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IIT Class XI Chem Structure of Atoms
IIT Class XI Chem Structure of Atoms
S T U D Y M A T E R I A L
PHASE - I
STRUCTURE
OF
ATOM
IIT-JEE
CHEMISTRY
FNS
HOUSE,
63
KALU
SARAI
MARKET
SARVAPRIYA VIHAR, NEW DELHI-110016
PH.: (011) 32001131/32/50 FAX : (011) 41828320
Website
:
w w w . n a r a y a n a i c c . c o m
E-mail
:
i n f o @ n a r a y a n a i c c . c o m
PREFACE
Dear Student,
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C O N T E N T S
CONTENTS
STRUCTURE OF ATOM
1.
Theory
2.
Solved Problems
(i)
(ii)
3.
Assignments
(i)
Subjective Questions
(ii)
(v)
4.
Answers
STRUCTURE OF ATOM
IIT-JEE Syllabus
Electron, proton and neutron; Constitution of nucleus, Properties of alpha, beta and
gamma rays; Rutherfords scattering experiment; Bohrs atomic model (mathematical
details excluded); Quantum numbers; Paulis exclusion principle; Hunds rule; Aufbau
principle; Electronic configuration of elements (upto atomic number 36); Shapes of s, p,
and dorbitals.
CONTENTS
Daltons Theory of atom
Subatomic particles
Various atomic models
Photoelectric effect
Particles & wave nature of electron
Heisenberg uncertainty principle
Schrodinger wave equation
Quantum numbers
Rules for filling electrons
Shapes and size of orbitals
Quantum mechanical treatment of
Hatom
INTRODUCTION
The classical view of atomic structure was
constructed with the body of knowledge
accumulated in physics over several
centuries. We begin with the focus on
atomic nucleus with its protons and
neutron. This includes obtaining atomic
masses and atomic number. Electrons are
at the heart of our modern view of atomic
structure.
This chapter, firstly provides experimental
evidence for the picture of atom. After that
it deals with nature of light and finally
explains the behaviour of electrons in
atoms leading to the modern view of atomic
structure.
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Atoms of the same element are alike; in particular all atoms of an element have the
same mass.
Atoms of different elements are not alike; in particular, their masses are different.
1.1 REASON FOR FAILURE OF DALTONS THEORY
In 1833, Michael Faraday showed that there is a relationship between matter and electricity.
This was the first major break through to suggest that atom was not a simple indivisible
particle of all matter but was made up of small particles. Discovery of electrons, protons and
neutrons discarded the indivisible nature of atom proposed by John Dalton.
2. SUBATOMIC PARTICLES
The researches done by various eminent scientists and the discovery of radioactivity have
established beyond doubt, that atom is not the smallest indivisible particle but had a
complex structure of its own and was made up of still smaller particles like electrons,
protons, neutrons etc. At present about 35 different subatomic particles are known but the
three particles namely electron, proton and neutron are regarded as the fundamental
particles.
We shall now take up the brief study of these fundamental particles.
2.1 CATHODE RAYS (DISCOVERY OF ELECTRON)
Gases are normally poor conductor of electricity at ordinary or high pressure. However
when a tube filled with a gas is evacuated to a pressure of 0.01 mm Hg or lower and an
electric potential is applied across a pair of electrodes into the tube discharge takes place
between the electrodes during which a stream of rays moves from cathode to anode,
William Crookes (1879) called these rays as cathode rays.
2.1a PROPERTIES OF CATHODE RAYS
1.
Cathode rays travel in straight lines with a high speed approaching to that of light.
Their linear propagation is shown by the fact that they caste shadows of the solid
objects placed in their path.
2.
3.
They pass through thin films of metals but are stopped by thicker foils.
4.
Cathode rays can produce mechanical effect e.g. when allowed to fall on a small
paddle wheel they cause rotation of wheel. This experiment shows that cathode rays
consist of material particles.
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5.
The cathode rays can be deflected by electric and magnetic field. The direction of
deflection is always such that these particles bear a negative charge.
6.
Finally no matter what the nature of the cathode or the gas in the discharge tube, the
negatively charged particles are always the same as reflected by the same e/m ratio by
J.J. Thomson.
These particles constituting cathode rays have been named electron by J.J. Thomson. The
fact that electrons are independent of the nature of source from which they come suggest
that they are constituent of all elements.
