3  1.4  10 13  191/3  3.73  10 13 cm (A for F=19)
4 3 4
Volume of a fluorine atom  r   3.14  (3.73  1013 )3  2.18  1037 cm3
3 3
Mass of one mol of nucleus 19
Mass of single nucleus   g
Avogadro's number 6.023  1023
Mass of single nucleus
Thus Density of nucleus 
Volume of single nucleus
19 1
 23
  7.616  1013 gcm1
6.023  10 2.18  1037
Example: 3 Assuming that a 25 watt bulb emits monochromatic yellow light of wave length 0.57.
What will be the rate of emission of quanta per sec.?
Solution: Let n quanta are evolved per sec.
 hc  6.626  10 34  3  108
n    25Jsec 1 ; n  25 ;
  0.57  106
n  7.18  1019 sec 1
Example: 4 Calculate number of photon coming out per sec. from the bulb of 100 watt. If it is 50%
efficient and wavelength coming out is 600 nm.
Solution: energy = 100J
hc 6.625  10 34  3  108 6.625
energy of one photon = = = × 10–19
 600  109 2
100
No. of photon = × 1019 = 15.09 × 1019
6.625

ATOMIC STRUCTURE 17
Example: 5 The therehold frequency 0 for a metal is 6 × 1014 s–1. Calculate the kinetic energy of an
electron emitted when radiation of frequency  = 1.1 × 1015 s–1 hits the metal.
1
Solution: K.E. = meV2 = h ( – 0)
2
 K.E. = (6.626 × 10–34) (1.1 × 1015 – 6 × 1014)
 K.E. = (6.626 × 10–34) (5 × 1014)
= 3.313 × 10–19 J
Example: 6 When electromagnetic radiation of wavelength 310 nm fall on the surface of Sodium,
electrons are emitted with K.E. = 1.5 eV. Determine the work function (W 0) of Sodium.
12400
Solution: h = = 4 eV
3100
1
m V2 = 1.5 eV
2 e
1
 h0 = W 0 = h – m V2
2 e
= 4 – 1.5 = 2.5 eV
Example: 7 If the radius of 2nd Bohr orbit of hydrogen atom is r2. Calculate the radius of third Bohr
orbit.
n2h2 r2 22 9
Solution: r 2 2
  2  r3  r2
4 mZe r3 3 4
Example: 8 Calculate the Number of waves made by a Bohr electron in one complete revolution in 3rd
orbit.
Solution: Circumference of 3rd orbit = 2r3
According to Bohr angular momentum of electron in 3rd orbit is
h h 2r3
mvr3 = 3 or 
2 mv 3
by De-Broglie equation,
h

mv
2r3
  2r3  3
3
i.e. circumference of 3rd orbit is three times the wavelength of electron or number of
waves made by Bohr electron in one complete revolution in 3rd orbit is three.
18 ATOMIC STRUCTURE
RH
Example: 9 Calculate the degeneracy of the level of hydrogen atom that has energy 
16 .
RH R R
Solution: En   2
  2H   H
n n 16
i.e. for 4th sub-shell

i.e. 1+3+5+7=16,  degeneracy is 16
Example: 10 How many chlorine atoms can you ionize in the process Cl  Cl  e  , by the energy
liberated from the following process:
Cl  e  Cl for 6  1023 atoms
Given electron affinity of Cl  3.61eV, and IP of Cl  17.422eV
Solution: Energy released in conversion of 6  1023 atoms of Cl ions = 6  1023 × electron affinity
= 6× 10 23  3.61  2.166  1024 eV.
Let xCl atoms are converted to Cl ion
Energy absorbed  x  ionization energy
x  17.422  2.166  1024 ; x  1.243  1023 atoms
Example: 11 The binding energy of an electron in the ground state of the He atom is equal to 24eV.
What will be the energy required to remove both the electrons from the atom?
Z2 22
Solution: Ionization energy of He   13.6   13.6  54.4eV
n2 12
Energy required to remove both the electrons
 binding energy + ionization energy
 24.6  54.4  79Ev
–1
Example: 12 The ionization energy of He is 19.6  1018 Jatom . Calculate the energy of the first
stationary state of Li2
Solution: I.E. of He   E  22 (Z for He  2)
I.E. of Li2   E  33 (Z for Li=3)
I.E.(He  ) 4 9 9
  or I.E. (Li2  )   I.E.(He )   19.6  1018
I.E.(Li2  ) 9 4 4
= 4.41 1017 J atom–1

ATOMIC STRUCTURE 19
Example: 13 What is the principal quantum number of H atom orbital is the electron energy is – 3.4
eV? Also report the angular momentum of electron.
Solution: E1 for H = – 13.6 eV
E 13.6
Now En = 21  – 3.4 =  n=2
n n2
h
Now, Angular momentum (mur) = n .
2
2  6.626  10 34
= = 2.1 × 10–34 J-sec–1
2  3.14
Example: 14 The lyman series of H-atom can be represented by the equation

 1
  = 3.2881 × 1015 sec–1 1  2  . Calculate max. and min. for the series.
 n 
Solution: E = h
 Emax = hmax (for n =  to n = 1)
 Emin = hmin (for n =  to n = 1)
 1
  max. = 3.2881 × 1015 sec–1  1  2  .........(1)
 n 
Put n =  for max we get
 max. = 3.2881×1015 sec–1.
Put n = 2
 1
min = 3.2881 × 1015 sec–1  1  
 4
3
= × 3.2881 × 1015 sec–1
4
2.4661 × 1015 sec–1
Example: 15 What is the maximum precision with which the momentum of an electron can be known if
the uncertainty in the position of electron is 0.001Å ? Will there be any problem in
h
describing the momentum if it has a value of , where a0 is Bohr’s radius of first orbit,
2a0
i.e., 0.529Å?
h
Solution: x. p 
4
 x  0.001Å  1013 m
6.625  10 34
 p   5.27  10 22
4  3.14  10 13
20 ATOMIC STRUCTURE
Example: 16 An electron is moving with a kinetic energy of 4.55 × 10 25 J. What will be de-Broglie
wavelength for this electron ?
1
Solution: KE  mv 2  4.55  10 25 J
2
2  4.55  10 25
v 2 110 6 ; v  10 3 m / s
9.1 10 31
h 6.626  10 34
De-Broglie wavelength     7.28  10 7 m
mv 9.110 3110 3
Example: 17 Radius of two different orbits in a H like sample is 4R and 16R respactively then find out
the ratio of the frequency of revolution of electron in these two orbits.
r1 0.529n12 4R n12 1 n1 1
Solution: = 2
=  2
= or =
r2 0.529n2 16R n2 4 n2 2
2 3
f1 v / 2r1 n3 n   2
Now, = 1 = 32 =  2  =   = 8 : 1
f2 v 2 / 2r2 n1 n
 1  1
Example: 18 In a hydrogen like sample, ions are in a particular excited state, if electrons
make transition upto 1 st excited state, then it produces maximum 15
diff erent types of spectral lines then electrons were in which state?
n  n  1
Solution: = 15  n = 5  n – 2 = 5  n = 7
2


ATOMIC STRUCTURE 21
EXERCISE # 01 OBJECTIVE EXERCISE # 01
1. Consider the ground state of Cr(Z = 24). The no. of electrons with the azimuthal quantum no.
 = 1 & 2 respectively are –
(A) 16 & 4 (B) 12 & 5 (C) 12 & 4 (D) 16 & 5
2. As we go away from the nucleus, the difference between the successive energy levels -
(A) increases (B) decreases
(C) remains constant (D) first increases, then decreases
3. The energy of electron in first Bohr’s orbit of H-atom is –13.6 eV. What will be its potential energy
in n = 4th orbit -
(A) – 13.6 eV (B) –3.4 eV (C) –0.85 Ev (D) –1.70 eV
4. What is the total number of orbitals in the shell to which the g-subshell first arise?
(A) 9 (B) 16 (C) 25 (D) 36
5. If E1, E2 and E3 represent respectively the kinetic energies of an electron, an -particle and a
proton each having same de Broglie wavelength , then
(A) E1 > E2 > E3 (B) E3 > E2 > E1
(C) E1 > E3 > E2 (D) E1 = E2 = E3
6. The radii of two of the first four Bohr orbits of the hydrogen atom are in the ratio 1 : 4. The energy
difference between them may be :
(A) Either 12.09 eV or 3.4 eV (B) Either 2.55 eV or 10.2 eV
(C) Either 13.6 eV or 3.4 eV (D) Either 3.4 eV or 0.85 eV
7. A beam of electrons is accelerated by a potential difference of 10000 volts. The wavelength of the
wave associated with it will be -
(A) 0.0123 Å (B) 1.23 Å (C) 0.123 Å (D) None of these
8. Energy difference between the states n = 2 and n = 3 is E eV, in hydrogen atom. The ionisation
potential of H atom is -
(A) 3.2 E (B) 5. 6E (C) 7.2 E (D) 13.2 E
9. The ratio of the energy of a photon of 2000 Å wavelength radiation to that of 4000 Å radiation is
(A) 1 / 4 (B) 4 (C) 1 / 2 (D) 2
10. The energy of electron is maximum at

(A) Nucleus (B) Ground state
(C) First excited state (D) Infinite distance from the nucleus
11. Which electronic level would allow the hydrogen atom to absorb a photon but not to emit a photon
(A) 3s (B) 2p (C) 2s (D) 1s
22 ATOMIC STRUCTURE
12. The third line in Balmer series corresponds to an electronic transition between which Bohr’s orbits
in hydrogen
(A) 53 (B) 52 (C) 43 (D) 42
13. The orbital angular momentum of an electron in 2s orbital is:

1   
(A)  . (B) Zero (C) (D) 2.
2 2 2 2
14. The shortest wavelength of He atom in Balmer series is x, then longest wavelength in the
Paschene series of Li+2 is
36x 16x 9x 5x
(A) (B) (C) (D)
5 7 5 9
15. An electron in a hydrogen atom in its ground state absorbs energy equal to the ionisation energy
of Li+2. The wavelength of the emitted electron is:
(A) 3.32 ×10–10 m (B) 1.17 Å
(C) 2.32 × 10–9 nm (D) 3.33 pm
16. An electron, a proton and an alpha particle have kinetic energies of 16E, 4E and E respectively.
What is the qualitative order of their de Broglie wavelengths?
(A) e > p =  (B) p =  > e
(C) p > e >    (D)  < e » p
17. Given H for the process Li(g)  Li+3(g) + 3e– is 19800 kJ/mole & IE1 for Li is 520 then IE2
& IE3 of Li+ are respectively (approx, value)

(A) 11775, 7505 (B) 19280, 520
(C) 11775, 19280 (D) Data insufficient
18. The ratio of difference in wavelengths of 1st and 2nd lines of Lyman series in H–like atom to
difference in wavelength for 2nd and 3rd lines of same series is:
(A) 2.5 : 1 (B) 3.5 : 1 (C) 4.5 : 1 (D) 5.5 : 1
19. If radius of second stationary orbit (in Bohr's atom) is R. Then radius of third orbit will be
(A) R/3 (B) 9R
(C) R/9 (D) 2.25R
20. The ratio of wave length of photon corresponding to the -line of Lyman series in H-atom and
-line of Balmer series in He+ is
(A) 1:1 (B) 1:2 (C) 1:4 (D) 3 : 16

ATOMIC STRUCTURE 23
21. Three energy levels P, Q, R of a certain atom are such that EP < EQ < ER. If 1, 2 and 3 are
the wave length of radiation corresponding to transition R  Q ; Q  P and R P respectively.

The correct relationship between 1, 2 and 3 is
1 1 1 2 1 1
(A) 1 + 2 = 3 (B)   (C) 3 = 12 (D)  
 3 1  2  3 1  2
22. The value of  n2  n1  and  n22  n12  for He+ ion in atomic spectrum are 4 and 8 respectively. The
wavelength of emitted photon when electron jump from n2 to n1 is
32 9 9 32
(A) RH (B) RH (C) (D)
9 32 32RH 9RH
23. Number of possible spectral lines which may be emitted in bracket series in H atom, if electrons
present in 9th excited level returns to ground level, are
(A) 21 (B) 6 (C) 45 (D) 5
24. The first use of quantum theory to explain the structure of atom was made by :
(A) Heisenburg (B) Bohr (C) Planck (D) Einstein
25. The longest wavelength of He+ in Paschen series is "m", then shortest wavelength of Be+3 in
Paschen series is (in terms of m):
5 64 53 7
(A) m (B) m (C) m (D) m
36 7 8 64
26. What is uncertainity in location of a photon of wavelength 5000Å if wavelength is known to an

accuracy of 1 pm?
(A) 7.96  10 14 m (B) 0.02 m (C) 3.9  108 m (D) None
27. Consider the following nuclear reactions involving X & Y.

X  Y + 42 He Y  8O18 + 1H1
If both neutrons as well as protons in both the sides are conserved in nuclear reaction then moles
of neutrons in 4.6 gm of X
(A) 2.4NA (B) 2.4
(C) 4.6 (D) 0.2NA
28. Electromagnetic radiations having  = 310 Å are subjected to a metal sheet having work
function = 12.8 eV. What will be the velocity of photoelectrons with maximum Kinetic Energy..
(A) 0, no emission will occur (B) 2.18  106 m / s
(C) 2.18 2  106 m / s (D) 8.72  10 6 m / s
24 ATOMIC STRUCTURE
29. Assuming Heisenberg Uncertainity Principle to be true what could be the minimum uncertainty in
de-broglie wavelength of a moving electron accelerated by Potential Difference of 6 V whose
7
uncertainty in position is n.m.
22
(A) 6.25 Å (B) 6Å (C) 0.625 Å (D) 0.3125 Å
30. It is known that atoms contain protons, neutrons and electrons. If the mass of neutron is assumed
to be half of its original value whereas that of electron is assumed to be twice of this original
value. The atomic mass of 6 C12 will be -
(A) Twice (B) 75% less
(C) 25% less (D) One-half of its original value
31. When a certain metal was irradiated with light of frequency 1.6 × 1016 Hz, the photoelectrons
emitted had twice the kinetic energy as did photoelectrons emitted when the same metal was
irradiated with light of frequency 1.0 × 1016 Hz. Calculate 0 (threshold frequency) for the metal ?
(A) 6 × 1015 Hz (B) 5 × 1015 Hz (C) 4 × 1015 Hz (D) 7 × 1015 Hz
32. Ionisation potential of hydrogen atom is 13.6eV. If hydrogen atom in the ground state is excited
by monochromatic light of energy 12.1 eV, then the spectral lines emitted according to Bohr's
theory will be –
(A) One (B) Two (C) Three (D) Four
33. Photoelectric emission is observed from a surface for frequencies 1 and 2 of the incident
radiation (1 > 2). If the maximum kinetic energies of the photoelectrons in the two cases are in
ratio 1 : K, then the threshold frequency 0 is given by :
 2  1 k1   2
(A) (B)
k 1 k 1
k  2  1  2  1
(C) (D)
k 1 k 1
34. The critical wavelength for producing the photoelectric effect in tungsten is 2600 Å. What
wavelength would be necessary to produce photoelectrons from tungsten having twice the K.E. of
those produced at 2200 Å :
(A) 2900 Å (B) 3000Å
(C) 1900 Å (D) 3500 Å
35. O2 undergoes photochemical dissociation into 1 normal oxygen atom and 1 oxygen atom 1.967
eV more energetic than normal. The dissociation of O2 into 2 normal oxygen atoms is known to
require 498 kJ/mol O2. What is the maximum wavelength effective for the photochemical
dissociation of O2 :
(A) 240 Å (B) 174 nm (C) 174 Å (D) 200 Å

ATOMIC STRUCTURE 25
36. In a measurement of the quantum efficiency of photosynthesis in green plants, it was found that 8
quanta of red light at 6850 Å were needed to evolve 1 molecule of O2. The average energy
storage in the photosynthetic process is 112 K cal/mol O2 evolved. What is the energy conversion
efficiency in this experiment :
(A) 33.5 % (B) 66.5 % (C) 64.5 % (D) 15 %
37. Photoelectric work function of a metal 1 eV. If a light of wavelength 500 Å falls on the metal, the
speed of the photoelectron emitted approximately will be- ( h = 6.625 × 10–34 J s)
1
(A) Equal to velocity light (B) × velocity of light
10
1 1
(C) × velocity of light (D) × velocity of light
100 1000
38. Photons having energy equivalent to binding energy of 4th state of He+ ion is used the metal
surface of work function 1.4 eV. If electrons are further accelerated through the potential
difference of 4 V then the minimum value of de-Broglie wavelength associated with the electron is-
(A) 1.1 Å (B) 9.15 Å (C) 5 Å (D) 11 Å
39. The transition, so that the de-Broglie wavelength of electron becomes 3 times of its initial value in
He+ ion will be
(A) 25 (B) 32 (C) 26 (D) 12
40. If the uncertainty in velocity & position is same, then the uncertainty in momentum will be
hm h h 1 h
(A) (B) m (C) (D)
4 4 4 m m 4
41. In a collection of H-atom, electrons make transition from 5th excited state to 2nd excited state
then maximum number of different types of photons observed are
(A) 3 (B) 4 (C) 6 (D) 15
42. The difference in the wavelength of the 1st line of Lyman series and 2nd line of Balmer series in a
hydrogen atom is
9 4 88
(A) (B) (C) (D) None
2R R 15R
43. The wave number of electromagnetic radiation emitted during the transition of electron in
between two levels of Li2+ ion whose principal quantum numbers sum is 4 and difference is 2 is
8
(A) 3.5 R (B) 4R (C) 8R (D) R
9

26 ATOMIC STRUCTURE
EXERCISE # 02 ADVANCED EXERCISE

(COMPREHENSION TYPE, MULTIPLE TYPE, MATRIX MATCH TYPE, INTEGER TYPE)
PASSAGE # 01
The single quantum number suggested by Neil’s Bohr and the appearance of several spectral
lines in a particular series of H-spectrum, suggest that there must be more than one quantum
number to explain all the quantized properties of an electron in a particular energy level inside the
atom.
In fact when the properties of the electron is transformed from Cartesian co-ordinate to polar co-
ordinates then it becomes the function of r, , and  suggesting three independent quantum
numbers. In addition to this a fourth quantum number is required to consider the spinning
behaviour of an electron.
The principal quantum number n, suggest the orbit number in which electron revolves; Azimuthal
quantum number l suggest the shape of orbitals, magnetic quantum number m, gives orientation
of orbital in presence of external magnetic field, while spin quantum number s, gives direction of
rotation of an electron about it’s own axis.
n  0 values of “l” ranges in between 0 to (n –1) , while m depends upon l. Total number of values
1
of m = 2l + l, and “m” ranges in between –l to +l including 0. For each electron spin will be  .
2
1 1
S  S
2 2
Clock wise spin Anti clock wise spin
Questions based on the above passage:
1. Which of the following is not possible

(A) 2s (B) 2d (C) 3f (D) (b) & (c)
2. The two unpaired electron present in C-atom are different w.r.t their
(A) n (B) l (C) m (D) s
3. d-orbital may contain maximum of 10 electron as for d-orbital

(A) l = 2 (B) total values of m = 5
(C) both (a) and (b) (D) None
4. The maximum number of electrons with n = 3, l = 3 is

(A) 14 (B) 10 (C) 6 (D) 0
5. If n = 3, l = 0, m = 0 then the possible atomic number may be

(A) 10, 11 (B) 11, 12 (C) 12, 13 (D) 13, 14

ATOMIC STRUCTURE 27
6. Two electrons A and B in an atom have the following set of quantum numbers; what is true for A
and B
For A; n = 3, l = 2, m = –2, s = +1/2 For B; n = 3, l = 0, m = 0, s = +1/2
(A) A and B have same energy (B) A has more energy than B
(C) B has more energy than A (D) A and B represent the same electron
PASSAGE # 02
Bohr model which is based on planck's Quantum theory and newton's laws gave atomic structure
which can explain atomic structure of Hydrogen and Hydrogen like atom (one electron system).
By the use of this model radius of atom and energy of electron for one electron can be determine
by following formula.
n2 Z2
rn = 0.529 × Å En = – 13.6 × 2 eV/atom
Z n
7. What is the ratio of energy of first three orbit of Hydrogen -