Thomson determined e/m ratio of electrons by applying electric and magnetic field
2.1b METHOD OF EXPERIMENTAL DETERMINATION OF E/M
Tube was evacuated
through here and then
sealed off.
Anode +
(metal plugs with slits)
3 Magnetic only
1 Both or neither
2 Electric only
Cathode
Cathode ray
Aluminum plates
(5 cm 2 cm, 1.5 cm apart)
e
Determination of m ratio of electron
e
of electron = 1.7588 1011 C / kg = 1.7588 108 C / g
m
e
= 9.1 1028 g
e
m
Eyepiece of telescope
with three equally spaced
crosshairs
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They are deflected in electric and magnetic field just as cathode rays but in the
opposite direction showing that they consist of positively charged particles.
(ii) the charge and mass of the particles constituting anode rays vary and depend upon the
nature of gas contained in the discharge tube.
(iii) Positive rays are not emitted by anode but originate between the electrodes from the
ionization of gas atoms.
The mass of positively charged particle is virtually the same as that of the atoms from which
they are derived, Wein (1898) determined the value of e/m for positive particles and found
that it was different for different gases. When hydrogen gas was taken in the discharge tube,
the lightest positively charge particle was found. Its mass was nearly the same as that of H
atom (1.673 1024 g) and carried a positive charge exactly equal and opposite to that of an
electron. This positively charged particle was named proton.
2.3 DISCOVERY OF NEUTRON
The electrically neutral charge particle, neutron was discovered by James Chadwick by
bombarding boron or beryllium with -particles.
9
4
1
Be + 24 He
12
6 C + 0n
1/1836
+1
No charge
Mass in kg
9.109 10 31
1.673 10 27
1.675 10 27
Mass in amu
5.485 10 4
1.007
1.008
1.602 10 19
1.602 10 19
4.8 10 10
4.8 10 10
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INSTITUTE OF CORRESPONDENCE COURSES
he observed
(i) Majority of the -particles pass straight through the gold strip with little or no
deflection.
(ii) Some -particles are deflected from their path and diverge.
(iii) Very few -particles are deflected backwards through angles greater than 90.
(iv) Some were even scattered in the opposite direction at an angle of 180 [Rutherford was
very much surprised by it and remarked that "It was as incredible as if you fired a 15
inch shell at a piece of tissue paper and it came back and hit you"].
3.2a CONCLUSIONS
1. The fact that most of the particles passed straight through the metal foil indicates the
most part of the atom is empty.
2. The fact that few particles are deflected at large angles indicates the presence of a
heavy positively charged body i.e., for such large deflections to occur -particles must
have come closer to or collided with a massive positively charged body, and he named
it nucleus.
3. The fact that one in 20,000 have deflected at 180 backwards indicates that volume
occupied by this heavy positively charged body is very small in comparison to total
volume of the atom.
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Ordinary light rays, Xrays,rays, etc. are called electromagnetic radiations because
similar waves can be produced by moving a charged body in a magnetic field or a magnet
in an electric field. These radiations have wave characteristics and do not require any
medium for their propagation.
(i) Wave length () : The distance between two neighbouring troughs or crests is known
as wavelength. It is denoted by and is expressed in cm, m, nanometers (1nm=109m)
or Angstrom (1=1010m).
(ii) Frequency () : The frequency of a wave is the number of times a wave passes
through a given point in a medium in one second. It is denoted by (nu) and is
expressed in cycles per second (cps) or hertz (Hz) 1Hz = 1cps.
The frequency of a wave is inversely proportional to its wave length ()
1
c
or =
(iii) Velocity : The distance travelled by the wave in one second is called its velocity. It is
denoted by c and is expressed in cm sec1.
c = or =
(or) =
(v) Amplitude: It is the height of the crest or depth of the trough of a wave and is denoted
by a. It determines the intensity or brightness of the beam of light.
If all the components of Electromagnetic Radiation (EMR) are arranged in order of
decreasing or increasing wavelengths or frequencies, the pattern obtained is known as
Electromagnetic Spectrum. The following table shows all the components of light.
S.No.
Name
1.
Radio wave
Wavelength
Frequency(Hz)
3 1014 3 107
1 105 1109
2.
Microwave
3 107 6 106
1 109 5 1011
Source
Alternating current
high frequency
Klystron tube
3.
Infrared (IR)
Incandescent objects
4.
Visible
6 106 7600
76003800
5.
Ultraviolet(UV)
3800150
6.
X-Rays
1500.1
2 1016 3 1019
7.
-Rays
0.10.01
3 1019 3 1020
8.
Cosmic Rays
0.01zero
3 1020 Infinity
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n1 n 1
= wave number
= wave length
R = Rydberg constant (109678 cm 1 )
n1 and n 2 have integral values as follows
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Series
Lyman
Balmer
Paschen
Brackett
Pfund
Note :
n1
n2
1
2
3
4
5
2, 3, 4, etc
3, 4, 5 etc
4, 5, 6 etc
5, 6, 7 etc
6, 7, 8, etc
Ultra-vio
Visible
Infra-red
Infra-red
Infra-red
All lines in the visible region are of Balmer series but reverse is not true, i.e., all Balmer lines will not fall in
visible region
Solution :
Given
= 480 nm = 480 109 m [1 nm = 109 m]
c = 3 108 m/s
Frequency,
Illustration 2:
Solution :
v=
c 3 108 ms 1
=
= 6.25 1014 s 1 = 6.25 1014 Hz.
48 109
Find the quantum numbers of the excited state of electrons in He+ ion which
on transition to ground state and first excited state emit two photons of
wavelengths. 30.4 nm and 108.5 nm respectively. (RH = 1.09678 107 m1).
1
1
1
= R H Z2 2 2
n1 n 2
n1 = 1, n2 = ?
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1 1
1
= 1.09678 107 4 2 2 n2 = 2
9
30.4 10
11 n 2
Illustration 3:
Solution :
hc
7.81 1019
100 = 33.66%
8 2.9 1019
EXERCISE 1
1.
Calculate the energy associated with photon of light having a wavelength 6000 .
2.
How many photons of light having a wavelength 4000 are necessary to provide 1.00
J of energy?
3.
How many moles of photon would contain sufficient energy to raise the temperature of
225 g of water 21C to 96C? Specific heat of water is 4.18 J g1 K1 and frequency of
light radiation used is 2.45 109 s1.
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nh
2
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(ii) Bohrs concept of stationary state of electron explains the emission and absorption
spectra of hydrogen like atoms.
(iii) The experimental values of the spectral lines of the hydrogen spectrum are in close
agreement with the calculated by Bohrs theory.
3.6C LIMITATIONS OF BOHRS THEORY
(i) It does not explain the spectra of atoms or ions having more than one electron.
(ii) Bohrs atomic model failed to account for the effect of magnetic field (Zeeman effect)
or electric field (Stark effect) on the spectra of atoms or ions. It was observed that
when the source of a spectrum is placed in a strong magnetic or electric field, each
spectral line further splits into a number of lines. This observation could not be
explained on the basis of Bohrs model.
(iii) de-Broglie suggested that electrons like light have dual character. It has particle and
wave character. Bohr treated the electron only as particle.
(iv) Another objection to Bohrs theory came from Heisenbergs Uncertainty Principle.
According to this principle it is impossible to determine simultaneously the exact
position and momentum of a small moving particle like an electron. The postulate of
Bohr, that electrons revolve in well defined orbits around the nucleus with well defined
velocities is thus not attainable.
3.6d BY BOHRS THEORY
(i) Radius and Energy levels of hydrogen atom: Consider an electron of mass `m and
charge `e revolving around a nucleus of charge Ze (where, Z = atomic number and e is
the charge of the proton) with a tangential velocity v.r is the radius of the orbit in
which electron is revolving.
By Coulombs Law, the electrostatic force of attraction between the moving electron
KZe2
and nucleus is Coulombic force = 2
r
1
K=
(where 0 is permitivity of free space)
40
K = 9 109 Nm2 C 2
In C.G.S. units, value of K = 1 dyne cm 2 (esu) 2
mv 2
r
Since the electrostatic force balance the centrifugal force, for the stable electron orbit.