(A) 36 : 9 : 4 (B) 1 : 4 : 9 (C) 1 : 2 : 3 (D) None of these
8. What the energy of 3rd excited state of Be3+ in eV/atom -

(A) – 13.6 (B) – 7.65 (C) – 24.17 (D) None of these
9. What is the ratio of circumference of 3rd orbit of He+ and 5th orbit of Hydrogen -
(A) 3 : 5 (B) 2 : 1 (C) 9 : 50 (D) None of these
PASSAGE # 03
Electron moves around the nucleus in circular orbitals in fixed energy paths. As far as electron
moves in these orbits neither energy is absorbed nor liberated. But when electron move from
lower energy level to higher energy level energy is absorbed while when it comes back from
higher energy level to lower energy level energy is liberated in the form of photon & a spectral line
is formed. Corresponding to different possible transitions different lines are formed which form the
particular serieses viz. lyman, balmer, paschen, bracket, pfund, humphery etc. Suppose e– in
hydrogen atom is present in 10th excited state, then answer the following questions based on
paragraph :
10. If electron present in 10th excited state liberate one visible quanta then next quanta liberated will
correspond to following transition –
(A) 10  2 (B) 11  2
(C) 11  1 (D) 21
11. Total number of spectral lines which can be obtained during the transition to ground level –
(A) 45 (B) 55 (C) 66 (D) 36
28 ATOMIC STRUCTURE
12. Minimum value of wavelength that can be obtained during the transition –
121 11 100 10
(A) (B) (C) (D)
120 R 10 R 99 R 9R
Where R is Rydberg constant.
PASSAGE # 04
The radius of the nucleus of an atom can be approximately determined as,

rnu = (1.4×10–13)A1/3
where A is mass number of the atoms and M is the charge of the electron = 4.8 × 10–10 esu.
10
The mass of -particle = 4 × mass of H-atom mass of hydrogen atom = ×10–24 gm.
6
Consider during collision kinetic energy of -particle just equal to coulombic force of repulsion.
The mass number of Au = 197
The mass number of He = 4
The atomic number of Au = 79
Given : (4) 1/3 = 1.59 and (197) 1/3 = 5.82
2  79  (4.8) 2
= 351
10.374
3.51 3 = 3.245
Plank’s constant, h = 6.625 × 10 –34 Js
13. What is the distance between the -particle and Au nucleus during the collision –
(A) 10.374 × 10–13 cm (B) 10.374 Å
(C) 10.374 × 10–10 cm (D) 10.374 nm
197
14. What should be the minimum velocity of the -particle to strike the nucleus of 79Au ?
(A) 3.245 108 m / s (B) 3.245 109 m / s

(C) 3.245 105 m / s (D) 3.245 107 m / s
15. What is the de-broglie’s wave length associated with a -particle while it is moving to colloide
with the Au nucleus ?
6.625  6 6.625  6
(A)  10 25 m (B)  1015 m
4  3.245 3.245
6.625  6 6.625  6
(C)  1015 m (D)  1015 m
4  3.245 5  3.245

ATOMIC STRUCTURE 29
PASSAGE # 05
The emission of electrons from a metal surface when exposed to light radiations of appropriate
wavelength is called photoelectric effect. The emitted electrons are called photoelectrons. Work
function or threshold energy may be defined as the minimum amount of energy required to eject
electrons from a metal surface. For ejected photoelectrons –
1 2 1 1 
Maximum kinetic energy = absorbed energy – work function  mVmax = hc  – 
2   0 
Here 0 is threshold wavelength.
16. In the photoelectric effect the slope of straight line graph between stopping
V0
potential (V0) and frequency of incident light () gives -
(A) charge on electron
(B) work function of emitter
(C) planck's constant 
(D) ratio of planck's constant to charge on electron
17. The stopping potential as a function of frequency is plotted for two different
photoelectric surfaces A and B. The graph shows that the work function of A A
B
is – V0
(A) greater than that of B
(B) smaller than that of B
(C) Same as that of B 
(D) Such that no comparison can be done from given grap.
18. The following figure indicates the energy levels of a certain atom. When the system moves from
2E level to E, a photon of wavelength  is emitted. The wavelength of photon produced during the
4E 2E
transitions from level to level E is-
3
4E/3
(A) / 3 (B) 3/4
(C) 4/3 (D) 3 E
PASSAGE # 06
The behaviour of an electron in an atom is described mathematically by a wave function, or

orbital. It turns out that each wave function contains three variables, called quantum numbers,
which are represented as n, l and ml. These quantum numbers describe the energy level of an
orbital and define the shape and orientation of the region in space where the electron will be
found.
30 ATOMIC STRUCTURE
19. Which quantum number determined orientation of the electron ?

(A) Principal (B) Secondary (C) Magnetic (D) Spin
20. Orbital angular momentum is quantised and is given by -

h h h h
(A) l (l  1) (B) n(n  2)  (C) m(m  1) (D) s(s  1)
2 2 2 2
21. Radial nodes are maximum in -
(A) 4s (B) 4p (C) 3d (D) 5ƒ
22. Total number of electrons in any energy level is-

l n l  n 1 l  n 1 l  n 1
(A)  2(2l  1)
l 1
(B) 
l 1
2(2l  1) (C) 
l0
2(2l  1) (D)  2(2l  1)
l0
23. Consider following statements :

I : Splitting of spectral line occurs when placed in a magnetic field or in an electric field
II : In case of 1s-orbital, the density of the charge cloud is the greatest at the nucleus and falls
off with the distance. The density (at a particular distance is uniform)
III : Electron-density is concentrated along a particular direction in case of 2p-orbital
IV : A p-orbital can take maximum of six electrons
Select correct statements-
(A) I, II, IV (B) I, II, III
(C) II, III, IV (D) I, III, IV
PASSAGE # 7
1 1
Assume that there were four possible values (–1, ,+ , +1 ) for the spin quantum number ms.
2 2
Principal quantum number n is defined as usual. However, quantum number  & m are defined
as follows :
 :1 to (n +1) in integral steps
 
m :  to +  (including zero, if any) in integral steps.
2 2
The orbitals corresponding to   1, 2, 3....... designated as A, B, C........respectively. Further, the
values of m for a given value of  give the number of sub-orbitals in an orbital. The principles for
filling electrons in the shells remain unchanged. The order of energies of various orbitals is : A < B <
C.......for the same shell.
24. The number of elements that would be present in the second period of the periodic table is–
(A) 9 (B) 20 (C) 24 (D) 36

ATOMIC STRUCTURE 31
25. The second period would begin with–

(A) Fluorine (B) Sodium
(C) Calcium (D) Scandium
26. If Aufbau’s principle is not to be violated i.e. (n + l) rule must be followed, the outermost
electronic configuration of an element with at. no. 100 would be –
(A) 3 B 8 4 A4 (B) 3C16 4 A8
(C) 3C12 4 B8 (D) 4 B12 5 A8
27. The number of sub-orbitals & the maximum number of electrons that can be filled in an E–orbitals
are respectively–
(A) 6, 24 (B) 5 , 20
(C) 7, 28 (D) can’t be determined
More than one may be correct (Advanced Objective)
28. Choose the incorrect statement(s) :

(A) Increasing order of wavelength is
Micro waves > Radio waves > IR waves > visible waves > UV waves
(B) The order of Bohr radius is (rn: where n is orbit number for a given atom) r1< r2< r3< r4
(C) The order of total energy is (En: where n is orbit number for a given atom)
E1> E2> E3> E4
(D) The order of velocity of electron in H, He+, Li2+, Be3+

species in second Bohr orbit is Be3+> Li+2> He+> H
29. Select the correct curve(s) :

If v = velocity of electron in Bohr's orbit
r = Radius of electron in Bohr's orbit
P.E. = Potential energy of electron in Bohr's orbit
K.E. = Kinetic energy of electron in Bohr's orbit.
(A) (B)
(C) (D)
32 ATOMIC STRUCTURE
30. Which is / are correct statement.

(A) The difference in angular momentum associated with the electron present in consecutive
h
orbits of H-atom is  n  1
2
(B) Energy difference between energy levels will be changed if, P.E. at infinity assigned value
other than zero.
(C) Frequency of spectral line in a H-atom is in the order of
(2  1) < (3  1) < (4  1)
(D) On moving away from the nucleus, kinetic energy of electron decreases.
– –
31. X is isoelectronic with CO and has (Z+2) number of neutrons where Z is the atomic number of X
. Therefore,
(A) ionic mass of X– is 28
(B) ionic mass of X–is 30
(C) atomic number of X–is 13
(D) atomic number of X– is 14
32. Which of the following statements are correct?

(A) The total spectral lines obtained from a single line during Zeeman effect is (2l + 1).
(B) In the Lyman series as the energy liberated during transition increases then the distance
between the spectral lines goes on decreasing.
(C) The highest probability of finding an electron in 1s orbital is in the vicinity of the
circumference.
(D) The highest probability of finding an electron in 1s orbital is exactly at the middle between
nucleus and circumference.
33. Which of the following statements are incorrect?

(A) There are five unpaired electrons in (n –1) d suborbit in Fe3+
(B) Fe3+, Mn+ and Cr all having 24 electrons will have same value of magnetic moment
(C) Copper (I) chloride is coloured salt (D) Every coloured ion is paramagnetic
34. If Aufbau rule and Hund’s rule are not considered, which of the following statements are correct?
(A) Fe2+ will have configuration as [Ar]
(B) Cu2+ is colourless ion

(C) Magnetic moment of the Mn is 3 BM (D) K+ is of d-block
35. Rutherford’s experiment established that:

(A) Inside the atom there is a heavy positive centre
(B) Nucleus contains protons and neutrons
(C) Most of the space in the atoms is empty (D) Size of the nucleus is very small

ATOMIC STRUCTURE 33
36. Which of the following transition in H–atom would result in emission of radiations of same
frequency?
(A) 4s  3p (B) 4s  3s (C) 5s  4s (D) 3s  2p
37. The radii. of two Bohr orbit of the hydrogen atom are in the ratio 4: 9, The energy difference
between them may be -
(A) 1.89 eV (B) 3.4 eV (C) 12.09 eV (D) 0.472 eV
38. When photons of energy 4.25 eV strike the surface of a metal A, the ejected photoelectrons have
maximum kinetic energy TA (expressed in eV) and de Broglie wavelength A. The maximum
kinetic energy of photoelectrons liberated from another metal B by photons of energy 4.2 eV is
TB = TA – 1.50 eV. If the de Broglie wavelength of these photoelectrons is B = 2A , then which is
correct -
(A) The work function of A is 2.25 eV (B) The work function of B is 3.70 eV
(C) TA = 2.00 eV (D) TB = 2.75 eV
39. For electron, proton, deuterium molecule (D2) and -particle a curve between  (De broglie
wavelength) v/s v (speed) is plotted select the correct statements(s)

I
II
III
V
(A) Curve I is for electrons (B) Curve III is for proton
(C) Curve II is for -particle (D) Curve III is for Deuterium (D2)
40. Which of the following sets of quantum number are correct

n  m s
(A) 3 2 –2 1/2
(B) 4 0 0 1/2
(C) 3 2 –3 1/2
(D) 5 3 0 –1/2
41. Radiation of wavelength 200 Å falls on a platinum surface. If the work function of the metal is 5
eV. Which of the following results are correct about experiment?
(A) The velocity of photoelectrons increases with increase in intensity of radiation
(B) Photo-emission of electrons takes place
(C) The threshold frequency of the metal is 1.21 × 1015 sec–1
(D) The velocity of the photo-electrons is 4.48 × 106 m/sec.
34 ATOMIC STRUCTURE
42. When the KE of released electron (y-axis) is plotted against the frequency,  of the incident light
(x-axis) then, which of the following is/are correct?
(A) The plot is straight line passing through the origin and slope equal to h.
(B) The plot is straight line with an intercept on Y-axis and slope equal to h.
(C) The plot is straight line with an intercept with x-axis and slope equal to h.
(D) The intercept of the plot with x-axis represent threshold frequency, 0.
2 2
43. Regarding the radial probability distribution (4r R n ) vs r plot which of the following is/are
correct?
(A) The number of maxima is (n –)
(B) The number of nodal points is (n –  –1)
(C) The radius at which the radial probability density reaches to maxima is 3s <3p < 3d
(D) The number of angular nodes is .
44. Choose the correct statement among the following

2 2
(A) Radial distribution function (  ·4 r dr ) give probability at a particular distance along one
chosen direction
(B)  2 (r ) give probability density at a particular distance over a spherical surface
(C) For 's' orbitals  ( r )  ( )  ( )   ( x, y , z ) is independent of  and 
(D) '2p' orbital with quantum numbers. n = 2,  = 1, m = 0, also shows angular dependence
45. Correct statement(s) regarding 3Py orbital is/are
(A) Angular part of wave function is independent of angles ( and )
(B) No. of maxima when a curve is plotted between 4 r2R2(r) vs r are '2'
(C) 'xz' plane acts as nodal plane
(D) Magnetic quantum number must be '–1'

ATOMIC STRUCTURE 35
Match the column (Advaned Objective)
46. Column I & column II contain data on Schrondinger Wave–Mechanical model, where symbols
have their usual meanings. Match the columns.
Column I Column II (Type of orbital)
(A) (P) 4s
(B) (Q) 5px
(C) (, ) = K (independent of &) (R) 3s

(D) atleast one angular node is present (S) 6dxy
47. Column-I Column-II

(A) Electron moving in 2nd orbit in He+ ion electron (P) Radius of orbit in which
is o
moving is 0.529 A
(B) Electron moving in 3rd orbit in H-atom (Q) Total energy of electron is
(–) 13.6 × 9ev
(C) Electron moving in 1st orbit in Li+2 ion (R) Velocity of electron is
2.188 106
m / sec
3
(D) Electron moving in 2nd orbit is Be+3 ion (S) De-broglie wavelength of
150
electron is Å
13.6
48. Column-I Column-II
K .E
(A) (P) 2
P.E
1
(B) P.E + 2 K. E (Q) 
2
P.E
(C) (R) –1
T .E
K .E
(D) (S) 0
T .E
36 ATOMIC STRUCTURE
49. Column I Column II

(A) Ratio of velocity of electron in 5th& 3rdexcited (P) 4/1
level for H atom is
(B) Ratio of wavelength of series limit of Balmer to (Q) 2/3

lyman series for H atom is
(C) Ratio of wavelength of photon corresponding to (R) 1/4

-line of lyman series and -line of paschen series
for a H-atom is
rd st
(D) Ratio of energy difference between 3 and 1 orbit (S) 3/32
of H atom and He+ion is
50. If in Bohr's model, for unielectronic atom following symbols are used
Un, z Potential energy of e– ; Kn, z Kinetic energy of e– ;
Vn, z Velocity of e– ; Tn, z Time period of revolution;
Column I Column II
(A) U1, 2: K1, 1 (P) 1: 8
(B) r2, 1: r1, 2 (Q) – 8: 1
(C) v1, 3: v3, 1 (R) 9: 1
(D) T1, 2: T2, 2 (S) 8: 1
51. Electron of charge e (coulombs) and mass me. (kg) is accelerated by a potential of 50V
Column I Column II
h
(A) Velocity of electron (m/s) (P)
10 e me
(B) KE of electron (Q) 10 e me

(C) Momentum of electron (R) 50 e
e
(D) Wavelength associated with electron (S) 10
me

ATOMIC STRUCTURE 37

(A) KE of electron is proportional to Z2
(P)
n3
(B) The product of velocity of electron and the Z2
principal Quantum number is proportional to (Q)
n2
(C) frequency of revolution of the electron in an Z3
orbit is proportional to (R)
n4
(D) Coulombic force of attraction on the electron is (S) Z
proportional to

(A) (P) Violation of Aufbau rule
(B) (Q) Violation of pauli exclusion principle
(C) (R) Violation of Hund’s rule
(D) (S) Appropriate configuration

(A) (P) Singlet C in ground state
(B) (Q) Triplet C in ground state
(C) (R) Excited state C having maximum exchange energy
(D) (S) Singlet C in excited state
INTEGER ANSWER TYPE PROBLEMS (Advanced Objective)
55. The velocity of an electron in a certain Bohr’s orbit of H-atom bears the ratio 1: 275 to the velocity
of light. Then find the quantum number (n) of orbit.
56. An ion Mn a  has the magnetic moment equal to 4.9 BM. What is the value of a?
57. The wavelength of m th line Balmer series for an orbital is 4103Å. What is the value of m?
58. Find out the number of angular nodes in the orbital to which the last electron of Cr enter.
th
59. Given that r n1  rn  r n1 , where rn , rn 1 and rn 1 are Bohr’s radius for H-atom in nth ,  n  1
th
and  n  1 shell respectively, then find the value of n.
60. The magnetic moment of a transition metal ion is 15 B.M . . Find out the number of unpaired
electrons in it.

38 ATOMIC STRUCTURE
EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01)
1. 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.
2. Wavelength of the Balmer H  line is 6565 Å. Calculate the wavelength of H , line of same
hydrogen like atom.
3. 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.
4. What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition, n=4 to n=2 of He+ spectrum.
5. 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.
6. A photon having  = 854 Å causes the ionization of a nitrogen atom. Give the I.E. per mole of
nitrogen in KJ.
7. 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.
21.7  1012
8. The electron energy in hydrogen atom is given by En  ergs. Calculate the energy
n2
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.
9. 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.
10. 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 quatum state (n+1) to the ground state.
11. 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.

ATOMIC STRUCTURE 39
12. 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.
12
If I.P. of H is 21.7  10 erg. Calculate 
(i) No. of atoms present in III & II energy level.
(ii) Total energy evolved when all the atoms return to ground state.
13. The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e– in the given
orbit.
14. The vapours of Hg absorb some electrons accelerated by a potential difference 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.
15. 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.
16. 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.
17. 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.
18. 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 wave number.
19. 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 others concepts and parameter to be same as we considered in Bohr's
model.]
20. A photon of 300 nm is absorbed by a gas and then re-emitted two photons. One re-emitted
photon has wavelength 500 nm. Calculate the energy of other photon re-emitted out.
21. A metal was irradiated by light of frequency 3.2 × 1015s–1. The photoelectron produced had its KE,
2 times the K.E of photoelectron which was produced when the same metal was irradiated with a
light of frequency 2 × 1015 s–1. What is work function?
40 ATOMIC STRUCTURE
1 1
22. If the spin quantum number, ms would have the values of – , 0 and + , how many elements
2 2
would be present in third period?
23. Electron of Be3+ ion is present in an orbital which has 2 angular nodes and 2 radial nodes. Give
sum of (n + ) for orbital in which electron is present.
(Given: In this question n is principal quantum number &  is azimuthal quantum number).
24. 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.
25. An electron has a speed of 40 m/s, accurate up to 99.99%. What is the uncertainity in locating its
position.