The centrifugal force acting on the electron is
mv 2 KZe 2
= 2
r
r
(i)
KZe 2
(ii)
mr
According to Bohrs postulate of angular momentum quantization, we have
(or) v 2 =
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nh
2
nh
v=
2mr
mvr =
n2h2
4 2 m 2 r 2
Equating (2) and (3)
v2 =
(iii)
KZe 2
n 2h 2
= 2 2 2
mr
4 m r
Solving for r we get r =
n2h2
4 2 mKZe 2
where n = 1, 2, 3,
Hence only certain orbits whose radii are given by the above equation are available for
the electron. The greater the value of n, i.e., farther the level from the nucleus the
greater is the radius.
The radius of the smallest orbit (n = 1) for hydrogen atom (Z = 1) is r0 .
r0 =
n 2h 2
12 (6.626 10 34 ) 2
=
= 5.29 10 11 m
42 me2 K 4 (3.14)2 9 10 31 (1.6 1019 )2 9 109
r0 = 0.5629
Radius of nth orbit for an atom with atomic number Z is simply written as
n2
n2
= 0.529
z
z
(ii) Energy level of Hydrogen atom: The total energy, E of the electron is the sum of
kinetic energy and potential energy. Kinetic energy of the electron = 1 2 mv 2
rn = r0
Potential energy =
KZe 2
r
KZe2
r
From equation (1) we know that
Total energy = 1 2 mv 2
(iv)
mv 2 KZe 2
= 2
r
r
KZe2
2r
Substituting this in equation (iv)
2
2 mv =
KZe2 KZe2
KZe 2
=
2r
r
2r
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1
KE = PE, KE = TE
2
Substituting for r, gives us
2 2 mZe 2e 4 K 2
where n = 1, 2, 3,
n 2h 2
This expression shows that only certain energies are allowed to the electron. Since this
energy expression consists so many fundamental constant, we are giving you the
following simplified expressions.
E=
E = 21.8 10 12
= 21.8 10 19
E n = 13.6
Z2
erg per atom.
n2
Z2
Z2
J
per
atom
=
13.
6
eV per atom
n2
n2
z2
eV per atom
n2
H
H + + e (ionization).
(iii) Velocity of electron
nh
nh
;v=
2
2mr
By substituting for r we are getting
We know that, mvr =
v=
2 KZe 2
nh
Z
cm / sec.
n
Further application of Bohrs work was made, to other one electron species
(Hydrogenic ion) such as He + and Li2 + . In each case of this kind, Bohrs prediction of
the spectrum was correct.
Where excepting n and z all are constant, v = 2.18 108
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(iv) Explanation for hydrogen spectrum by Bohrs theory: According to the Bohrs
theory electron neither emits nor absorbs energy as long as it stays in a particular orbit.
However, when an atom is subjected to electric discharge or high temperature, and
electron in the atom may jump from the normal energy level, i.e., ground state to some
higher energy level i.e., excited state. Since the life time of the electron in excited state
is short, it returns to the ground state in one or more jumps.
During each jumps, energy is emitted in the form of a photon of light of definite
wavelength or frequency. The frequency of the photon of light thus emitted depends
upon the energy difference of the two energy levels concerned ( n1 , n 2 ) and is given by
hv = E 2 E1 =
2 2 mZ2 e 4 K 2
h2
1
1
n2 n2
2
1
22 mZ2 e 4 K 2 1
1
2 2
3
h
n1 n 2
The frequencies of the spectral lines calculated with the help of above equation are
found to be in good agreement with the experimental values. Thus, Bohrs theory
elegantly explains the line spectrum of hydrogen and hydrogenic species.
Bohr had calculated Rydberg constant from the above equation.
v=
C 2 2 mZ2 e 4 K 2
=
h3
1
1
2 2
n1 n 2
1
22 mZ2 e 4 K 2
==
h 3c
1
1
2 2
n1 n 2
where
2 2 me 4 K 2
= 1.097 10 7 m 1 or 109678 cm 1
3
hc
1
1
1
= RZ2 2 2
n1 n 2
= wave number.
Illustration 4:
Solution:
Calculate the ratio of the radius of Li+2 ion in 3rd energy level to that of He+
ion in 2nd energy level.
n2
r
z
2
r1 n1 z 2
=
r2 n 2 z1
n1 = 3
n2 = 2
z1 = 3
(for Li2+ )
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(for He + )
z2 = 2
2
r1 3 2 3
= =
r2 2 3 2
Illustration 5:
How far from the nucleus is the electron in a hydrogen atom if it has energy
of 0.850 eV.
Solution:
En =
Z2
21.69 10 19
n2
Z2
2 21.69 10 19 = 0.85 1.6 10 19
n
Find the wavelengths of the first line of He+ ion spectral series whose
1 1
= 2.7451 10 4 cm 1
interval between extreme lines is
1 2
Illustration 6:
Solution:
1 1
1
1
RZ2
= RZ2 2 2 R 2 2
=
2
2
2
n1
n1 (n1 + n) (n1 + 1)
2.7451 104 =
109677.76 2 2
(n1 + 1)2
(n1 + 1) = 4
n1 = 3
Wavelength of first line,
1
1 1
= 109677.76 2 2 2 2
3 4
= 4689 108 cm = 4689
Illustration 7 :
The velocity of electron in a certain Bohr's orbit of hydrogen atom bears the
ratio of 1 : 275 to the velocity of light
(a) What is the quantum number (n) of orbit?
(b) Calculate the wave number of radiations emitted when electron jumps
from (n+1) state to ground state
Solution :
1
3 108 m/sec
=
= 1.09 106 m/sec
275
275
2ZKe 2
2.18 106 Z
=
m/sec
nh
n
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For hydrogen
Vn =
2.18 106
m/sec
n
1.09 106 =
2.18 106
n=2
n
1
= 1.09678 107
Illustration 8:
1
1 1
= RH = 2 2
1 3
1 1
2
1
1 9 = 9.75 10 m
Two hydrogen atoms collide head on and end up with zero kinetic energy.
Each then emits a photon of wave length 121.6 nm which transition leads to
this wavelength? How fast were the hydrogen atoms travelling before
collision?
RH = 1.09678 107 m1
MH = 1.672 1027 Kg
Solution:
1
1 1
= RH 2 2
1 n
1
= 1.09678 107
121.6 109
1 1
1 n 2
n=2
Energy released is due to collision and all the kinetic energy released in form
of radiant energy
1
hc
mv2 =
2
1
6.625 1034 3 108
1.67 1027 V2 =
2
121.6 109
EXERCISE 2
1.
2.
Ionisation energy of H-atom is 13.6 eV. Calculate ionization energy of He+, Li2+ and
Be3+ (all isoelectronic of H).
3.
If the electron in a hydrogen atom were in the energy level with n = 3, how much
energy would be required to ionize the atom ?
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4. PHOTOELECTRIC EFFECT
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.
According to Einstien,
Maximum kinetic energy of the ejected electron = absorbed energy work function
1
2
2 mv max
1 1
= hv hv0 = hc
0
Solution:
As,
= h + KE
.E. = hc o =
hc hc
=
+ K.E
o
hc( o )
=
1
m2 = 1.6565 1019
2
h
6.625 1034
=
= 1.2 109 m
25
mv 5.49 10
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Illustration 10 : Photo - electrons are liberated by ultraviolet light of wavelength 3000 from
a metallic surface for which the photoelectric threshold is 4000. Calculate
de-Broglie wavelength of electrons emitted with maximum kinetic energy
Solution:
hc hc
=
+ K.E
o
As,
h = h + KE
K.E. = hc o =
hc( o )
=
1
m2 = 1.6565 1019
2
m = 5.49 1025
=
h
6.625 1034
=
= 1.2 109 m
mv 5.49 1025
(i)
(ii)
c
= mc 2
h
h
=
mc p
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h
h
=
p
2Em
(a)
(b)
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If the two ends of the electron wave meet to give a regular series of crests and troughs, the
electron wave is said to be in phase, i.e., the circumference of Bohrs orbit is equal to whole
number multiple of the wavelength of the electron wave.
So,
2r = n
or
2r
n
h
mv
Thus,
h
2r
=
mv
n
or
mvr = n
h
2
h
2
This proves that the de Broglie and Bohrconcepts are in perfect agreement with each other.
Illustration 11 : What is the mass of a photon of sodium light with a wavelength of 5890 .
=
h
mc
or
m=
h
c
So,
m=
6.63 1027
= 3.752 1033 g
8
10
5890 10 3 10
Solution:
h
mu
(ii)
h
m
21
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h2
1/2 m
= e V V = 2m 2 c
m
=
(6.625 1034 ) 2
= 63.3 volt
2 9.108 10 (1.54 1010 )2 1.602 1019
31
According to de Broglie.