ATOMIC STRUCTURE 41
EXERCISE # 04 SUBJECTIVE EXERCISE (LEVEL # 02)
1. 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.
2. The critical wavelength for producing photoelectric effect in tungsten is 2600 Å. What wavelength
would be necessary to produce photoelectrons from tungsten having twice the kinetic energy of
these produced at 2200 Å?
3. 4000 Å photon is used to break the iodine molecule, then the % of energy converted to the K.E. of
iodine atoms if bond dissociation energy of I2 molecule is 246.5 kJ/mol. (hc = 1240 eV– nm) , (one
23
mole = 6 × 10 photon)
4. An excited hydrogen atom when comes directly to ground state, emits a photon which when falls
on a metal surface causes the emission of a photoelectron with de Broglie wavelength 4.09Å. If
work function of metal is 3.75 eV, then find out number of orbit of hydrogen atom in which
electron was present in excited state.
5. H-atom is excited by a photon and this excited atom comes back to the ground state by loss of
two photons of wavelength 4341.7 Å and 1215.6 Å find out principal quantum number of electron
in excited state of H-atom –
6. 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.
13 1
7. Find the number of photons of radiation of frequency 5  10 s that must be absorbed in order
to melt one gm ice when the latent heat of fusion of ice is 330 J/g.
17
8. Suppose 10 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.
9. The reaction between H 2 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.
2
10. A base ball of mass 200 g is moving with velocity 30  10 cm / s. If we can locate the base ball
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 base ball.
42 ATOMIC STRUCTURE
11. An energy of 68 eV is required to excite a hydrogen like atom from its second Bohr orbit to the
third. The nuclear charge is Ze. Find the value of Z, the kinetic energy of the electron in the first
Bohr orbit and the wavelength of the radiation required to eject the electrons from the first Bohr
orbit to infinity.
12. A particle of charge equal to that of an electron and mass 208 times the mass of the electron
moves in a circular orbit around a nucleus of charge +3e. Assuming that the Bohr model of the
atom is applicable to this system, (a) derive an expression for the radius of the nth bohr orbit, (b)
find the value of n for which the radius of the orbit is approximately the same as that of the first
Bohr orbit for the hydrogen atom, and (c) find the wavelength of the radiation emitted when the
revolving particle jumps from the third orbit to the first.
6
13. An alpha particle after passing through a potential difference of 2  10 volt falls on a silver foil.
The atomic number of silver is 47. Calculate (i) the K.E. of the alpha-particle at the time of falling
on the foil. (ii) K.E. of the  – particle at a distance of 5 × 10–14m from the nucleus, (iii) the
shortest distance from the nucleus of silver to which the particle reaches.
ke 2
14. Suppose the potential energy between electron and proton at a distance r is given by  .
3r 3
Use Bohr’s theory to obtain energy of such a hypothetical atom.
15. A proton captures a free electron whose K.E. is zero & forms a hydrogen atom of lowest energy-
level (n = 1). If a photon is emitted in this process, what will be the wavelength of radiation? In
which region of electromagnetic spectrum, will this radiation fall? (Ionisation potential of hydrogen
= 13.6 volt, h = 6.6 × 10–34 Js, C = 3.0 × 108 m/s)
16. The ionisation energy of the hydrogen atom is given to be 13.6 eV. A photon falls on a hydrogen
atom which is initially in the ground state and excites it to the (n = 4)state.
(a) show this transition in the energy-level diagram &
(b) calculate the wavelength of the photon.
17. Find the wavelength of the first line of He+ ion spectral series whose interval between extreme
line is
1 1 4 1 
   2.7451 10 cm 
 1 2 
18. The ionisation energy of a H-like Bohr atom is 4 Rydbergs

(i) What is the wavelength of radiation emitted when the e– jumps from the first excited state to the
ground state.
(ii) What is the radius of first Bohr orbit for this atom. [ 1 Rydberg = 2.18 × 10–18 J]

ATOMIC STRUCTURE 43
19. Photon having wavelength 12.4 nm was allowed to strike a metal plate having work function 25
eV. Calculate the
(a) Maximum kinetic energy of photoelectrons emitted in eV.
(b) Wavelength of electron with maximum kinetic energy in Å.
(c) Calculate the uncertainity in wavelength of emitted electron if the uncertainity in the momentum is
6.62 × 10–28 Kg m/sec.
20. Electron present in single electron specie jumps from energy level 3 to 1. Emitted photons when
passed through a sample containing excited He+ ion causes further excitation to some higher
Z2
energy level (Given En = –13.6 2 ). Determine
n
(i) Atomic number of single electron specie.
(ii) principal quantum number of initial excited level & higher energy level of He+.
21. The angular momentum of an electron in a Bohr's orbit of H-atom is 3.1652×10–34 kg-m2/sec.
Calculate the wavenumber in terms of Rydberg constant (R) of the spectral line emitted when an
electron falls from this level to the ground state.
[Use h = 6.626 × 10–34 Js]
22. In the Bohr's model, for unielectronic species following symbols are used
rn,z  Radius of nth orbit with atomic number "z"
Un,z  Potential energy of electron in nth orbit with atomic number "z"
Kn,z  Kinetic energy of electron in nth orbit with atomic number "z"
vn,z  Velocity of electron in nth orbit with atomic number "z"
Tn,z  Time period of revolution of electron in nth orbit with atomic number "z"
Calculate z in all in cases.
(i) U1, 2 : K1,z = – 8 : 1 (ii) r1,z : r2, 1 = 1 : 8
(iii) v1, z : v3, 1 = 9 : 1 (iv) T1, 2 : T2, z = 9 : 32
Represent your answer as abcd, where a, b, c and d represent number from 0 to 9. a, b, c and d
represents the value of "z" in parts (i), (ii) ,(iii) & (iv). Suppose your answer is 1, 2, 3 & 4 then the
same must be filled in OMR sheet as1234.00.
1 1
23. He atom can be excited to 1s 2 p by   58.44 nm. If lowest excited state for He lies 4857
cm1 below the above. Calculate the energy for the lower excitation state.

44 ATOMIC STRUCTURE
EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS
1. If the radius of the hydrogen atom is 53 pm, the radius of the He ion is closest to
[KVPY 2014]
(a) 108 pm (b) 81 pm (c) 27 pm (d) 13 pm
2. Maximum number of electrons that can be accommodated in the subshell with azimuthal
quantum number l = 4, is- [KVPY 2015]
(a) 10 (b) 8 (c) 16 (d) 18
3. The electronic configuration which obeys Hund’s rule for the ground state of carbon atom is-
[KVPY 2016]
(a) (b)
2p
Energy 2s
1s
(c) (d)

ATOMIC STRUCTURE 45
4. The graph that deplets Einstein’s photoelectric effect for a monochromatic source of frequency
above the threshold frequency is- [KVPY 2016]
Photoelectric
Current
Intensity of
(a) radiation (b)
Photoelectric
Current
Intensity of
(c) radiation (d)
5. Helium can be singly ionized by losing one electron to become the He cation. Which of the
following statements is true concerning this helium cation? [NSEC 2014]
(a) The line spectrum of this helium cation will resemble the line spectrum of a hydrogen atom.
(b) The line spectrum of this helium cation will resemble the line spectrum of a lithium atom.
(c) The line spectrum of this helium cation will remain the same as for unionized helium.
(d) The line spectrum of this helium cation will resemble the line spectrum of a hydrogen ion.
6. The magnetic moment of a divalent ion of an element with atomic number 24 in an aqueous
solution is - [NSEC 2014]
(a) 4.90 BM (b) 2.45 BM (c) 2.83 BM (d) 1.73 BM
7. From the following the species that are isoelectronic are [NSEC 2014]
  
(I) NH3  (II) CH3 (III) NH2 (IV) NH4
(a) (I), (II), (III) (b) (II), (III), (IV) (c) (I), (II), (IV) (d) (I), (III), (IV)
8. The set of quantum numbes that cannot be allotted to an electron in an atom is

[NSEC 2014]
1 1
(a) n  3, l  2, m1  2, ms   (b) n  2, l  0, m1  1, ms  
2 2
1 1
(c) n  1, l  0, m1  0, m s   (d) n  4, l  3, m1  0, ms  
2 2
46 ATOMIC STRUCTURE
st nd
9. If the energy of an electron in the 1 and 2 energy levels of an H atom are 13.6 eV and
3.4 eV, respectively, the energy required in eV to excite an electron from the 1st to the 2nd
energy level is - [NSEC 2014]
(a) 17.0 (b) 17.0 (c) 10.2 (d) 10.2
10. If 0 and  are the threshold wavelength and the wavelength of the incident light, respectively on
a metal surface, the velocity of the photoelectron ejected from the metal surface is ( me  mass of
electron, h = Planck’s constant, c = speed of light) [NSEC 2015]
2h   0    2hc  0    2hc  0    2h  1 1 
(a) (b) (c)   (d)   
me me me  0  me   0  
11. The de Brogile wavelength of an object of mass 33 g moving with a velocity of 200ms1 is of the
order of - [NSEC 2015]
31 34 37 41
(a) 10 m (b) 10 m (c) 10 m (d) 10 m
12. Imagine that in any atom about 50% of the space is occupied by the atomic nucleus. If a silver foil
is bombarded with   particles, majority of the   particles would- [NSEC 2015]
(a) be scattered (b) be absorbed by the nuclei
(c) pass through the foil undeflected (d) get converted into photons
13. For an electron whose x  positional uncertainty is 1.0  10 10 m, the uncertainty in the
x  component of the velocity in ms1 will be of the order of [NSEC 2015]
(a) 106 (b) 109 (c) 1012 (d) 1015
14. The energy of an electron in the first Bohr orbit is 13.6 eV. The energy of Be3  in the first
excited state is - [NSEC 2015]
(a) 30.6 eV (b) 40.8 eV (c) 54.4 eV (d) 40.8 eV


ATOMIC STRUCTURE 47
EXERCISE # 06 JEE (MAIN) CORNER
1. According to Bohr’s theory, the angular momentum of an electron in 5th orbit is:
[2006]
h h h h
(a) 25 (b) (c) 10 (d) 2.5
   
2. Uncertainty in the position of an electron  mass 9.1 1031kg moving with a velocity 300ms1 ,
accurate 0.001% will be: [2006]
2 2 2 2
(a) 19.2  10 m (b) 5.76  10 m (c) 1.92  10 m (d) 3.84  10 m
3. The spin only magnetic moment (in Bohr magneton, MB) of Ni2  in aqueous solution would be:
(a) 2.84 (b) 4.90 (c) 0 (d) 1.73
4. Which one of the following sets of ions represents a collection of isoelectronic species: [2006]
  2 3 2 2  2
(a) K , Cl ,Ca , Sc (b) Ba , Sr ,K , Ca
(c) N3  ,O2  ,F ,S2  (d) Li ,Na  ,Mg2  ,Ca 2
5. Which of the following sets of quantum numbers represent the highest energy of an atom? [2007]
(a) n  3,   1, m  1, s  1/ 2 (b) n  3,   2, m  1, s  1/ 2
(c) n  4,   0, m  0, s  1/ 2 (d) n  3,   0, m  0, s  1/ 2
6. The ionization enthalpy of hydrogen atom is 1.312  106 J mol1 . The energy required to excite the
electron in the atom from n = 1 to n = 2 is: [2008]
5 1 5 1
(a) 8.51 10 Jmol (b) 6.56  10 Jmol
(c) 7.56  105 Jmol1 (d) 9.84  105 Jmol1
7. In an atom, an electron is moving with a speed of 600 m/s with an accuracy of 0.005%. Certainity
with which the position of the electron can be located is:
 h  6.6  10 34
kg m2 s1, mass of electron,em  9.1 1031kg :  [2009]
(a) 1.52  10 4 m (b) 5.10  10 3 m

(c) 1.92  10 3 m (d) 3.84  10 3 m
8. Ionisation energy of He is 19.6  1018 J atom1 . The energy of the first stationary state  n  1 of
Li2  is: [2010]
16 1 17 1
(a) 4.41 10 J atom (b) 4.41 10 J atom
(c) 2.2  10 15 J atom1 (d) 8.82  1017 J atom1
48 ATOMIC STRUCTURE
9. The electrons identified by quantum numbers n and l: [2012]

(a) n = 4, l = 1 (b) n = 4, l = 0 (c) n = 3, l = 2 (d) n = 3, l = 1
can be placed in order of increasing energy as:
(a) (c) < (d) < (b) < (a) (b) (d) < (b) < (c) < (a)
(c) (b) < (d) < (a) < (c) (d) (a) < (c) < (b) < (d)
 Z 
10. Energy of an electron is given by E  2.178  10 18 J  2  . Wavelength of light required to excite
n 
an electronin an hydrogen atom from level n = 1 to n = 2 will be:
 h  6.62  10 34
Js and c  3.0  108 ms 1  [2013]
(a) 1.214  10 7 m (b) 2.816  10 7 m

(c) 6.500  10 7 m (d) 8.500  107 m
11. The correct set of four quantum numbers for the valence electrons of rubidium atom (Z=37) is :
[2014]
1 1
(a) 5, 1, 1,  (b) 5, 0, 1, 
2 2
1 1
(c) 5, 0, 0,  (d) 5, 1, 0, 
2 2
12. Which of the following is the energy of a possible excited state of hydrogen? [2015]
(a) 6.8eV (b) 3.4eV (c) 6.8eV (d) 13.6eV
13. A stream of electrons from a heated filament was passed between two charged plates kept as a
potential difference V esu. If e and m are charge and mass of an electron, respectively, then the
h
value of (where  is wavelength associated with electron wave) is given by : [2016]

(a) 2meV (b) meV (c) 2meV (d) meV
14. The radius of the second Bohr orbit for hydrogen atom is : [2017]
34
(Plank’s Const. h  6.6262  10 Js; mass of electron  9.10911031 kg ; charge of electron
e  1.60210 1019 C; permittivity of vacuum 0  8.854185  1012 kg 1m 3 A2 )
(a) 4.76 A (b) 0.529A (c) 2.12 A (d) 1.65A


ATOMIC STRUCTURE 49
EXERCISE # 07 JEE (ADVANCED) CORNER
1. Given in hydrogenic atom rn , Vn , E , K n stand for radius, potential energy, total energy and kinetic
energy in nth orbit. Find the value of U, v, x, y. [2006]

Column I Column II
Vn
(A) U (P) 1
Kn
1
(B)  Ex (Q) –2
rn
(C) rn Zy (Z = Atomic number) (R) –1
(D) v = (Orbital angular momentum of electron in its lowest energy) (S) 0
2. Match the entries in Column I with the correctly related quantum number(s) in Column II.
Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.
[2008]
Column I Column II
(A) Orbital angular momentum of the electron in (P) Principal quantum number
a hydrogen-like atomic orbital
(B) A hydrogen-like one-electron wave function (Q) Azimuthal quantum number
obeying Pauli principle
(C) Shape, size and orientation of hydrogen like (R) Magnetic quantum number
atomic orbitals
(D) Probability density of electron at the nucleus (S) Electron spin quantum number
in hydrogen-like atom
3. Assuming that Hund’s rule is violated, the bond order and magnetic nature of the diatomic
molecule B2 is: [2010]
(a) 1 and diamagnetic (b) 0 and diamagnetic
(c) 1 and paramagnetic (d) 0 and paramagnetic
4. The kinetic energy of an electron in the second Bohr orbit of a hydrogen atom is
 a0 is Bohr radius : [2012]
h2 h2
(a) (b)
4 2 ma02 16 2 ma02
h2 h2
(c) (d)
32 2 ma02 64 2 ma02
50 ATOMIC STRUCTURE
5. The atomic masses of He and Neare 4 and 20 a.m.u., respectively. The value of the de Broglie
wavelength of He gas at 73C is “M” times that of the de Broglie wavelength of Ne at 727C .
M is [2013]
1
6. In an atom, the total number of electrons having quantum numbers n  4, ml  1 and ms   is
2
[2014]
7. Not considering the electronic spin, the degeneracy of the second excited state (n = 3) of H atom
is 9, while the degeneracy of the second excited state of H is [2015]
COMPREHENSION
Answer Q. 8, Q. 9 and Q. 10 by appropriately matching the information given in the three

columns of the following table.
The wave function,  n ,l ,ml is a mathematical function whose value depends upon spherical polar
coordinates  r , ,   of the electron and characterized by the quantum numbers n, l and m1 .
Here r is distance from nucleus,  is colatitude and  is azimuth. In the mathematical functions
given in the Table, Z is atomic number and a0 is Bohr radius.
Column I Column II Column III
(I) 1s orbital (i) 3/ 2 Z  (P)
Z  
 n0 
 n ,l ,m1   e
 a0 
 n,l ,mi r 
0
r / a0
(II) 2s orbital (ii) One radial node (Q) Probability density at nucleus
1

a03
(III) 2 pz (iii) 5/ 2  Z  (R) Probability density is maximum at
Z  
 2 a0 
orbital
 n ,l ,m1   re cos  nucleus
 a0 
(IV) 3d z2 (iv) Xy-plane is a nodal plane (S) Energy needed to excite electron
from n = 2 state to n = 4 state is
27/32 times the energy needed to
excite electron from n = 2 state to
n = 6 state

ATOMIC STRUCTURE 51

8. For He ion, the only INCORRECT combination is : [2017]
(a) (I) (iii) (R) (b) (II) (ii) (Q)
(c) (I) (i) (R) (d) (I) (i) (S)
9. For hydrogen atom, the only CORRECT combination is : [2017]

(a) (II) (i) (Q) (b) (I) (i) (P)
(c) (I) (iv) (R) (d) (I) (i) (S)
10. For the given orbital in Column I, the only CORRECT combination for any hydrogen-like species
is : [2017]
(a) (I) (ii) (S) (b) (IV) (iv) (R)
(c) (II) (ii) (P) (d) (III) (iii) (P)


52 ATOMIC STRUCTURE
ANSWER KEY
ANSWER KEY EXERCISE # 01 OBJECTIVE EXERCISE
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. B B D C C B C C D D
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. D B B B B A A B D A
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. B C B B D B B C C C
Qs. 31 32 33 34 35 36 37 38 39 40
Ans. C C B C B A C C C A
Qs. 41 42 43
Ans. C B C
ANSWER KEY EXERCISE # 02 ADVANCED EXERCISE
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. D C C D B B A A C D
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. B A A D C D B D C A
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. A D B B D B A AC BCD CD
Qs. 31 32 33 34 35 36 37 38 39 40
Ans. AC AB BC ACD ACD AB AD ABC AD ABD
Qs. 41 42 43 44 45 46
Ans. BCD CD ABD CD BC (A) P (B) PQS (C) PR (D) QS
Qs. 47 48
Ans. (A) S; (B) R; (C) Q; (D) P (A) Q (B) S (C) P (D) R
Qs. 49 50
Ans. (A) Q (B) P (C) S (D) R (A) Q (B) S (C) R ( D) P
Qs. 51 52
Ans. (A) S (B) R (C) Q (D) P (A) Q (B) S (C) P (D) R
Qs. 53 54
Ans. (A) PQR (B) PQ (C) S (D) R (A) Q (B) P (C) S (D)R
Qs. 55 56 57 58 59 60
Ans. 2 3 4 2 4 3

ATOMIC STRUCTURE 53
ANSWER KEY EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01)
1. – 1.36 × 10 –19 Joules 2. 4863 Å

3. 1.096 × 10 7 m –1 4. n 1 =1, n 2 =2
5. 1.827 × 10 5 J/mol 6. 1403 KJ/mol

7. 6563 Å ; 1216 Å ; 1026 Å 8. 5.425×10 –12 ergs, 3.7×10 –5 cm
9. 1220 Å 10. 2 ; 9.75 × 10 4 cm –1
11. 10.2 eV , z = 2 12. 292.68×1021 atoms, 162.60×1021 atoms, 832.50 KJ
13. h/ 14. 3.63 ×106m–1
15. 8×106 16. 340 ev , – 680 eV
17. 3.09 × 108 cm/sec 18. Brackett ; 2.63 ×10–4 cm
19. – 13.6 × 32 Ev 20. 2.65  1019 J
21. 319.2 kJ / mol 22. 12 23. 7
24. 3.68 10 65 m 25. 0.0144 m
1. 0.527 2.  = 1900 Å 3. 17 4. 4
5. 5 6. 1.35 105 7. 1022 8. 28 Photons
9. 6235A 10. 1.75 1029 11. 6 ; 489.6 eV , 25.28 Å

n2 h2
12. rn = n = 25 ; 55.2 pm
4 K  2  3e 2  208 me
n6 h6
13. 6.4×10 – 1 3 J, 2.1×10 – 1 3 J, 3.4×10 – 1 4 m 14. E=
384 m3 K 2 e 4  6
15. 910 Å ;U.V. 16. 973.5 Å

17. 4689 Å 18. 303.89 Å , 2.645 × 10 – 9 cm
19. (a) 75 eV ; (b) 1.414 Å ; (c) 2 × 10–14 m
20. Energy of emitted photons can not be greater than 13.6 eV (otherwise He+ will ionise)
therefore single electron specie must be hydrogen energy emitted
= E3 – E1 = –1.51 + 13.6 = 12.09 For He+ ion this energy corresponds to excitation from 2 to 6.
8
21. R  22. 1233.00 23. 3.3 1018 J
9
54 ATOMIC STRUCTURE
ANSWER KEY EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. C D A C A A D B C C
Qs. 11 12 13 14
Ans. B A A C
ANSWER KEY EXERCISE # 06 JEE (MAIN) QUESTIONS
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. D C A A B D C B B A
Qs. 11 12 13 14
Ans. C B C C
ANSWER KEY EXERCISE # 07 JEE (ADVANCED) QUESTIONS
Qs. 1 2
Ans. (A) Q, (B) P, (C) R, (D) S (A) Q, R (B) P, Q, R, S (C) P, Q, R (D) P, Q
Qs. 3 4 5 6 7 8 9 10
Ans. A C 5 6 3 A D C

GASEOUS STATE
INDEX
 CONCEPTS IN BRIEF (GASEOUS STATE) 55 – 77

 SOLVED EXAMPLES 78 – 85
 EXERCISE # 01 OBJECTIVE EXERCISE 86 – 91
 EXERCISE # 02 ADVANCED EXERCISE 92 – 100
 EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS 107 – 108
 EXERCISE # 06 JEE (MAIN) CORNER 109 – 111
 EXERCISE # 07 JEE (ADVANCED) CORNER 112 – 115
 ANSWER KEYS 116 – 118
WEIGHTAGE OF ‘GASEOUS STATE’ IN JEE (MAIN & ADVANCED) in Last Three Years
JEE (MAIN) Formely known as AIEEE
MARK /
YEAR No. Of Qs.
2015 0 0/120
2016 1 4/120
2017 4 16/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2015 1 4/168
2016 1 4/124
2017 1 3/122
GASEOUS STATE
INT RODUCT ION:
A given substance may occur in solid, liquid or gaseous phase depending upon the relative value
of two tendencies namely Mutual Attraction (MA) and Escaping Tendency (ET)
(i) if MA is greater than ET then substance will occur in solid state
(ii) if MA is slightly greater than ET then substance will occur in liquid state
(iii) if MA is very much less than ET then substance will occur in gaseous state
Out of the three states of matter, the most simplest one is the gaseous state.
The state is characterized by sensitivity of volume change with change of pressure and
temperature. It is due to large distance between molecules as compared to their own dimensions.
There exist weak Vander Waal's forces, molecules move independent of each other with speed
about 400 ms–1.
Gases show maximum equality in their behaviour irrespective of their nature.
MEASURABLE PROPERTIES OF GAS:

1. Mass
The gases do possess mass. The mass of gas is generally used in the form of number of moles
which is related as
wt. in gm  w
(i) no. of moles = n = 
molecular mass of gases  M
Two other useful formulae to calculate number of moles of gas are –
no. of molecules of given gas  N 
(ii) number of moles =  n= 
Avogadro's number of molecules  N A 
volume of given gas in litres at STP
(iii) no. of moles =
22.4 L
When container contains more than one gas then molecular mass of mixture is termed as
effective molecular mass (EMM) which is intermediate between molecular masses of all the
gases present in the container.
Total mass of all the gases present in the container
Effective molecular mass =
Total no. of moles of all gases present in the container
2. Volume
Volume of gas is nothing but volume of the container in which it is present.
Relation between different units of volume
1 m3 = 103 dm3 = 103 litre =106 cm3 = 106 ml = 109 mm3.
3. Temperature
Degree of hotness or coldness of a body is measured by temperature
C = K  273 = F  32
100 100 180
C – Celcius scale, K – Kelvin scale, F – Fahrenheit scale
56 GASEOUS STATE
Note : In all the problems of gaseous state (i.e. in all gas law equations), temperature must be
expressed in kelvin scale. i.e. , t °C + 273 = TK
4. Pressure
Force acting per unit area
P= F
A
Units :
CGS : dyne/cm2
MKS : Newton/m2 (1N/m2 = 1Pa)
Relation : 1 N/m2 = 10 dyne/cm2
Units of pressure :
1 atm = 76 cm of Hg = 760 mm of Hg = 760 torr = 1.01325×105 N/m2 = 101.325 kPa
= 1.01325 bar
= 14.7 lb/In2 (Psi)
= 10.33 meters of H2O
MEASUREMENT OF PRESSURE
Barometer :
A barometer is an instrument that is used for the measurement of pressure.The construction of
the barometer is as follows
Cross sectional view of the capillary column

GASEOUS STATE 57
Depending on the external atmospheric pressure, the level of the mercury inside the tube will
adjust itself, the reading of which can be monitored. When the mercury column inside the
capillary comes to rest, then the net forces on the column should be balanced.
Applying force balance, we get,
Patm × A= m×g (‘A’ is the cross-sectional area of the capillary tube)
If ‘  ’ is the density of the fluid, then m=  × g × h (‘h’ is the height to which mercury has risen in
the capillary)
hence, Patm × A = (  × g × h) × A or, Patm =  gh
1 atm, is defined as the pressure exerted by the atmosphere at mean sea level. It comes
out to be 760 mm of Hg = 76 cm of Hg. (at mean sea level the reading shown by the barometer is
76 cm of Hg)
1 atm = (13.6 × 103) 9.8 × 0.76 = 1.013 × 105 Pas.
1 torr = 1 mm of Hg. 1 barr = 105 N/m2 (Pa)
Faulty Barometer : An ideal barometer will show a correct reading only if the space above the
mercury column is vacuum, but in case if some gas column is trapped in the space above the
mercury column, then the barometer is classified as a faulty barometer. The reading of such a
barometer will be less than the true pressure.
For such a faulty barometer
P0A = Mg + Pgas A
P0 =  gh + Pgas or  gh = P0 – Pgas
5. Density
Mass per unit volume d = m
v
Units : CGS : g/cm3
MKS : kg/m3
Relation : 1 kg/m3 = 10–3 g/cm3
Density of gases
Absolute density Relative density
(mass per unit volume) (Relative to hydrogen turned as vapour density)
(i) d= m (i) VD =
molecular mass
v 2
(ii) unit : g/l (ii) No unit
(iii) function of temp., pressure, no. of moles (iii) independent of Pressure , Temperature
58 GASEOUS STATE
Analysis of gaseous mixture :

Vapour density :
Vapour density of any gas is defined as the density of any gas with respect to density of the H2
gas under identical conditions of temperature T and pressure P.
density of gas at T & P
vapour density =
density of H2 under same P & T
m RT RT PM
P= . P=  =
V M M RT
PMgasRT Mgas Mgas
vapour density = = =
RT PMH2 MH2 2
Mgas = 2 × vapour density
Average molecular mass of gaseous mixture :

total mass of the mixture divided by total no. of moles in the mixture
Total mass of mixture
Mmix =
Total no. of moles in mixture
If we have
‘n1’ , ‘n2’ and ‘n3’ are moles of three different gases having of molar mass ‘M1’, ‘M2’ and ‘M3’
n1 M1  n2 M2  n3 M3
respectively. Mmix =
n1  n2  n3
Note : Mass , volume and no. of moles are extensive properties that depend on mass hence then all
divertly additive in nature.
Note : Density, Pressure and Temperature are intensive properties they does not depend on mass
hence they are non-additive in nature.
Boyle’s Law :
Boyle’s law states that , “at constant temperature, the volume of a sample of a gas varies
inversely with the pressure”.
P  1 (when temperature and number of moles are kept constant)
V
P = k or PV = k
V
Boyle’s law can be verified by any one of the following three ways graphically.

GASEOUS STATE 59
The value of the constant depends upon the amount of a gas and the temperature.
Mathematically, it can be written as,
P1V1 = P2V2 = P3V3 = ..............
Location of straight line and curve changes with temperature in the isotherm shown in the
following figure.
According to Boyle’s law, PV = Constant at constant temperature
log P + log V = constant
log P = – log V = constant
Charles law :
For a fixed amount of gas at constant pressure volume occupied by the gas is directly
proportional to temperature of the gas on absolute scale of temperature.
V T or V = kt
V
 constan t where ‘k’ is a proportionality constant and is
T
dependent on amount of gas and pressure.
V1 V2
 Temperature on absolute scale, kelvin scale or ideal gas scale.
T1 T2
By considering –273.15°C as the lowest approachable limit, Kelvin developed temperature scale
which is known as absolute scale.
60 GASEOUS STATE
Calculation of pay load :
Pay load is defined as the maximum weight that can be lifted by a gas filled ballon.
For maximum weight that can be lifted, applying force balance
Fbuoyancy = Mballoon × g + Mpay load × g
 air v.g. =  gas v.g + Mg + mg.
mass of balloon = m net force on
volume of balloon = v balloon = 0
density of air =  air (at equilibrium / when balloon is incoming
density of gas inside the with constant speed)
balloon =  gas
Pressure-Temperature Law : (Gaylussac’s Law)
It relates the pressure and absolute temperature of a given mass of a gas at constant volume.
Volumes remaining constant, the pressure of given mass of a gas increases or decreases by
1 of its pressure at 0°C per degree change of temperature.
273
P t  273  t 
Pt = P 0 + 0
273
or Pt = P0 1  t
273 or Pt = P0 
 273
T
 = P0 T
 0
Pt P0
or  or P  T (if volume and number of moles are kept constant)
T T0
At constant volume, the pressure of a given amount of a gas is directly proportional to its absolute
temperature.
Avogadro’s Law
(i) For Solid, liquid and gas

1 mole of any substance contains Avogadro’s number (NA) of molecules/atoms/particles etc.
NA = 6.023 × 1023
(ii) For gases:
In 1812, Amadeo Avogadro stated that samples of different gases which contain the same
number of molecules (any complexity, size, shape) occupy the same volume at the same
temperature and pressure. It follows from Avogadro’s hypothesis that V  n (T and P are
constant).
V  n (T, P constant) V1 V2
 
n1 n 2
STP : 273.15 K 1 atm
SATP : 298.15 K 1 bar

GASEOUS STATE 61
Ideal Gas Equation
Combining all these gas laws , a simple equation can be derived at, which relates P , V , n
and T for a gas
PV = nRT (for n moles of gas)
P1 V1 PV
= 2 2 (Combined gas law)
T1 T2
P is the pressure of the gas and can be expressed in atm or Pa . Correspondingly , the volume
must be expressed in litres or m3 respectively. n is the number of moles and T is the
temperature in Kelvin. R is called the universal gas constant.
Numerical Values of R
(i) In litre atmosphere = 0.0821 litre atm deg–1 mole–1
(ii) In ergs  8.314  107 erg deg1 mole 1
(iii) In jouls = 8.314 jouls deg–1 mol–1

(iv) In calories  1.937 cal deg1 mole 1
Relation between Molecular Mass and Gas Densities

w
(1) Actual density : For an ideal gas PV = nRT or PV  RT , where w = mass of the gas in gms
M
and M = Molecular wt. in gms.
w w
 PM  RT or PM =  RT, (where  is the density of the gas =
V V
PM
ρ
RT
d1 T1 d2 T2
(i) = (for same gas at different temperatrue and pressure)
P1 P2
d1 M
(ii) = 1 (for different gases at same temperature & pressure)
d2 M2
(Where d = density of gas)
(2) Vapour Density: For gases another term which is often used is vapour-density. Vapour density
of a gas is defined as the ratio of the mass of the gas occupying a certain volume at a certain
temperature and pressure to the mass of hydrogen occupying the same volume at the same
PVM
temperature and pressure i.e. W (gas) =  .
RT
PV  2
and WH2  ( mol. wt. of hydrogen is 2)
RT
Wgas M
  (Vapour density of gas)
WH2 2
Vapour density of a gas is same at any temperature, pressure and volume.
62 GASEOUS STATE
Dalton’s Law of Partial Pressures:
The total pressure of a mixture of non-reacting gases is equal to the sum of their partial
pressures.
By Dalton’s Law PT = P1 + P2 + ..............
By the partial pressure of a gas in a mixture is meant, the pressure that the gas will exert if it
occupies alone the total volume of the mixture at the same temperature.
Derivation: n = n1 + n2 + …
PV PV P1V P2 V
n  n    ....  P = P1 + P2 + …
RT RT RT RT
Assumption: Volume of all the gases is same as they are kept in same container.
Relationship between partial pressure and number of moles

Important formula
 n1 
(i) P1    P  x1P where x1 = mole fraction of gas
 n1  n2 
Volume of the gas
(ii) Partial pressure of a gas in the mixture  P
Total Volume
Partial pressure and aqueous tension: Dalton’s law is used to calculate the pressure of a dry
gas when it is collected over water at atmospheric pressure.
By Dalton’s law,
Pressure of dry gas = atmospheric pressure - aqueous tension
Aqueous tension depends on temperature. It increases with temperature and becomes 760 mm
at 100°C.
Graham’s Law of Diffusion
Diffusion is the tendency of any substance to spread throughout the space available to it.
Diffusion will take place in all direction and even against gravity.
The streaming of gas molecules through a small hole is called effusion.
According to Graham, the rate of diffusion (or effusion) of a gas at constant pressure and
temperature is inversely proportional to the square root of its molecular mass.
, at constant P and T , at constant P and T
Since molecular mass of gas = 2 × vapour density, , at constant P and T

GASEOUS STATE 63
The rate of diffusion (or effusion) r of two gases under different pressure can be given by
r1 M2 P1
  at constant T only.
r2 M1 P2
Therefore, according to Graham’s law of diffusion (effusion) at constant P and T.
d1 and d2 are the respective densities and V1 and V2 are volumes diffused (effused) in time t1
and t2 .
where n1, n2 are moles diffused (effused) in time t1 and t2.
where x1 and x2 are distances travelled by molecules in narrow tube in time t1 and t2.
moles diffused
r=
time taken
dis tance travelled in a narrow tube
=
time taken
pressure drop I
=
pressure drop II
Note: It should be noted that the rate of diffusion or effusion actually depends on pressure difference of
the gas and not simply on its pressure. Moreover the pressure difference is to be measured for
this gas only i.e. if a container holds [He] at a pressure of 0.1 atm and if a small pin-hole is made
in the container and if the container is placed in a room, then the rate of effusion of He gas from
the container to outside depends only on its pressure difference, which is 0.1-0 (as their is no He
in the atmosphere). This implies that the diffusion of a gas is not dependent on the diffusion of
any other gas.
Whenever we consider the diffusion of gas under experimental conditions, we always assume
that the gas diffuses in vacuum and during the time period for which the diffusion is studied the
rate of diffusion (or the composition of diffusing or effusing mixture of gases) remains constant.
64 GASEOUS STATE
The Kinetic Theory of Gases :
In order to derive the theoretical aspect of the various gas laws based on simple experiment
facts, Maxwell proposed the following postulates under the heading of kinetic theory of gases:
The postulates of kinetic theory of gas are
(i) Each gas is made up of a large number of small (tiny) particles known as molecules.
(ii) The volume of a molecule is so small that it may be neglected in comparison to total volume of
gas.
(iii) The molecules are never in stationary state but they are believed to be in chaotic (random)
motion. They travel in straight line in all possible directions with altogether different but constant
velocities. The direction of motion is changed by the collision with container or with the other
molecules.
(iv) The collision between molecules is perfectly elastic i.e., there is no change in the energies of the
molecules after collision.
(v) The effect of gravity on molecular motion is negligible.
(vi) The kinetic energy of the gases depends on the temperature.
(vii) The pressure of the gas arises due to collision of molecules with the walls of the container.
The Kinetic Equation :
Maxwell also derived an equation on the basis of above assumptions as

1
PV = mNu2 where
3
P = Pressure of gas
V = Volume of gas
m = mass of one molecule of gas
N = no. of molecules of gas
u = root mean square velocity of molecules
For 1 mole N= NA (Avogadro number)
m × NA = Molecular mass M.
3PV 3RT
 or u 
M M
Derivation
m = mass of one molecule

U = Ux î + Uy ĵ + Uz k̂
Consider collision with ABCD
 
inital Pi = mUx î ; final Pf = – mUx î
change in momentum due to collision = 2 Ux m
2
time taken between two successive collision with force ABCD = t =
Ux
1 U
frequency of collision = = x
t 2

GASEOUS STATE 65
Ux  Ux mU2x
change in momentum in one sec. = force = 2 m =
2 
m 2
force due to all the molecules = {Ux1  U2x2  ........  UxN2 }

Ux12  U2x2  ...........U2xN
average value of UN2 = UN2 =
N
M
Fx = {N U2x }

all the three direction are equal as the motion is totally random in all directions, hence
U2x = U2y = U2z
2 2 2 2
U2 = Ux  Uy  Uz = 3 Ux
M 1
Fx = .N U2
 3
Fx 1 N 2
Pressure = = U The volume of the container ‘v’ = l3
 2
3 3
1
PV = mN U2 Kinetic equation of gases
3
where U2 is mean square speed
 U12  U22  U32  ......UN2 

root mean square speed = Urms = U2 =  
 N 
Verification of Gaseous Laws Using Kinetic Equation :

1
(i) From postulates ; PV = mN U2
3
1
m U2  T =  T Where ’  ‘ is a proportionality constant
2
2 1 2 2
PV =  mU  N ; PV =  NT
3 2  3
(ii) Boyle’s Law : N : constant
T : constant
PV = constant
(iii) Charles law : N : constant
P : constant
VT
(iv) Kinetic energy of gaseous molecule (translation K.E.)
To calculate  we have to use ideal gas equation (experimental equation)
PV = nRT
66 GASEOUS STATE
2 2
kinetic equation PV =  nRT =  (nNA) T
3 3
3 R
on comparing  = ×
2 NA
3 R
 = K where K = = Boltzmann constant
2 NA
1
Average K.E. of molecules = m U2 =  T
2
3
Average K.E. = KT (only dependent on temperature not on nature of the gas.)
2
1  3 3
Average K.E. for one mole = NA  m U2  = K NA T = RT
 2  2 2
(v) Root mean square speed
3kT 3R T
Urms = U2 = = Where m-mass of one molecule
m mNA
(vi) Dependent on nature of gas i.e mass of the gas
3R T
Urms = molar mass must be in kg/mole.
M
Distribution of Molecular Velocities: tion of Molecular Velocities

Maxwell and Boltzmann proposed that gas molecules are always in rapid random motion colliding
with each other and with the walls of container. Due to such collisions, their velocities always
changes. A fraction of molecules have a particular molecular velocity at a time. James Clark
Maxwell calculated the distribution of velocity among fraction of total number of molecules, on the
basis of probability.
The distribution of velocities of different gas molecules may be shown by the following curve.
From the curve it may be concluded that

(i) Only a small fraction of molecules have either very low or very high velocity.
(ii) Curve becomes flat when temperature is raised i.e. distribution around average velocity becomes
wider. Average molecular velocity increases with rise in temperature.
(iii) Most of the molecules have velocity close to most probable velocity represented by the top of
curve.
(iv) At higher temperature greater number of molecules have high velocity, while few molecules have
lower velocity.

GASEOUS STATE 67
Average Velocity :
As per kinetic theory of gases, each molecule is moving with altogether different velocity. Let ‘n’
molecules be present in a given mass of gas, each one moving with velocity u1,u2, u3, …,un.
The average velocity or Uav = average of all such velocity terms.
8RT
Average velocity = Uav 
πM
Root Mean Square Velocity :
Maxwell proposed the term Urms as the square root of means of square of all such velocities.
3RT
Also U rms 
M
2RT
Most probable velocity: It is the velocity possessed by maximum no. of molecules. U mpv 
M
8
Furthermore = 2: : 3 = 1 : 1.128 : 1.224
π
Also
Kinetic Energy of Gas:
As per kinetic equation PV = .
For 1 mole m × n = Molecular Mass (M)
 or
Also KE per molecule . Where k is the Boltzmann constant
Kinetic Energy of gas sample :
3 R 3
(i) Average kinetic energy of a single molecule = . T = KT
2 N 2
K = boltzman constant = 1.38 × 10–23 J/deg
3
(ii) Total Kinetic Energy for one mole of gas = RT
2
3
(iii) Kinetic Energy for n mol of gas = n × RT
2
68 GASEOUS STATE
Deviations from ideal behaviour
An ideal gas is one which obeys the gas laws of the gas equation PV = RT at all pressure and
temperatures. However no gas in nature is ideal. Almost all gases show significant deviations
from the ideal behaviour. Thus the gases H2, N2 and CO2 which fail to obey the ideal-gas
equation are termed as non-ideal or real gases.
Real gases :
(i) Real gases do not obey the ideal gas laws exactly under all conditions to temperature
and pressure.
(ii) Real gases deviates from ideal behaviour because
(iii) Real gaseous molecules have a finite volume.
{since on liquefaction real gases occupy a finite volume}
(iv) Inter molecular attraction focus between real gas molecules is not zero.
{Real gases can be converted into liquid where as ideal gases cant be}
(v) Deviation of real gases from ideal behaviour can be measured by using compresibility factor :
(Z)
(PV)real
Z= (PV)ideal = nRT
(PV)ideal
PV PVm
Z= = (VM is volume of one mole)
nRT RT
Vm
Z=
Vm ideal
Compressibility Factor :
The extent to which a real gas departs from the ideal behaviour may be depicted in terms of a
new function called the compressibility factor, denoted by Z. It is defined as
PV
Z
nRT
The deviations from ideality may be shown by a plot of the compressibility factor Z, against P.
For an ideal gas, Z = 1 and it is independent of temperature and pressure.
The deviations from ideal behaviour of a real gas will be determined by the value of Z being
greater or less than 1.
The difference between unity and the value of the compressibility factor of a gas is a measure of
the degree of non ideality of the gas.
For a real gas, the deviations from ideal behaviour depends on :
(i) pressure ; and (ii) temperature.
This will be illustrated by examining the compressibility curves of some gases discussed below
with the variation of pressure and temperature.

GASEOUS STATE 69
Effect of Pressure Variation on Deviations:
Effect of Temperature on Deviations:
From the above curves we can conclude that:

1. At low pressure and fairly high temperatures, real gases show nearly ideal behaviour and the
ideal-gas equation is obeyed.
2. At low temperatures and sufficiently high pressures, a real gas deviates significantly from ideality
and the ideal-gas equation is no longer valid.
3. The closer the gas is to the liquefication point, the larger will be the deviation from the ideal
behaviour.
Greater is the departure of Z from unity, more is the deviation from ideal behaviour.
(i) When Z < 1, this implies that gas is more compressible.
(ii) When Z > 1, this means that gas is less compressible.
(iii) When Z = 1, the gas is ideal.
Vander Waals Equation of State for a Real Gas:

The equation of state generated by Vander Waals in 1873 reproduces the observed behaviour
with moderate accuracy. For n moles of gas, the Vander Waals equation is
 n2a 
 P  2  (V – nb) = nRT
 V 
where a and b are constants characteristic of a gas. This equation can be derived by
considering a real gas and converting it to an ideal gas.
1). Volume correction :

Ideal gas equation : Pi Vi = nRT ; In the equation ‘Vi’ stands for the volume which is available for
free movement of the molecules.
Videal = volume available for free movement of gasesous molecule
hence, Vi = V – {volume not available for free movement}
70 GASEOUS STATE
For an ideal gas , Vi = V {V = volume of container}

but for a real gas
Vi  V , as all the volume is not available for free movementbe thought of, as an ideal gas in a
container of volume (V – nb)
Molecules have finite volume :

1 4 3
Excluded volume per molecule =   (2r)  = Co-volume per
2  3 
molecule.
The volume that is not available for free movement is called
excluded volume.
let us see, how this excluded volume is calculated.
For example 2, the entire shaded region is excluded, as its centre
of mass cannot enter this region.
If both molecules were ideal, then they would not have experienced any excluded volume but not
in the case, of real gas as the centre of mass of ‘2’ cannot go further.
Hence for this pair of real gas molecules.
1 4 3 4 3 
Excluded volume per molecule =   (2r)  = 4   r 
2 3  3 
4 
= excluded volume per mole of gas b = NA 4   r 3 
3 
= 4 x NA x Volume of individual molecule

for n moles excluded volume = nb
Vi = V – nb, volume correction
Pressure Correction :
Let us assume that the real gas exerts a pressure P. The molecules that exert the force on the
container will get attracted by molecules of the immediate layer which are not assumed to be
exerting pressure.
It can be seen that pressure the real gas exerts would be less than the pressure an ideal gas
would have exerted. Therefore if a real gas exerts a pressure P, then an ideal gas would exert a
pressure equal to P + p(p is the pressure lost by the gas molecules due to attractions). This small
pressure p would be directly proportional to the extent of attraction between the molecules which
are hitting the container wall and the molecules which are attracting these.
Therefore (concentration of molecules which are hitting the container’s wall)

GASEOUS STATE 71
(concentration of molecules which are attracting these molecules )
an 2
p
V2
where a is the constant of proportionality which depends on the nature of gas. Higher value of ‘a’
reflects the increased attraction between gas molecules.
The Vander Waals constant b (the excluded volume) is actually 4 times the volume of a single
molecule. i.e. b = 4 NAV where NA 
 Avogadro number.
b = 4 × 6.023 × 1023 , where r is the radius of a molecule.
The constant a and b:
Vander Waals constant for attraction (a) and volume (b) are characteristic for a given gas. Some
salient features of ‘a’ and ‘b’ are:
(i) For a given gas Vander Waal’s constant of attraction ‘a’ is always greater than Vander Waals
constant of volume (b).
(ii) The gas having higher value of ‘a’ can be liquified easily and therefore H2 and He are not liquified
easily.
(iii) The units of a = litre2 atm mole–2 and that of b = litre mole–1
(iv) The numerical values of a and b are in the order of 10–1 to 10–2 to 10–4 respectively.
(v) Higher is the value of ‘a’ for a given gas, easier is the liquification.
Explanation of deviation by Vander Waals equation
1. AT LOW PRESSURE (at separate temp.)

At low pressure Vm will be high.
a
Hence b can be neglected in comparision to Vm. but 2 cant be neglected as pressure is low,
Vm
Thus equation would be
 a 
 P  2  Vm = RT
 Vm 
a
PVm + = RT
Vm
PVm a
+ =1
RT VmRT
a
Z=1– Z<1
VmRT
Real gas is easily compressible in comparision to an ideal gas.
72 GASEOUS STATE
2. AT HIGH PRESSURE (moderate temp.)

VM will be low
so b cant be neglected in comparision to Vm
a
but can be neglected in comparision to much high values of P.
Vm2
Then vander Wall equation will be
P(Vm – b) = RT
PVm – Pb = RT
PVm Pb
= +1
RT RT
Pb
Z= +1 Z>1
RT
If Z > 1 then gas is more difficult to compress in comparision to an ideal gas.
3. At low pressure and very high temperature.

Vm will be very large
a
hence ‘b’ can be neglected and can also be neglected as Vm is very large
Vm2
PVm = RT (ideal gas condition)
4. For H2 or He a ~ 0 because molecules are smaller in size or vander wall forces will be very
weak, these are non polar so no dipole-dipole interactions are present in the actions.
P(Vm – b) = RT
Pb
So, Z=1+
RT
5. ‘a’ factor depends on inter molecular attraction forces. ‘a’ factor for polar molecule > ‘a’ factor for
non polar molecule.
6. For non polar molecules :
Greater the size surface area greater will be vander wall forces so greater will be ’a’ constant.
More ‘a’ factor means high boiling point.
7. Liquefaction pressure :
Is the pressure required to convert gas into liquid.
for easy liquefaction a  and P 
When Z < 1, Vm < Vm, ideal  easily liquifiable
Z < 1, Vm < Vm, ideal  more difficult to compress.
8. b is roughly related with size of the molecule. (Thumb rule)
4 
b = NA 4   r 3 
 3 

GASEOUS STATE 73
Dieterici Equation :
P (V - nb) = n R T ea/VRT (for ‘n’ mole of a gas)
Berthelot Equation :
 n 2a 
 P  
2  (V - nb) = n R T
 T V 
Virial Equation of state :

It is a generalised equation of gaseous state all other equation can be written in the form of virial
equation of state.
 1 
Z is expressed in power series expansion of P or  
 Vm 
B C D
Z=1+ + 2 + 3 + .....................
Vm Vm Vm
B – second virial coefficient , C – third virial coefficient , D – fourth virial coefficient
Vander wall equation in virial form :

 a 
 P  2  (Vm – b) = RT
 Vm 
RT a
P= – 2
(Vm  b) Vm
PVm Vm a
Z= = –
RT (Vm  b) Vm RT
1 a
= –
(1  b / Vm ) Vm RT
1
= 1 + x + x2 + x3 + ..........
1 x
 b b2 b3  a 1  a  b2 b3
Z = 1   2  3  .........  – =1+  b   + + + .................
 Vm Vm Vm  Vm RT Vm  RT  Vm2 Vm3
comparing with virial equation
according to vander walls equation
a
B=b– , C = b2, P = b3
RT
at low pressure : Vm will be larger
1 1
hence , 3 ................ can be neglected
Vm2 Vm
1  a 
Z=1+ b  
Vm  RT 
74 GASEOUS STATE
 a  a
If b   =0  at T=
 RT  Rb
Z=1 (ideal gas)
a
so at Z = gas will behave an ideal gas (or follows boyle’s law)
Rb
a
But at constant temperature ideal gas equation is obeying Boyle’s law as T = , so the temp is
Rb
called Boyle’s temp.
a
TB =
Rb
a
Z=1–
Vm RT
for a single gas if we have two graphs as above we must conclude T2 < T1 at Boyle’s
temperature ‘a’ factor is compensated by factor so Z = 1.
Critical constant of a gas :
When pressure is incerases at constant temp volume of gas decreases

AB  gases
BC  vapour + liquid
CD  liquid
critical point : At this point all the phydical properties of
liquid phase will be equal to phsical properties in vapour
such as
density of liquid = density of vapour
T C or critical temp :
Temperature above which a gas can not be liquidied
PC or critical pressure :
minimum pressure which must be applied at critical temp to convert the gas into liquid.
VC or critical volume :
volume occupied by one mole of gas at TC & PC
a
PC =
27b2

GASEOUS STATE 75
Critical constant using vander wall equations :

 a 
 P  2  (Vm – b) = RT
 Vm 
( PVm2  a ) (Vm – b) = RT Vm2
PVm3 + aVm – PbVm2 – ab – RTVm2 = 0
 RT  a ab
Vm3 + Vm2  b   + Vm – =0
 P  P P
Cubic can hence there will be three roots of equation at any temperature of pressure.
At critical point all three roots will coincide and will give singles dx = VC
at critical point Vander Waal equation will be
 RT  a ab
Vm3 – Vm2  b  C  + Vm – =0 ...(1)
 PC  PC PC
But at critical point all three roots of the equation should be equal, hence equation should be :
Vm3 – 3Vm2 VC + 3Vm VC2 – VC3 = 0 ...(2)
comparing with equation (1)

RTC
b+ = 3VC ....(i)
PC
a
= 3 VC2 ...(ii)
PC
ab
= VC3 ...(iii)
PC
a a a
PC = substituting PC = =
3 VC2 3 (3b)2 27b2
RTC
by (i) = 3 VC – b = 9b – b = 8b
PC
8a
TC =
27Rb
At critical point, the slope of PV curve (slope of isotherm) will be zero
 P 
  =0 ...(i)
 Vm TC
at all other point slope will be negative
O is the maximum value of slope.
  P 
  =0 ....(ii)
Vm  Vm T
C
76 GASEOUS STATE
{Mathematically such points an known as point of inflection (where first two duivation becomes
zero)}
using the two TC PC and VC can be calculate
by
By any two a can be calculated but a by VC and TC and a by TC and PC may differ as these
values are practical values and VC can’t be accuratly calculated so whwn we have VC TC & PC
given use PC & TC to deduce ‘a’ as thet are more reliable.
Reduced Equation of state :
Reduced Temp : Temperature in any state of gas with respect to critical temp of the gas
T
Tr =
TC
P
Reduced pressure : Pr =
PC
Vm
Reduced volume : Vr =
VC
 a 
Vander wall equation  P  2  (Vm – b) = RT
 Vm 
 a 
Substitute values :  Pr PC  2 2  (Vr VC – b) = R Tr TC
 Vr VC 
Substitute the value of PC TC and VC
 a  a a  8a
 Pr P
2   r 2
 2 2 
(3b Vr – b) = RTr
 27b   27b Vr (3b)  27Rb
 Pr 1 8R Tr
   (3 Vr – 1) =
 3 Vr  3
 3 
 Pr  2  (3Vr – 1) = 8 Tr Reduced equation of state
 Vr 
Equation is independent from a, b and R so will be followed by each and every gas independent
of its nature.

GASEOUS STATE 77
Mean free path

d1  d2  ..........  dn 3
 =  (  = coefficient of viscosity)
n Pd
Average velocity / RMS velocity kT
 =
collisionnumber or frequency 2  2 P
k = Boltzman constant ;  = collision diameter.
Collision frequency (z) : no. of collision taking place per second per unit volume.
Collision diameter : Closest distance between the centre of two molecule which are
participating in collision.
Relative Humidity (RH) :

At a given temperatrue
Partial pressure of water vapour in air at T
RH =
vapour pressure of water at T
Loschmidth Number
The number of molecules present in 1 cc of gas (or) vapour at STP.
value : 2.617 × 1019/cc
Eudiometry : The analysis of gaseous mixtures is called eudiometry. The gases are identified by
absorbing them in specified and specific reagents.
Some Common Facts :

(i) Liquids and solutions can absorb gases.
(ii) If a hydrocarbon is burnt gases liberated will be CO2 & H2O. [H2O is seperated out by cooling
the mixture & CO2 by absorption by aqueous KOH]
(iii) If organic compound contains S or P then these are converted into SO2 & P4O10 by burning the
organic compound.
(iv) If nitrogen is present then it is converted into N2.
[The only exception : if organic compound contains – NO2 group then NO2 is liberated]
(v) If mixture contains N2 gas & this is exploded with O2 gas, do not assume any oxide formation
unless specified.
(vi) Ozone is absorbed in turpentine oil and oxygen in alkaline pyragallol.
78 GASEOUS STATE
SOLVED EXAMPLES
Ex. 1 The reading of a faulty barometer is 700 mm of Hg. When actual pressure is 750 mm of Hg. The
length of the air column trapped in this case is 10 cm .Find the actual value of the atmospheric
pressure when reading of this barometer is 750 mm of Hg. Assume that the length of the
Barometer tube above mercury surface in the container remains constant.
Sol. P0 = Pgas + 700 rg
Pgas = 750 rg – 700 rg = 50 rg
Now for the gas column in the capillary, amount and temp are
constant hence
P1V2 = P2 V2
(50 rg) (100 A) = Pgas × (50 A), Pgas = 100 rg
Now, applying force balance in the new scenario.
Patm = Pgas + 750 rg = 100 rg + 750 rg = 850 rg

Hence, the atmospheric pressure is now, 850 cm of Hg.
Ex. 2 In each of the following examples, find the pressure of the trapped gas.
Sol. Total pressure of gas column

= 75 + 10 = 85 cm of Hg.
Ex. 3
Sol. Pgas = 65 cm of Hg.

GASEOUS STATE 79
Ex.4
Pg = 75 + 10 sin q.
Sol. From the above problem, it can be generalised that, applying force balance every single time is
not necessary. If we are moving up in a fluid, then substract the vertical length, and while moving
down add the vertical length.
Ex.5 The diameter of a bubble at the surface of a lake is 4 mm and at the bottom of the lake is 1 mm. If
atmospheric pressure is 1 atm and the temperature of the lake water and the atmosphere are
equal. what is the depth of the lake ?
(The density of the lake water and mercury are 1 g/ml and 13.6 g/ml respectively.
Also neglect the contribution of the pressure due to surface tension)
Sol. P1V1 = P2V2
4 4
(760 mm × 13.6 × g) p (4 mm/2)3 = (760 mm × 13.6 × g + h × 1 × g) p (1 mm/2)3
3 3
760 × 13.6 × 64
= (760 × 13.6 + h)
h = 64 × 760 × 13.6 – 760 × 13.6
h = 63 × 760 × 13.6 mm
63  760  13.6
h= km
1000  1000
= 0.6511 km
= 651.1 m Ans.
Ex.6 A gas column is trapped between closed end of a tube and a mercury column of length (h) when
this tube is placed with its open end upwards the length of gas column is (l1) the length of gas
column becomes (l2) when open end of tube is held downwards. Find atmospheric pressure in
terms of height of Hg column.
80 GASEOUS STATE
Sol. For gas P1 = (PO + h) P2 = (PO – h)
V1 = p r2l1 V2 = p r2l2
at const T. and moles.
P1V1 = P2V2 ; (PO + h) p r2l1 = (PO – h) p r2l2
POl2 + hl1 = POl2 – hl2
POl2 – Pol1 = hl, + hl2
h(  1   2 )
P0 = cm of Hg column Ans.
( 2   1 )
Ex.7 A gas is present at a pressure of 2 atm. What should be the increase in pressure so that the
volume of the gas can be decreased to 1/4th of the initial value if the temperature is maintained
constant.
Sol. PV = constant for a given mass of gas at constant pressure
Þ P1V1  P2 V2 P1  2atm V1 = V V2 = V/4 P2 =?
V
Now, 2  V  P2   P2 = 8 atm
4
 Pressure should be increased from 2 to 8 atm
 total increase = 8 – 2 = 6 atm.
Ex.8 A balloon of diameter 20 metre weights 100 kg. Calculate its pay-load, if it is filled with He at 1.0
atm and 27ºC. Density of air is 1.2 kg m–3. [R = 0.0082 dm3 atm K–1 mol–1]
Sol. Weight of balloon = 100 kg = 10 × 104 g

3
4 3 4 22  20 
Volume of balloon = r     100 
3 3 7  2 
= 4190 × 106 cm3 = 4190 × 103 litre
PVM  w 
Weight of gas (He) in balloon =  PV  RT 
RT  M 
1 4190  103  4
= = 68.13 × 104 g
0.082  300
Total weight of gas and balloon
= 68.13 × 104 + 10 × 104 = 78.13 × 104 g
1.2  4190  106
Weight of air displaced = = 502.8 × 104 g
103
Pay load = wt. of air displaced – (wt. of balloon + wt. of gas)
Pay load = 502.8 × 104 – 78.13 × 104 = 424.67 × 104 g

GASEOUS STATE 81
Ex.9 Some spherical balloon each of volume 2 litre are to be filled with hydrogen gas at one atm &
27°C from a cylinder of volume V litres. The pressure of the H2 gas inside the cylinder is 20 atm
at 127°C. Find number of balloons which can be filled using this cylinder. Assume that temp of
the cylinder is 27°C.
P1V1 PV 1 x  2 60
Sol. = 2 2 = =x x = 30 balloons
T1 T2 300 2
Ex.10 An open vessel at 27°C is heated until 3/5th of the air in it has been expelled. Assuming that the
volume of the vessel remains constant find
(A) the air escaped out if vessel is heated to 900K.
(B) temperature at which half of the air escapes out.
Sol. One should clearly note the fact that on heating a gas in a vessel, there are the number of moles
of gas which go out, the volume of vessel remains constant.
Let initial no. of moles of gas at 300 K be ‘n’. On heating 3/5 moles of air escape out at
temperature T.
 3  2n
 Moles of air left at temperature T   n  n  
 5  5
(A) On heating vessel to 900 K, let n1 moles be left,
1 n 2
n1T1 = n2T2  n1  900  300  n  n1  n  moles escaped out = n   n moles
3 3 3
(B) Let n/2 moles escape out at temperature T, then
n
n1 T1 = n2 T2   T  n  300
2
 T = 600 K
Ex.11 When 3.2 g of sulphur is vapourised at 450°C and 723 mm pressure, the vapours occupy a
volume of 780 ml. What is the molecular formula of sulphur vapours under these conditions?
Calculate the vapour density also.
723 780 3.2
Sol. PV = nRT  × = × 0.082 × 723
760 760 M
M = 255.9
M
no. of catoms of sulpher in one molecule = =8
32
Molecular formula of sulphur = S8
M 255.9
V. D. = =  127.99
2 2
Ex.12 A gaseous mixture contains 55% N2, 20% O2, and 25% CO2 by mass at a total pressure of 760
mm. Calculate the partial pressure of each gas.
Sol. Total mass of the gases = 100 g
82 GASEOUS STATE
WN2 = 55g, WO2 = 20 g, WCO2 = 25g
nN2 = 55/28 = 1.964, nO2 = 20/32 = 0.625, nCO 2 = 25/44 = 0.568
Total moles = 3.157
Ex.13 The stop cock connecting the two bulbs of volume 5 litre and 10 litre containing as ideal gas at 9
atm and 6 atm respectively, is opened. What is the final pressure if the temperature remains
same.
Sol. After the opening of the stop cock the pressure of the each bulb will remain same.
10 x 6
At the beginning, the no. of moles of gas in A =
RT
5x9
At the beginning, the no. of moles of gas in B =
RT
105
total no. of mole at the beginning =
RT
Total no. of mole of gas before opening the stop cock
105
= total no. of moles of gas after opening stop cock =
RT
105 RT 105
pressure after the opening of the stop cock P = x = = 7 atm
RT Vtotal 10  5
Ex.14 Pure O2 diffuses through an aperture in 224 seconds, whereas mixture of O2 and another gas
containing 80% O2 diffuses from the same in 234 sec under similar condition of pressure and
temperature. What is molecular wt. of gas?
Sol. The gaseous mixture contains 80% O2 and 20% gas.
 Average molecular weight of mixture … (i)
Now for diffusion of gaseous mixture and pure O2
or … (ii)
 By (i) and (ii) mol weight of gas (m) =46.6.

GASEOUS STATE 83
Ex.15 In is a tube of length 5 m having 2 idendical holes at the opposite ends. H2 & O2 are made to
effuse into the tube from opposite ends under identical conditions. Find the point where gases will
meet for the first time.
r1 ax dt m2 dx1 32
Sol. = × = = =
r2 dt dx m1 dx 2 2
dx1 dis tance travelled by H2
=4  =4
dx 2 dis tance travelled by O2
x
=4
(5  x)
x=4 from H2 side
Ex.16 (i) Calculate the pressure exerted by 1023 gas molecules, each mass 10–22 g in a container of
volume one litre. The rms velocity is 105 cm/sec.
(ii) What is the total kinetic energy (in cal) of these particles?
(iii) What must be the temperature?
Sol. (i) Here N = 1023 molecules m = 10–22g , V = 1L = 1000 cm3
rms velocity = 105 cm/second
1
PV = Nm U2
3
1
P= Nm U2
3
1
= × 1023 × 10–22g × (105)2cm2/s2
3  1000cm3
= 3.33 × 107 dyne/cm2 Ans.
1
(ii) Total K . E of the molecules = Nm U2
2
1
= × 1023 × 10–25 kg × (103m/s)2
2
10000J
= = 5000 J  1195.0 Cal Ans.
2
1 2 3
(iii) Avg K . E of one molecule = U = kT
2 2
2
T=
1
×
mU2
=
1
×
 
10–25 Kg  103 m / s  6.023  1023 
K  k 
R 

3 k 3 8.314  NA 
= 2414.8 K Ans.
84 GASEOUS STATE
Ex.17 Calculate the average and total kinetic energy of 0.5 mole of an ideal gas at 0°C.
3 3
Sol. Average kinetic energy = KT = ×1.38 ×10–23 × 273 = 5.65× 10–21J
2 2
3 3
Total kinetic energy of n mole of gas = n × RT = 0.5 × × 8.314 × 273
2 2
= 1.702kJ
Ex.18 The compressibility factor for 1 mole of a van der Waals gas at 0ºC and 100 atm pressure is
found to be 0.5. Assuming that the volume of a gas molecule is negligible, calculate the van der
Waals constant, a.
Sol. For 1 mole of the gas,
pV 100  V
Z= Þ 0.5 = ; V = 0.112 L
RT .0821 273 '
 a 
Neglecting b, van der Waals equation reduces to  P  2  V = RT
 V 
a
or pV + = RT
V
a
or 100 × 0.112 + = .0821 × 273
0.112
a = 1.25 L2atm mol–2
Ex.19 The vander waals constant for HCI are a = 371.843 KPa and b = 40.8 cm3 mol–1 find the critical
constant of this substance.
a
Sol. The critical pressure, PC =
27b2
371.843 103
=
27  (40.8)2 10 6
371.843 109
= = 8.273 x 106
27  (40.8)2
Pa = 8.273 MPa
8a
The critical pressure, TC =
27Rb
R = 8.314 KPa dm3 K–1 mol–1
8a 8  371.843
TC = =
27Rb 8.314  27  40.8  10 3
= 324.79 = 324.8 K
The critical volume, VC = 3b = 3 x 40.8 = 122.4 cm3

GASEOUS STATE 85
Ex.20 In a container of capacity 1 litre, air and some liquid water is present in equilibrium at total
pressure of 200 mm of Hg this container is connected to another one litre evacuated container
find total pressure inside the container when equilibrium is again stablised (aqueous tension or
vapour pressure at this temp. is 96 mm Hg).
Sol. Total pressure = 100 mm of Hg = Pgas + Pvapour water

Pgas + 96 = 200
Pgas = 107 mm of Hg Initially
when second coataitive connected
P1 = 107 mm of Hg P2 = ?
V1 = 1 V2 = 2 litre
P1 V1 = P 2 V2
107 × 1 = P2 × 2
53.5 = P2
After equilibrium is established
Ptotal = 53.5 + 93 = Pgas + Pwater = 146.5 mm of Hg at equilibrium
Ex.21 One litre of oxygen gas is passed through a ozonizer & the final volume of the mixture becomes
820 ml. If this mixture is passed through oil of turpentine. Find final volume of gas remaining.
Sol. The reaction that takes place in ozonizer as 3O2  2O3.
2
If Vml of O2 out of 1000 ml is ozonized then vol of O3 obtained = V
3
 Final vol of ozonized oxygen
2
= (1000 – V + V) mL = 820 mL
3
1
1000 – V = 820
3
 V = 540
 O2 remaining = (1000 – 540) mL ( O3 is absorbed in oil of turpentine)
= 460 mL Ans.
Ex.22 Calculate the mean molar mass of a mixture of gases having 7 g of Nitrogen, 22 g of CO2 and
5.6 litres of CO at STP.
Sol. Moles of N2 = 7/28 = 1/4

Moles of CO2 = 22/44 = 1/2
Moles of CO = 5.6 / 22.4 = 1/4
n1 M1  n2 M2  n3 M3
mean molar mass = Mmin = = ( 7 + 7 + 22 ) / 1 = 36
n1  n2  n3

86 GASEOUS STATE

EXERCISE # 01 OBJECTIVE EXERCISE

1. Average K.E. of CO2 at 27ºC is E. The average kinetic energy of N2 at the same temperature will
be-
(A) E (B) 22E (C) E/22 (D) E/ 2
2. The velocity possessed by most of the gaseous molecules is -

(A) Average velocity (B) Most probable velocity
(C) R.M.S. velocity (D) None of these.
3. 10 gm of a gas at NTP occupies 5 litres. The temp. at which the volume becomes double for the
same mass of gas at the same pressure is -
(A) 273 K (B) -273ºC (C) 273ºC (D) 546ºC
4. A gas is said to behave like an ideal gas when the reaction PV/T = constant, holds. When do you
expect a real gas to behave like an ideal gas -
(A) When temperature and pressure are low
(B) When temperature and pressure are high
(C) When temperature is low and pressure is high
(D) When temperature is high and pressure is very low.
5. If temperature and volume are same, the pressure of a gas obeying Vander Waals equation is -
(A) Smaller than that of an ideal gas (B) Larger than that of an ideal gas
(C) Same as that of an ideal gas (D) None of these
6. Which of the following is true -

(A) urms >  >  . (B) urms <  <  . (C) urms >  <  . (D) urms <  >  .
7. The RMS velocity of an ideal gas at 27 ºC is 0.3 m sec–1. Its RMS velocity at 927 ºC is-
(A) 0.6 m sec–1 (B) 0.9 m sec–1 (C) 2.4 m sec–1 (D) 3.0 m sec–1
8. Ratio of O2 and N2 in a mixture .of these gases is 1 : 4, then what will be the ratio of numbers of
molecules in the mixture of the gases?
(A) 1:4 (B) 7 : 32 (C) 3 : 16 (D) 3:32
9. What should be the ratio of root mean square velocity of molecular hydrogen and molecular
oxygen, respectively?
(A) 4 : 1 (B) 1 : 4 (C) 1 : 2 (D) 1 : 8
10. Volume of a gas at 35° C and 1 atmospheric pressure is 3.75 litre. If volume is to be made 3.0
litre at same pressure, then the temperature will be
(A) –26.6ºC (B) 0ºC (C) 3.98ºC (D) 28ºC
11. Which of the following is incorrect relation in the critical constants Vc, Tc and Pc?
(A) a = 3 PcVc2 (B) b = Vc/3 (C) Tc = 8a/27Rb (D) b = 3 x Vc

GASEOUS STATE 87
12. At what temperature, the RMS velocities of hydrogen (1 atm. pressure) and oxygen (NTP) will be
same
(A) 37 K (B) 17 K (C) 512K (D) 27 K
13. 5 grams each of HF, HCI, HBr and HI have been taken at 87° C and 750 mm pressure. Which of
the following should have maximum volume?
(A) HF (B) HCI (C) HBr (D) HI
14. Value of average free path at 1 atmospheric pressure is L, then what should be its value at 5
atmospheric pressure?
(A) 2/5 L (B) 5 L (C) L/5 (D) Uncertain
15. If the density of a gas A is 1.5 times that of B then the molecular mass of A is M. The molecular
mass of B will be
(A) 1.5M (B) M/1.5 (C) 3M (D) M/3
16. While He is allowed to expand through a small jet under adibetic condition heating effect is
observed. This is due to the fact that
(A) Helium is an inert gas (B) Helium is a noble gas
(C) Helium is an ideal gas
(D) The inversion temp. of helium is very low
17. A gas ‘A’ having molecular weight 4 diffuses thrice as fast as the gas B. The molecular weight of
gas B is
(A) 36 (B) 12 (C) 18 (D) 24
18. Longest mean free path stands for

(A) Nitrogen (N2) (B) Oxygen (O2) (C) Hydrogen (H2) (D) Chlorine (CI2)
19. Two flasks X and Y have capacity 1 Land 2L respectively and each of them contains 1 mole of a
gas. The temperature of the flask are so adjusted that average speed of molecules in X is twice
as those in Y. The pressure in flask X would be
(A) Same as that in Y (B) Half of that in Y
(C) Twice of that in Y (D) 8 times of that in Y
20. The partial pressure of hydrogen in a flask containing 2gm of H2 & 32gm of SO2 is
1 1
(A) of total pressure (B) of total pressure
16 2
2 1
(C) of total pressure (D) of total pressure.
3 8
21. Collision frequency (Z) of a gas at a particular pressure

(A) Decreases with the rise in temperature (B) Increases with the rise in temperature
(C) Decreases initially and thereafter increases (D) Unpredictable.
88 GASEOUS STATE
22. If X is the total number of collision which a gas molecule registers with others per a gas molecule
registers with others per unit time under particular conditions, then the collision frequency of the
gas containing N molecules per unit volume is
(A) X/N (B) NX (C) 2NX (D) NX/2
23. A football bladder contains equimolar proportions of H2 and O2. The composition by mass of the
mixture effusing out of punctured football is in the ratio (H2 : O2)
(A) 1:4 (B) 2. 2 : 1 (C) 1 : 2 2 (D) 4: 1
24. An open vessel containing air is heated from 27°C to 127°C. The fraction of air originally present
which goes out of it is
3 1 2 1
(A) (B) (C) (D)
4 4 3 8
25. The behaviour of temporary gases like CO2 approaches that of permanent gases like N2, O2 etc.
as we go - .
(A) Below critical temp. (B) Above critical temp.
(C) Above absolute zero (D) Below absolute zero.
26. Reducing the pressure from 1.0 atm to 0.5 atm would change the number of molecules in one
mole of ammonia to -
(A) 75% of initial volume (B) 50% of initial volume
(C) 25% of initial volume (D) None of these
27. The density of a gas at 27°C and 1 atm pressure is  . Pressure remaining constant, the
temperature at which its density is 0.5  is-
(A) 200 K (B) 400 K (C) 600 K (D) 800 K
28. At a given temperature  (X) = 2  (Y) and M(Y) = 3 M(X), where  and M stand respectively for
density and molar mass of the gases X and Y, then the ratio of their pressures will be -
(A) p(X) / p(Y) = 1/4 (B) p(X) / p(Y) = 4 (C) p(X) / p(Y) = 6 (D) p(X) / p(Y) = 1/6
29. Which of the following expressions of compression factor Z (= pVm / RT) of a real gas is
applicable at low pressure -
(A) Z = 1 – a / Vm RT (B) Z = 1 + a / Vm RT
(C) Z = 1 + pb / RT (D) Z = 1 – pb / RT
30. The value of compression factor at the critical state of a van der Waals gas is -
(A) 3/8 (B) 8/3 (C) 1 (D) 5/8
31. A gas with formula CnH2n+2 diffuses through the porous plug at a rate one sixth of the rate of
diffusion of hydrogen gas under similar conditions. The formula of gas is –
(A) C2H6 (B) C10H22 (C) C5H12 (D) C6H14

GASEOUS STATE 89
32. Two flasks X and Y have capacity 1 Land 2L respectively and each of them contains 1 mole of a
gas. The temperature of the flask are so adjusted that average speed of molecules in X is twice
as those in Y. The pressure in flask X would be
(A) Same as that in Y (B) Half of that in Y
(C) Twice of that in Y (D) 8 times of that in Y
33. The partial pressure of hydrogen in a flask containing 2gm of H2 & 32gm of SO2 is
1 1
(A) of total pressure (B) of total pressure
16 2
2 1
(C) of total pressure (C) of total pressure.
3 8
34. For a given one mole of ideal gas kept at 6.5 atm in a container of capacity 2.463 L. The
Avogadro proportionality constant (slope of graph) for the hypothesis is (see figure)
V
(A) 0.406 (B) 2.46 (C) 22.4 (D) none of these
35. A gas is heated in such a way that its pressure and volume both becomes double. Then by
decreasing temperature, some of the molecules of air has been added in container to maintain
1
the doubled volume and pressure. Assuming th of initial number of moles has been added in
4
for the purpose. By what fraction the temperature must has been raised finally of initial absolute
temperatue ?
16 4 1
(A) 4 times (B) times (C) times (D) times
5 5 5
36. At low pressure if RT = 2 a.P , (a is vander Waal's constant) then the volume occupied by a real
gas is-
2RT 2P RT 2RT
(A) (B) (C) (D)
P RT 2P P
37. For a real gas, whose intermolecular force is negligible, at low pressure the slope and intercept of
P
the graph vs P are respectively -

RT b MR M (RT ) 2  b   RT  M Mb
(A) , (B) , (C)   ,   (D) ,
M M (RT ) 2 T b M  M  RT (RT ) 2
90 GASEOUS STATE
38. A mixture of methane and ethene in a molar ratio of x : y has an average molecular mass of 20U.
The mean molar mass when they are mixed in the molar ratio of y : x will be -
(A) 20 U (B) 25 U (C) 24 U (D) 15 U
39. There are 201 equidistant rows of spectators sitting in a hall. A magician releases laughing gas,
N2O (mol wt = 44) from the front and the tear gas (mol wt = 176) from the rear of the hall
simultaneously. Which row of spectators will have a tendency to smile and weep simultaneously
at first ?
(A) At 134th row if the numbering of rows start from front.
(B) At 67th row if the numbering of rows start from front.
(C) At 134th row if the numbering of rows start from the rear.
(D) At 113th row if the numbering of rows start from front.
40. The Vander Waal’s parameters for gases W, X, Y and Z are –
Gas a (atm L2 mol 2 ) b(Lmol 1 )

W 4.0 0.027
X 8. 0 0.030
Y 6.0 0.032
Z 12.0 0.027
Which one of these gases has the highest critical temperature ?
(A) W (B) X (C) Y (D) Z
41. Collapsible balloon is inflated to a volume of 10 L at a pressure of 1 atm. When the balloon is
immersed to the bottom of a lake, its volume reduces to 1.25 L. Assuming 1 atm pressure to be
equivalent to 10m column of water and no change in temperature, the depth of the lake will be-
(A) 70 m (B) 80 m (C) 90 m (D) none of these
42. A 2m long tube closed at one end is lowered vertically into water until the closed end is flush with
the water surface. See figure below. Calculate 'h' as shown in fig.
2m
(Barometric pressure = 1atm = 10 m of hydrostatic water head, tempt.= 25ºC, density of water =
1g/ml, Neglect water vapour pressure)
(A) 1.01m (B) 0.29m (C) 1.71m (D) 0.92m
43. The ratio between the r. m. s. velocity of H2 at 50 K and that of O2 at 800 k is :

(A) 4 (B) 2 (C) 1 (D) 1/4

GASEOUS STATE 91
44. X ml of H2 gas effuses through a hole in a container in 5 sec. The time taken for the effusion of
the same volume of the gas specified below under identical conditions is :
(A) 10 sec, He (B) 20 sec, O2 (C) 25 sec, CO (D) 55 sec, CO2
45. According to Graham's law , at a given temperature the ratio of the rates of diffusion of gases A
and B is given by :
1/ 2 1/ 2 1/ 2 1/ 2
P M  M  P  P M  M P 
(A) A  A  (B)  A   A  (C) A  B  (D) A  B 
PB  MB   MB   PB  PB  M A  MB  PA 
46. The compressibility of a gas is less than unity at STP. Therefore

(A) Vm > 22.4 L (B) Vm < 22.4 L (C) Vm = 22.4 L (D) Vm = 44.8 L
47. The r. m. s. velocity of hydrogen is 7 times the r. m. s. velocity of nitrogen. If T is the

temperature of the gas :
(A) T(H2) = T(N2) (B) T(H2) > T(N2) (C) T(H2) < T(N2) (D) T(H2) = T(N2)
48. The root mean square velocity of an ideal gas at constant pressure varies with density as
(A) d2 (B) d (C) d1/2 (D) 1/d1/2
49. Which one of the following V, T plots represents the behaviour of one mole of an ideal gas at one
atmp?
(A) (B)
(C) (D)
50. Positive deviation from ideal behaviour takes place because of

PV
(A) molecular interaction between atoms and >1
nRT
PV
(B) molecular interation between atoms and <1
nRT
PV
(C) finite size of atoms and >1
nRT
PV
(D) finite size of atoms and <1
nRT

92 GASEOUS STATE

EXERCISE # 02 ADVANCED LEVEL EXERCISE
(COMPREHENSION TYPE, MULTIPLE TYPE, MATRIX MATCH TYPE, INTEGER TYPE)
MULTIPLE ANSWERS CORRECT TYPE

1. Rate of diffusion is/are independent on which of the following factors ?
(A) size of the molecules
(B) attractive interaction forces among the gas molecules
(C) molecular mass of the gas
(D) temperature of the gas
2. Which of the following is/are belong(s) to the characteristic of ideal gas ?

(A) Mass of the gas molecules are negligible
(B) There is no interaction forces among the gas molecules
(C) Volume of gas is equal to the volume of the container
(D) Number of collisions in unit area of the walls in unit time is same at every direction.
3. 50 ml of CO is mixed with 20 ml of oxygen and sparked. After reaction the mixture is treated with
an aq. KOH solution, choose correct option –
(A) the volume of CO that reacts = 40 ml
(B) the volume of CO2 formed = 40 ml
(C) the volume of CO that remained after treatment with KOH = 10 ml
(D) the valume of CO that remains after treatment with KOH = 20 ml
4. A mixture of CH4 and C2H2 occupied a certain volume at a total pressure equal to 63 torr. The
same gas mixture was burnt to CO2 and H2O (l). The CO2 (g) alone was collected in the same
volume and at the same temperature, the pressure was found to be 69 torr. What was the mole
fraction of CH4 in the original gas mixture ?
19 19
(A) (B)
21 20
17
(C)
18
15
(D)
16
4
5. One mole triatomic vapours of an unknown substance effuses times faster than 1 mole O2
3
under same conditions. If the density of unknown vapours at pressure P and temperature T is d,
which of the following holds true for the unknown substance -
(A) dN.T.P = 0.8035 g/l
(B) Z (atomic number) = 6
18P
(C) Z(compressibility factor) =
dRT
(D) Vapour density = 9

GASEOUS STATE 93
6. Select the correct statement:

(A) The value of compressibility factor 'Z' for H2 gas is greater than one at room temperature and
pressure
(B) The real gas behaves as an ideal gas at Boyle's temperature.
(C) For a real gas following van der Waals' equation of state, the expression of critical
8a
temperature is
27R.b
P.b
(D) At low pressure, the compressibility factor 'Z' = 1 + for a van der Waal's gas.
RT
7. Which of the following quantities is the same for all ideal gases at the same temperature?
(A) The kinetic energy of 1 mol
(B) the kinetic energy of 1 g
(C) The number of molecules in 1 mol
(D) The number of molecules in 1 g
8. Which of the following statements are correct?

(A) Helium diffuses at a rate 8.65 times as much as CO does.
(B) Helium escapes at a rate 2.65 times as fast as CO does.
(C) Helium escapes at a rate 4 times as fast as CO2 does.
(D) Helium escapes at a rate 4 times as fast as SO2 does.
9. A gas can be easily liquefied

(A) When its inversion temperature equals the Boyle temperature
(B) under reversible adiabatic expansion
(C) under pressure when it is cooled to below the critical temperature
(D) at low pressure and above the critical temperature.
10. Which of the following is correct for critical temperature?

(A) It is the highest temperature at which liquid and vapour can coexist.
(B) Beyond this temperature, there is no distinction between the two phases and a gas cannot be
liquefied by compression.
(C) At this temperature, the surface tension of the system is zero.
(D) At this temperature, the gas and the liquid phases have different critical densities.
11. For a gaseous system, the pressure can be increased by

(A) increasing the volume of container but keeping the amount and temperature constant
(B) increasing the amount of gas at constant temperature and volume
(C) decreasing the volume of container but keeping the amount and temperature constant
(D) decreasing temperature but keeping amount and volume constant
94 GASEOUS STATE
12. Three gases of densities A(0.82), B(0.25), C(0.51) are enclosed in a vessel of 4L capacity. Pick
up the correct statement :
I. Gas A will tend to lie at the bottom
II. The number of atoms of various gases A, B, C are same
III. The gases will diffuse to form homogeneous mixture.
IV. The average kinetic energy of each gas is same.
(A) I , IV (B) only III (C) III , IV (D) II, III
COMPREHENSION # 01 (Q.13 to 15)

A 15 cm column of air is trapped by a column of Hg, 12 cm long, in a capillary tube horizontally
fixed as shown below, at 1.5 atm. (Temperature constant.)
15cm
12cm
P atm
13. What is the length of air column when tube is fixed at the same temperature vertical open
end up-
(A) 18.5 cm (B) 14.7 cm
(C) 13.57 cm (D) None of these
14. What is the length of air column when vertical open end down -
(A) 17.51 cm (B) 16.50 cm
Hg
(C) 16.76 cm (D) None of these
1
15. When capillary is held at 45° to the vertical open end up (cos 45° = )
2 P atm
(A) 13.50 cm (B) 14.53 cm
(C) 13.96 cm (D) none of these

A gas column is trapped by the Hg column of length  0. Atmospheric pressure is P0 . If the tube
is held at an angle  with the vertical then pressure of the gas can be given as -
Pgas = P0 + (  0 cos  )  Hg g
0 Open end
TK
 gas
 Hg = 13.6 gm/ml ; g = 10 m/s2

Gas is ideal in nature and on rotating the glass tube, temperature of the system remain constant.

GASEOUS STATE 95
16. If  = 0° and P0 = 1 atm,  0 = 8 cm, then pressure of the gas is-

(A) 840 m.m. of Hg (B) 760 m.m. of Hg
(C) 680 m.m. of Hg (D) 800 m.m. of Hg
17. If  = 90°, if volume of the gas column is 8.21 L and mass of the gas is 8 gm and temperature of
the gas is 50 K, therefore molecular wt. of the gas (monoatomic) is-
(A) 4 (B) 2 (C) 8 (D) 1
18. For  = 180°, the pressure of the gas will be-

(A) 760 m.m. of Hg (B) 680 m.m. of Hg
(C) 840 m.m. of Hg (D) 720 m.m. of Hg
19. For  = 45°, the pressure of the gas will be-

(A) 760 m.m. of Hg (B) 814 m.m. of Hg
(C) 816.7 m.m. of Hg (D) 703.26 m.m. of Hg

The graph represents Z versus P for 1 mole of several gases at 300 K.
2.0 N2 CH4 H
1.5 2
PV 1.0 CO2
RT
0.5
0 200 400 600 800

0 0 0 0
P (atm)
20. The deviation of CO2 from ideal behaviour at 100 atm is best explained by-
(A) Intermolecular attractions (B) Molecular volume
(C) Molecular shape (D) Temperature
21. The greatest contributing factor for all gases to deviate from ideal behaviour at extremely high
pressure is
(A) Intermolecular attractions (B) Molecular volume
(C) Molecular shape (D) Temperature
22. Deviation from ideal behavior typically increase with which of the following molecular
characteristics?
(A) molecular complexity only
(B) molecular mass only
(C) Deviations from ideal behavior depend upon temperature and pressure and are independent
of molecular characteristics
(D) molecular mass and complexity
96 GASEOUS STATE
23. According to the graph, at what pressures of CO2 is the ideal gas law correct and the
proportionality constant R equal to 0.08206 L atmc K–1 mol–1 ?

(A) 0 atm and 500 atm (B) 75 atm
(C) 500 atm (D) 830 atm
24. According to the graph, which of the following would be true, if the ideal gas law, PV = nRT,
where used to calculate the volume of a sample of CH4 gas from measured variables at 200 atm
and 300K and again at 600 atm and 300 K ?
(A) The calculated volume would be less than the real volume for both calculations.
(B) The calculated volume would be greater than the real volume for both calculations.
(C) The calculated volume would be less than the real volume for the 200 atm sample and
greater than the real volume for the 600 atm sample.
(D) The calculated volume would be greater than the real volume for the 200 atm sample and
less than the real volume for the 600 atm sample.
25. The data graphed for CO2 actually pertain to a temperature of 313 K. The best explanation for
this is :
(A) CO2 liquefies under low pressure at 300 K.
(B) CO2 Liquifies under high pressure at 300 K
(C) At 300 K CO2 behave like an ideal gas
(D) At 300 K CO2 deviates from ideal behavior
26. Which of the following is indicated by the graph?

(A) If temperature is sufficiently low, deviations due to molecular attractions dominate.
(B) If temperature is sufficiently low, deviations due to molecular volume dominate
(C) If pressure is sufficiently high, deviations due to molecular attractions dominate
(D) If pressure is sufficiently high, deviations due to molecular volume dominate

The critical temperature is generally about 1.6 times to that of the normal boiling point of n-
butane. The normal boiling point of n - butane is 270 K. The critical molar volume is 2.7 times of
the molar volume at the normal boiling point. The compressibility factor at the critical point is
generally 0.3 for hydrocarbons. At the boiling point the molar volume of n-butane = 0.1 L/mole.
For a vanderwaals gas (X) pressure and temperature is so adjusted such that molar volume at
zero pressure become equal to critical molar volume.
27. What is the reduced pressure at the normal boiling point of n-butane ?
(A) 1 (B) 1.625
1
(C) 39.36 (D)
39.26

GASEOUS STATE 97
28. As per vanderwaals equation what is the reduced pressure of n-butane at boiling point ?
(A) 23.584 (B) 39.36 (C) 67.324 (D) 21.87
29. What is the corresponding temperature of the vanderwaals gas (X) ?

8a 3Rb 2a
(A) (B) 2b (C) (D)
27Rb 2a 9Rb
30. Which of the following statement (s) is /are correct regarding gas (x) ?
(A) For the given substance T > TC
(B) For the given substance T < TC
(C) The given substance is in the liquid state
(D) The given substance is in the vapour state
MATCH THE COLUMN TYPE

31. Match the column -
Four different gases and their vanderwaal's constant are as given-
2 –2
Gas a in atm L mol b in L/mol
A2 1.5 0.05
B2 2.0 0.08
C2 4.2 0.025
D2 5.0 0.1
COLUMN – I COLUMN – II
(A) Gas having highest inter-molecular (P) A2
force of attraction.
(B) Gas having smallest size of molecules. (Q) B2
(C) Gas that can be liquefied at 90 K. (R) C2
(D) Gas resembles with ideal gas at the (S) D2

boiling point of water
32. Match the column

(A) Rate of effusion proportional to (P) uavg
(B) No. of binary collision by a single (Q) (Pressure)2
molecule in 1sec. is proportional to
(C) Total no. of binary collisions in 1sec. in (R) (Pressure)
unit volume of gas.
(D) Mean free path proportional to (S) (Temperature)
98 GASEOUS STATE

Vander Waal’s equation for
(A) High pressure (P) PV = RT + Pb
(B) Low pressure (Q) PV = RT –a/V
(C) Force of attraction is negligible (R) PV = RT + a/V
(D) Volume of molecules is negligible (S)
P  Va  (V – b) = RT
2

Column I Column II
(i) T1 > T2 > T3 (a)
(ii) Charle’s Law (b)
(iii) Boyle’s law (c)
(iv) Avogadro’s law (d)
(A) (i) -cd; (ii) -cd; (iii)-d ; (iv) -b

(B) (i) -ad; (ii) -bc; (iii)-a ; (iv) -b
(C) (i) -ac; (ii) -cd; (iii)-a ; (iv) -d
(D) (i) -a; (ii) -d; (iii) –ac ; (iv) -b

(A) Tc/Pc (P) Z
(B) Tc/Vc (Q) a/Rb
(C) TB (R) 8b/R
(D) Ti/TB (S) 8a/81 Rb2

GASEOUS STATE 99
Column I Column II
(Gases X and Y (Ratio of
taken of diffusion ) times taken )
X  100ml of H 2 at 1 bar, 25º C

A. P. 1 : 1.225
Y  200ml of O 2 at 1 bar, 25º C
X  100ml of O 2 at 1 bar, 25º C

B. Q. 1 : 0.7
X  100ml of SO 2 at 1 bar, 25º C

C. R. 1 : 1.36
X  HCl gas to travel100 cm

D. length in a tube S. 1: 8
Y  NH 3 gas to travel 200 cm
length u sin g the same tube
(P, V, T  same in both cases)
INTEGER TYPE
37. At 20°C, two balloons both have equal volume and porosity are filled to a pressure of 2 atm. One
with 14 kg N2 and other with 1 kg of H2. The N2 balloon leaks to a pressure of 0.5 atm in 1 hr.
How long (in minute) (...........) will it take for H2 balloon to reach a pressure of 0.5 atm.
2
38. A gas is heated in a cyllinder fitted with a nozzle from 27°C for 20 minutes. It is found that rd of
3
the original gas is diffused out through the nozzle. What would be the difference in temperature
(give your answer in terms of multiples of 100K) between initial and final states ?
39. Two vessels of equal volume are connected to each other by a value of negligible volume. One of
the containers has 2.8 g of N2 12.7 g of I2 at a temperature T1. The other container is completely
evacuated. The container that has N2 and I2 is heated to temperature T2 while the evacuated
container is heated T2/3. The value is now opened. Calculate the mass of N2 in container (B) after
a very long time I2 sublimes at T2. (report your answer in nearst integer form in grams)
100 GASEOUS STATE
40. A mixture of non reacting gases exert a pressure of 5 atm. If one of the gases occupy 40%
volume of the mixture, what would be its partal pressure in atm?
41. A gas is found to have the formula  C3 O2 n . Its vapour density is 34. The value of n will be
______________ .
42. At 400 K, the root mean square (rms) speed of gas X (molecular mass =40) is equal to the most
probable speed of gas Y at 60 K. the molecular mass of the gas Y is _______.
43. How many moles of SO2 will occupy a volume of 10 litre at a pressure of 15 atm and
temperature 624 K? ( a  6.71 atm L2 mol2 ; b  0.0564 litre mol1 )
44. 3.2 g of oxygen and 0.2 g of hydrogen are placed in 1.12 litre flask at 0C . The total pressure in
atm of the gas mixture will be ________.
45. The weight of hydrogen gas obtained from 42 g of CaH2 by treatment with water is
___________ gm.


GASEOUS STATE 101
EXERCISE # 03 SUBJECTIVE EXERCISE # 01
1. 3.6 gm of an ideal gas was injected into a bulb of internal volume of 8L at pressure P atmp
and temp T-K. The bulb was then placed in a thermostat maintained at (T+ 15) K.0.6 gm of the
gas was let off to keep the original pressure. Find P and T if mol weight of gas is 44.
2. A toy balloon originally held 1.0 gm of He gas and had a radius 10 cm. During the night, 0.25 gm
of the gas effused from the balloon. Assuming ideal gas behaivour, under these constant P and T
conditions, what was the radius of the balloon the next morning.
3. If a scuba diver is to remain submerged for 1 hr, what pressure must be applied to force sufficient
air into the tank to be used . Assume 0.5 dm3 of air per breath at standard atmospheric pressure,
a respiration rate of 38 breaths per minute, and a tank capacity of 30 dm3.
4. While resting, the average human male use 0.2 dm3 of O2 per hour at S T P for each kg of body
mass. Assume that all this O2 is used to produce energy by oxidising glucose in the body . What
is the mass of glucose required per hour by a resting male having mass 60 kg . What volume, at
S T P of CO2 would be produced.
5. One mole of NH4Cl is kept in an open container & then covered with a lid. The container is now
heated to 600 K where all NH4Cl dissociates into NH3 & HCl. If volume of the container is 24.63
litres, calculate what will be the final pressure of gases inside the container. Also find whether the
lid would stay or bounce off if it can with stand a pressure difference of 5.5 atm. Assume that
outside air is at 300 K and 1 atm pressure.
6. 12 g N2, 4 gm H2 and 9 gm O2 are put into a one litre container at 27°C. What is the total
pressure.
7. 1.0×10–2 kg of hydrogen and 6.4×10–2 kg of oxygen are contained in a 10×10–3 m3 flask at 473
K. Calculate the total pressure of the mixture. If a spark ignities the mixture. What will be the final
pressure.
8. A gas mixture contains equal number of molecules of N2 and SF6 , some of it is passed
through a gaseous effusion apparatus . Calculate how many molecules of N2 are present in
the product gas for every 100 molecules of SF6.
9. Two gases NO and O2 were introduced at the two ends of a one metre long tube
simultaneously (tube of uniform cross- section). At what distance from NO gas end , Brown
fumes will be seen.
102 GASEOUS STATE
10. Pure O2 diffuses through an aperture in 224 sec, whereas mixture of O2 and another gas
containing 80 % O2 diffuses from the same in 234 sec. What is molecular weight of the gas?
11. Automobile air bags are inflated with N2 gas which is formed by the decomposition of solid
sodium azide (NaN3). The other product is Na - metal. Calculate the volume of N2 gas at 27°C
and 756 Torr formed by the decomposing of 125 gm of sod azide.
12. An iron cylinder contains helium at a pressure of 250 k pa and 27°C. The cylinder can withstand a
pressure of 1  106 pa . The room in which cylinder is placed catches fire. Predict whether the
cylinder will blow up before it metls or not. [melting point of cylinder = 1800 k ]
13. At what temperature in °C, the Urms of SO2 is equal to the average velocity of O2 at 27°C.
14. Calculate Urms of molecules of H2 at 1 atmp density of H2 is 0.00009 g/cc.
15. The mean kinetic energy of a molecule at 00C is 5.621 × 10–14 ergs. Calculate the number of
molecules in gm molecule of gas.
16. The density of CO at 273 K and 1 atm is 1.2504 kg m–3. Calculate (a) root mean square speed
(b) the average speed and (c) most probable speed.
17. Calculate the temperature at which the root mean square velocity, average velocity and most
probable velocity of oxygen gas are all equal to 1500 ms–1.
18. Calculate the mean free path in CO2 at 27°C and a pressure of 10–6 mm Hg. (molecular
diameter = 460 pm)
19. The compressibility factor for N2 at – 50°C and 800 atmp pressure is 1.95 and at 100°C and 200
atmp, it is 1.10. A certain mass of nitrogen occupied one litre at – 50°C and 800 atmp. Calculate
the volume occupied by the same quantity of N2 at 100°C and 200 atmp.
20. The density of mercury is 13.6 g/cm3. Estimate the b value.
21. Calculate the pressure exerted by 22 g of carbon dioxide in 0.5 dm3 at 298.15 K using:
(a) the ideal gas law and
(b) vander waals equation. Given:
[a = 363.76 kPa dm6 mol–2 and
b = 42.67 cm3 mol–1]
22. Calculate from the vander waal's equation, the temperature at which 192 gm of SO2 would
occupy a vol. of 10 dm3 at 15 atm pressure.[a = 6.7 atm lit2 mol2, b = 0.0564 lit mol–1]

GASEOUS STATE 103
23. N2 molecule is spherical of radius 100 pm.

(a) What is the volume of molecules is one mole of a gas?
(b) What is the value of vander waal's constant b?
(c) What is the free volume of the gas at STP?
24. The vander waals constant for O2 are a = 1.36 atm L2 mol–2 and b = 0.0318 L mol–1. Calculate
the temperature at which O2 gas behaves, ideally for longer range of pressure.
25. The vander Waals constants for gases A, B and C are as follows
Gas a/dm6 kPa mol–2 b/dm3 mol–1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has (i) the highest critical temperature, (ii) the largest molecular volume, and (iii) most
ideal behaviour around STP?


104 GASEOUS STATE
EXERCISE # 04 SUBJECTIVE EXERCISE # 02
1. In a basal metabolism measurement timed at 6.00 min, a patient exhaled 52.5 L of air, measured
over water at 20 ºC. The vapour pressure of water at 20 ºC is 17.5 torr. The barometric pressure
was 750 torr. The exhaled air analyzed 16.75 vol% oxygen and the inhaled air 20.32 vol%
oxygen, both on dry basis. Neglecting any solubility of the gases in water and any difference in
the total volumes of inhaled and exhaled air, calculate the rate of oxygen consumption by the
patient in ml (S.T.P) per minute.
2. At 20 ºC two balloons of equal volume and porosity are filled to a pressure of 2 atm, one with
1
14 kg N2 & other with 1 kg H2 . The N2 balloon leaks to a pressure of atm in one hour. How
2
1
long will it take for H2 balloon to leaks to a pressure of atm.
2
3. A space capsule is filled with neon gas at 1.00 atm and 290 K. The gas effuses through a pin-
hole into outer space at such a rate that the pressure drops by 0.3 torr/sec
(a) If the capsule were filled with ammonia at the same temperature and pressure, what would be
the rate of pressure drop.
(b) If the capsule were filled with 30.0 mol % helium, 20.0 mol % oxygen & 50.0 mol % nitrogen
at a total pressure of 1.00 atm & a temp. of 290 K, what would be the corresponding rate of
pressure drop.
4. The composition of the equilibrium mixture (Cl2 

 2 Cl) which is attained at 1200 ºC is
determined by measuring the rate of effusion through a pin hole . It is observed that at 1.8 mm Hg
pressure, the mixture effuses 1.16 times as fast as Kr effuses under the same conditions.
Calculate the fraction of chlorine molecules dissociated into atoms. [ Kr = 84 a. m. u.]
5. (a)How much H2 (in mol) is needed to inflate a balloon of radius 3m to a pressure of 1 atmp
in an ambient temp at 25 ºC at sea level.
(b) What mass can the balloon lift at sea level, where the density of air is 1. 22 Kg m–3.
(c) What would be the pay load if He were used instead of H2.
6. Calculate the pressure of a barometer on an aeroplane which is at an altitude of 10 Km.

Assume the pressure to be 101.325 Kpa at sea level & the mean temperature 243 K. Use the
average molar mass of air (80% N2 , 20 % O2)

GASEOUS STATE 105
7. The time taken for a given volume of gas E to effuse through a hole is 75 sec. Under identical
conditions the same volume of a mix of CO & N2 ( containing 40% of N2 by volume ) effused
in 70 seconds. Calculate
(i) the relative mol mass of E , and
(ii) the RMS velocity ( in ms–1 units ) of E at 0 ºC.
8. A bulb of capacity 1 dm 3 contains 1.03 × 1023 H2 molecules & pressure exerted by these
molecules is 101.325 kPa. Calculate the average square molecular speed and the temperature.
9. Calculate the temperature values at which the molecules of the first two members of the
homologous series, CnH2n+2 will have the same rms speed as CO2 gas at 770 K. The normal
b.p. of n-butane is 273 K. Assuming ideal gas behaviour of n-butane upto this temperature,
calculate the mean velocity and the most probable velocity of its molecules at this temperature.
10. Calculate the value of  ,  , Z1 and Z11 for nitrogen molecules at 25°C and at pressure of 10–3
mm Hg. Given that b for nitrogen is 39.1 cm3 mol–1.
11. At 273.15 K and under a pressure of 10.1325 MPa, the compressibility factor of O2 is 0.927.
Calculate the mass of O2 necessary to fill a gas cylinder of 100 dm 3 capacity under the given
conditions.
12. The molar volume of He at 10.1325 MPa and 273 K is 0.011075 of its molar volume at 101.325
KPa at 273 K.Calculate the radius of helium atom. The gas is assumed to show real gas nature.
Neglect the value of a for He.
13. The density of water vapour at 327.6 atm and 776.4 K is 133.2 gm/dm3.
Determine the molar volume, Vm of water and the compression factor.
14. A commercial cylinder contains 6.91 m 3 of O2 at 15.18 M Pa and º C. the critical constants for
O2 are TC = –118.4 º C , PC = 50.1 atmp. Determine the reduced pressure and reduced
temperature for O2 under these conditions.
15. A compound exists in the gaseous state both as a monomer (A) and dimer (A2). The molecular
weight of the monomer is 48. In an experiment, 96 g of the compound was confined in a vessel of
volume 33.6 litres and heated to 2730 C. Calculate the pressure developed, if the compound
exists as a dimer to the extent of 50 per cent by weight, under these conditions. (R = 0.082)
106 GASEOUS STATE
1
16. One mole of an ideal gas is subjected to a process in which P = V where P is in atm & V in
8.21
litre. If the process is operating from 1 atm to finally 10 atm (no higher pressure achieved during
the process) then what would be the maximum temperature obtained & at what instant will it
occur in the process.
17. A gas present in a container connected to frictionless, weightless piston operating always at one
atmosphere pressure such that it permits flow of gas outside (with no adding of gas). The graph
of n vs T (Kelvin) was plotted & was found to be a straight line with co-ordinates of extreme
points as (300, 2) & (200, 3). Calculate
(i) relationship between n & T
(ii) relationship between V & T
(iii) Maxima or minima value of 'V'
PV 3
18. Calculate the volume occupied by 14.0 g N2 at 200 K and 8.21 atm pressure if C C = and
RTC 8
Pr Vr
=2.2.
Tr


GASEOUS STATE 107
EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS
1. The density of acetic acid vapor at 300 K and 1 atm is 5 mg cm 3 . The number of acetic acid
molecules in the cluster that is formed in the gas phase is closest to [KVPY 2014]
(A) 5 (B) 2 (C) 3 (D) 4
2. The volume vs. temperature graph of 1 moe of an ideal gas is given below [KVPY 2015]
x y
Volume (L)
50
40
30
20
Z
100 200 300 400 500

Temperature (K)
The pressure of the gas (in atm) at X, Y and Z, respectively, are

(A) 0.328, 0.820, 0.820 (B) 0.328, 0.820, 3.28
(C) 0.238, 0.280, 0.280 (D) 32.8, 0.28, 82.0
3. Real gases behave indeally at [INCHO 2014]

(A) low pressure and low temperature (B) high pressure and low temperature
(C) low pressure and high temperature (D) high pressure and high temperture
4. The graph that wrongly represents the Boyle’s law for an ideal gas is [INCHO 2014]
PV
P
1/V P
I II
P PV
V P
III IV
(A) II (B) I (C) IV (D) III
108 GASEOUS STATE
5. In an experiment, it was found that for a gas at constant temperature, PV  C . The value of a C
depends on [NSEC 2015]
(A) atmospheric pressure (B) quantitiy of gas
(C) molecular weight of gas (D) volume of chamber
6. The quantity that does not change for a sample of a gas in a sealed rigid container when it is
cooled from 120C to 90C at constant volume is [NSEC 2015]
(A) average energy of the molecule (B) pressure of the gas
(C) density of the gas (D) average speed of the molecules
7. The rato of root mean square velocity of hydrogen at 50 K to that of nitrogen at 500 K is closest to
[NSEC 2016]
(A) 1.18 (B) 0.85 (C) 0.59 (D) 1.40
8. In the following compressibility factor (Z) vs. pressure graph at 300 K, the compressibility of CH4
at pressure  200 bar deviates from ideal behaviour because [NSEC 2016]
(A) the molar volume of CH4 is less than its molar volume in the ideal state
(B) the molar volume of CH4 is same as that in its ideal state
(C) intermolecular interactions between CH4 molecules decreases
(D) the molar volume of CH4 is more than its molar volume in the ideal state
9. Equal masses of ethane and hydrogen gas are present in a container at 25C . The fraction of
the total pressure exerted by ethane gas is : [NSEC 2016]
(A) 1/2 (B) 1/16 (C) 15/16 (D) 1/8


GASEOUS STATE 109
EXERCISE # 06 JEE (MAIN) CORNER
1. Equal masses of methane and oxygen are mixed in an empty container at 25ºC. The fraction of
the total pressure exerted by oxygen is – [2007]
2 1 273 1 1
(A) (B)  (C) (D)
3 3 298 3 2
4 3 3
2. If 10 dm of water is introduced into a 1.0 dm flask at 300 K, how many moles of water are in
the vapour phase when equilibrium is established? [2010]
(Given : Vapour pressure of H 2O at 300 K is 3170 Pa; R = 8.314 J K-1 mol -1)
(A) 5.56 103 mol (B) 1.53 102 mol (C) 4.46 102 mol (D) 1.27 103 mol
3. ‘a’ and ‘b’ are van der Waals’ constants for gases. Chlorine is more easily liquefied than ethane
because [2010]
(A) a and b for Cl2 > a and b for C2 H 6
(B) a and b for Cl2 < a and b for C2 H 6
(C) a for Cl2 < a for C2 H 6 but b for > b for C2 H 6
(D) a and b for Cl2 > a for C2 H 6 but b for < b for C2 H 6
4. When r, P and M represent rate of diffusion, pressure and molecular mass, respectively, then the
ratio of the rates of diffusion of two gases A and B, is given as : [2011]
1 1 1 1
 PA  M B  2  PA   M B 
2  PA  M A  2  P 2  M 
(A)    (B)     (C)    (D)  A   A 
 PB  M B   PB   M A   PB  M B   PB   M B 
5. The molecular velocity of any gas is: [2011]

(A) inversely proportional to absolute temperature.
(B) directly proportional to square of temperature.
(C) directly proportional to root of temperature.
(D) inversely proportional to the square root of temperature.
6. The compressibility factor for a real gas at high pressure is : [2012]

RT pb pb
(A) 1 (B) 1 (C) 1 (D) 1
pb RT RT
7. For gaseous state, if most probable speed is denoted by average speed by and mean square
speed by C, then for a large number of molecules the ratios of these speeds are : [2013]
(A) C* : C : C  1.225 :1.128 :1 (B) C* : C : C  1.128 :1.225 :1
(C) C* : C : C  1:1.128 :1.225 (D) C* : C : C  1:1.225 :1.128
110 GASEOUS STATE
8. The ratio of masses of oxygen and nitrogen in a particular gaseous mixture is 1:4. The ratio of
number of their molecule is: [2014]
(A) 3 : 16 (B) 1 : 4 (C) 7 : 32 (D) 1 : 8
9. If Z is a compressibility factor, van der Waals equation at low pressure can be written as: [2014]
RT
(A) Z  1  Pb (B) Z  1 
RT Pb
a
(C) Z  1  (D) Z  1  Pb
VRT RT
10. Two closed bulbs of equal volume (V) containing an ideal gas initially at pressure pi and
temperature T1 are connected through a narrow tube of negligible volume as shown in the figure
below. The temperature of one of the bulbs is then raised to T2. The final pressure pf is [2016]
 T1   T2 
(A) 2pi   (B) 2pi  
 T1  T2   T1  T2 
 T1T2   T1T2 
(C) 2pi   (D) pi  
 T1  T2   T1  T2 
11. The major product obtained in the following reaction is : [2017]
(A) C6H5 CH  CHC6H5 (B)    C6H5 CH O tBu  CH2C6H5
(C)    C6H5CH  OtBu  CH2C6H5 (D)    C6H5 CH O tBu  CH2C6H5
12. The increasing order of the reactivity of the following halides for the SN 1 reaction is : [2017]
(A) (II) < (I) < (III) (B) (I) < (III) < (II)
(C) (II) < (III) < (I) (D) (III) < (II) < (I)

GASEOUS STATE 111
13. Which of the following compounds will form significant amount of meta product during mono-
nitration reaction? [2017]
(A) (B) (C) (D)
14. Which of the following molecules is least resonance stabilized? [2017]
(A) (B) (C) (D)

112 GASEOUS STATE
EXERCISE # 07 JEE (ADVANCED) CORNER
PV
1. where Z  ,
nRT
a = Van der Waal’s constant for pressure correction

b = Van der Waal’s constant for volume correction
Pick the only incorrect statement [2006]
(A) for gas A, if a = 0, the compressibility factor is directly proportional to pressure
(B) for gas B, if b = 0, the compressibility factor is directly proportional to pressure.
(C) for gas C, a ¹ 0, b ¹ 0, it can be used to calculate a and b by giving lowest P value and its
intercept with Z = 1
(D) slope for all three gases at high pressure is positive.
2. A gas described by Van der waals equation - [2008]

(A) behaves similar to an ideal gas in the limit of large molar volumes
(B) behaves similar to an ideal gas in the limit of large pressures
(C) is characterised by van der Waals coefficients that are dependent on the identity of the gas
but are independent of the temperature
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally
3. The term that corrects for the attractive forces present in a real gas in the van der Waals equation
is - [2009]
an2 an 2
(A) nb (B) (C)  (D) nb
V2 V2
4. At 400 K, the root mean square (rms) speed of a gas X (molecular weight = 40) is equal to the
most probable speed of gas Y at 60 K. The molecular weight of the gas Y is [2009]
5. According to kinetic theory of gases [2011]

(A) collisions are always elastic
(B) Heavier molecules transfer more momentum to the wall of the container
(C) Only a small number of molecules have very high velocity
(D) Between collisions, the molecules move in straight lines with constant velocities
6. To an evacuated vessel with movable piston under external pressure of 1 atm, 0.1 mol of He and
1.0 mol of an unknown compound (vapour pressure 0.68 atm. at 0C ) are introduced.
Considering the ideal gas behaviour, the total volume (in litre) of the gases at 0C is close to
[2011]

GASEOUS STATE 113
1
7. For one mole of a van der Waal’s gas when b = 0 and T = 300 K, the PV vs, plot is shown
V
below. The value of the van der Waal’s constant a (atm. liter 2 mol2 ) is : [2012]
(A) 1.0 (B) 4.5

(C) 1.5 (D) 3.0
PASSAGE - 1
A fixed mass ‘m’ of a gas is subjected to transformation of states from K to L to M to N and back
to K as shown in the figure [2013]
8. The succeeding operations that enable this transformation of states are
(A) Heating, cooling, heating, cooling

(B) Cooling, heating, cooling, heating
(C) Heating, cooling, cooling, heating
(D) Cooling, heating, heating, cooling
9. The pair of isochoric processes among the transformation of states is

(A) K to L and L to M
(B) L to M and N to K
(C) L to M and M to N
(D) M to N and N to K
10. If the value of Avogadro number is 6.023  1023 mol1 and the value of Bolzmann constant is
1.380  10 23 JK 1 , then the number of significant digits in the calculated value of the universal
gas constant is [2014]
114 GASEOUS STATE
11. An ideal gas in a thermally insulated vessel at internal pressure  P1 volume  V1 and absolute
temperature  T1 expands irreversibly against zero external pressure, as shown in the diagram.
The final internal pressure, volume and absolute temperature of the gas are respectively. For this
expansion, [2014]
(A) q  0 (B) T2  T1 (C) P2 V2  P1V1 (D) P2 V2  P1V1
PASSAGE – 2
X and Y are two volatile liquids with molar weights of 10 g mol1 and 40 g mol1 respectively.
Two cotton plugs, one soaked in X and the other soaked in Y, are simultaneously placed at the
ends of a tube of length L = 24 cm, as shown in the figure. The tube is filled with an inert gas at 1
atmosphere pressure and a temperature of 300 K. Vapours of X and Y react to form a product
which is first observed at a distance d cm from the plug soaked in X. Take X and Y to have equal
molecular diameters and assume ideal behavior for the inert gas and the two vapours [2014]
12. The value of d in cm (shown in the figure), as estimated from Graham’s law, is
(A) 8 (B) 12
(C) 16 (D) 20
13. The experimental value of d is found to be smaller than the estimate obtained using Graham’s
law. This is due to
(A) Larger mean free path for X as compared to that of Y.
(B) Larger mean free path for Y as compared to that of X.
(C) Increased collision frequency of Y with the inert gas as compared to that of X with the inert
gas.
(D) Increased collision frequency of X with the inert gas as compared to that of Y with the inert
gas.

GASEOUS STATE 115
14. One mole of a monoatomic real gas satisfies the equation p(V – b) = RT where b is a constant.
The relationship of interatomic potential V(r) and interatomic distance r for the gas is given by
[2015]
(A) (B)
(C) (D)
15. The diffusion coefficient of an ideal gas is proportional to its mean free path and mean speed.
The absolute temperature of an ideal gas is increased 4 times and its pressure is increased 2
times. As a result, the diffusion coefficient of this gas increases x times. The value of x is [2016]
16. Among the following, the number of aromatic compound(s) is ………………………… . [2017]

116 GASEOUS STATE
ANSWER KEY
ANSWER KEY EXERCISE # 01 OBJECTIVE EXERCISE
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. A B C D A A A B A A
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. D B A C B D A C D C
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. B D D B B D C C A A
Qs. 31 32 33 34 35 36 37 38 39 40
Ans. C D C A B C C C A D
Qs. 41 42 43 44 45 46 47 48 49 50
Ans. A C C B C B C D C C
ANSWER KEY EXERCISE # 02 ADVANCED LEVEL EXERCISE
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. AB BCD ABC A ACD ABC AC BD BC ABC
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. BC C C C C A A B C A
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. B D A D B D D A D BD
Qs. 31 32
Ans. [A  S; B  R; C  PQRS; D  PQ] [A  PRS; B  PR; C  PQ; D  S]
Qs. 33 34 35
Ans. [A  P; B  Q; C  P; D  Q] D [A  R, B  S, C  Q , D  P ]
Qs. 36 37 38 39 40 41 42
Ans. [A  S; B  P ; C  Q; D  R] 16 6 2 2 1 4
Qs. 43 44 45
Ans. 3 4 4
Q.1 P = 0.062 atm , T = 75 K Q.2 9.08 cm

Q.3 3
3.8×10 kpa Q.4 16.07 gm ; 12 dm3
Q.5 6 atm, No Q.6 66.74 atm
Q.7 Ptotal = 27.54×10 N/m , Pfinal = 19.66×10 N/m2
5 2 5
Q.8 228 Q.9 50.8 cm
Q.10 46.6 Q.11 71.4 L

GASEOUS STATE 117
Q.12 yes Q.13 236.3°C

Q.14 183,800 cm/sec Q.15 6.06×1023 molecules mol–1
Q.16 URMS = 493 m/s ,Ump = 403m/s ,Uav=454.4 m/s
Q.17 TRMS= 2886 K, Tav = 3399 K, Tmp=4330K
Q.18 3.3×103 cm Q.19 3.77 L
Q.20 58.997 cm3 Q.21 (a) 2.479 × 103 kPa, (b) 2225.55 kPa
Q.22 350.5°C
Q.23 (a) 2.52× 10–3 l mol–1, (b) 10.08 × 10–3 dm3 mol–1, (c) 22397.48 cm3
Q.24 521 K Q.25 (i) B, (ii) C, (iii) A
Q.1 280 ml/min

Q.2 16 min
Q.3 (a) 0.33 Torr/sec , (b) 0.29 Torr/sec
Q.4 0.137
Q.5 4.62×103 moles, 128.79 Kg, 119.55Kg
Q.6 25.027 Kpa
Q.7 32.14 g / mol , 460.28 m/s
Q.8 8.88×105 (m /s)2 ; 71.27 K

Q.9 280 K, 525 K , 3.157 ×102 m/sec, 2.798×102 m/sec
Q.10 314 pm, 7.015 cm, 6742 s–1, 1.09 × 1017 cm–3s–1
Q.11 15.40 kg
Q.12 r = 1.33 × 10–8
Q.13 Molar vol = 0.1353 L/mol; Z = 0.6957
Q.14  = 2.99 ,  = 1.90

Q.15 2 atmp
Q.16 10,000 K
T RT 2
Q.17 n= 5 ,V=  5RT , 51.3125 l
100 100
Q.18 0.825 L
ANSWER KEY EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS
Qs. 1 2 3 4 5 6 7 8 9
Ans. B A C C B C A A B
118 GASEOUS STATE
ANSWER KEY EXERCISE # 06 JEE (MAIN) CORNER
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. C D D A C C C C C B
Qs. 11 12 13 14
Ans. A A B C
ANSWER KEY EXERCISE # 07 JEE (ADVANCED) CORNER
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. C AD B 4 ABCD 7 C C B D
Qs. 11 12 13 14 15 16
Ans. ABC C D C D 5

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XI MODULE - III

Step – I CatalyseR 's Practice Sheets & NCERT

Step – III Previous Years’ JEE Subjective & Objective Questions,

Step – IV After Completion of Step – III, if time permits, students can

This Study Package is Prepared by

 CONCEPTS IN BRIEF (ATOMIC STRUCTURE) 01 – 15

JEE (MAIN) Formely known as AIEEE

PROPERTIES OF CATHODE RAYS :

PRODUCTION OF ANODE RAYS (DISCOVERY OF PROTONS) :

PROPERTIES OF ANODE RAYS :

Thomson’s Model of the Atom :

CatalyseR Eduventures (India) Pvt. Ltd.

Rutherford’s nuclear concept of the atom.

 Most of the space in the atom is empty.

DRAWBACKS OF RUTHERFORD MODEL :

2. It could not explain the line spectrum of H-atom.

Particles Symbol Mass Charge Discoverer

Electron 0 9.1096 x 10-31 kg – 1.602 x l0–19

Proton 1 1.6726 x 10–27 kg + 1.602 x 10–19

Neutron 1 1.6749 x 10–27 kg

 Atomic number of an element

 Mass number of an element = No. of protons + No. of neutrons.

CatalyseR Eduventures (India) Pvt. Ltd.

SOME IMPORTANT CHARACTERISTICS OF A WAVE

QUANTUM THEORY OF LIGHT

The phenomenon is called Photoelectric effect.

CatalyseR Eduventures (India) Pvt. Ltd.

SOME IMPORTANT FORMULA

BOHR’S MODEL FOR HYDROGEN LIKE ATOMS

2 Ze2K 2.18  106  Z

DEFINITION VALID FOR SINGLE ELECTRON SYSTEM

CatalyseR Eduventures (India) Pvt. Ltd.

 Ionisation energy (E) :

 Ionisation Potential (.P.) :

  Binding Energy ‘or’ Seperation Energy :

Study of Emission and Absorption Spectra :

An instrument used to separate the radiation of different wavelengths (or frequencies) is

When some volatile salt

CatalyseR Eduventures (India) Pvt. Ltd.

EMISSION SPECTRUM OF HYDROGEN

SPECTRA LINES OF HYDROGEN ATOM

Series n1 n2 > n1 Region of Spectrum

Lyman 1 2,3,..... Ultraviolet

 For First line of a series n2  n1  1

 From the de–Broglie equation it follows that wavelength of a particle decrease

 If a charged particle Q is accelerated through potential difference V from rest

 de–Broglie concept is more significant for microscopic or sub–micrscopic

 Wavelength of electron is always calculated using De–broglie calculation.

HEISENBERG’S UNCERTAINTY PRINCIPLE

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(i) Principal Quantum Number (n) :

(ii) Azimuthal Quantum Number () :

(iii) Magnetic Quantum Number (m) :

present in a main energy level is ‘n2’.

(iv) Spin Quantum Number (s) :

Pauli’s Exclusion Principle :

 Total no. of e– in main energy shell = 2n2

Maximum no. of e– in an orbital = 2

No. of subshells in main energy shell = n