Matter wavelength, =
h
h
=
mv p
1
p2
h2
= 2
mv2 =
2
2m (2m)
h
2mE
= 2.07106 m J -1
dE
(6.62 1034 )2
at =14
EXERCISE 3
1. What accelerating potential must be imparted to a proton beam to give it an effective
wavelength of 0.050 ?
2. A 1.0 g projectile is shot from a gun with velocity of 100 m s1. What is the de Broglie
wavelength ?
3. Two particles A and B are in motion; if wavelength of A is 5 108 m, calculate
wavelength of B so that its momentum is double of A.
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measure any one of these two quantities with higher accuracy the other becomes less
accurate
Mathematical expression for the Heisenberg uncertainty principle is simply written as
x . p h / 4
where p = mv
Explaination of Heisenberg uncertainty Principle : Suppose we attempt to measure both
the position and momentum of an electron, to pinpoint the position of the electron we have
to use light so that the photon of light strikes the electron and the reflected photon is seen in
the microscope. As a result of the hitting, the position as well as the velocity of the electron
are disturbed. The accuracy with which the position of the particle can be measured depends
upon the wavelength of light used the uncertainty in position is . The shorter the
wavelength, the greater is the accuracy. But shorter wavelength means higher frequency and
hence higher energy. So if position is fixed velocity will not be fixed.
Illustration 14 : Why electron cannot exist inside the nucleus according to Heisenbergs
uncertainty principle?
Solution :
h
4
x (m.v) = h/4
v =
h
1
6.63 1034
1
=
15
22
4 x.m
10 9.1 10 31
4
7
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8 2 m
(E U) = 0
h2
This equation implies in essence that a body of mass m, velocity v, potential energy U and
total energy E has a wave associated with it of an amplitude given by wave function . The
schrodinger equation has an infinite many solution. For any physical situation must be
finite, single valued and continuous. The particular values of which yield satisfactory
solution of above equation are called wave functions. Wave function for an electron is
called an atomic orbital. Each solution is identified by three quantum numbers. A set of
three quantum numbers is needed to describe an electron because electrons in atoms are
moving in three dimensional space.
Schrodinger
equation
Solve
Wave function
The wave function has got no meaning but the square of the wave function 2 is a
mathematical expression of how the probability of finding an electron in a small volume
varies from place to place. Square of wave function is like the square of amplitude of an
electromagnetic wave. The intensity of electromagnetic radiation is proportional to square
of amplitude.
8. QUANTUM NUMBERS
To understand the concept of Quantum Numbers, we must know the meaning of some terms
clearly so as to avoid any confusion.
Energy Level: The non-radiating energy paths around the nucleus are called as Energy
Levels of Shells. These are specified by numbers having values 1, 2, 3, 4, ... or K, L, M, N,
... in order of increasing energies. The energy of a particular energy level is fixed.
Sub-Energy Level: The phenomenon of splitting of spectral lines in electric and magnetic
fields reveals that there must be extra energy levels within a definite energy level. These
were called as Sub-Energy Levels or Sub-Shells. There are four types of sub-shells namely;
s, p, d, f.
First energy level (K or ) has one sub-shell designated as 1s, the second energy level
(L or 2) has two sub-shell as 2s & 2p, the third energy level (M or 3) has three sub shell as
3s, 3p and 3d, and the fourth energy level (N or 4) has four sub-shells as 4s, 4p, 4d and 4f.
The energy of sub-shell increases roughly in the order: s < p < d <f.
Orbital: Each sub-energy level (sub-shell) is composed of one or more orbitals. These
orbitals belonging to a particular sub-shell have equal energies and are called as degenerate
orbitals. s-sub-shell has one orbital, p has three orbitals, d have five orbitals and f has seven
orbitals.
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To describe or to characterize the electrons around the nucleus in an atom, a set of four
numbers is used, called as Quantum Numbers. These are specified such that the states
available to the electrons should follows the laws of quantum mechanics or wave
mechanics.
8.1 PRINCIPAL QUANTUM NUMBER: (n)
This quantum number represents the main energy levels (principal energy levels) designated
as n = 1, 2, 3, ... or the corresponding shells are named as K, L, M, N, ... respectively. It
gives an idea of position and energy of an electron. The energy level n = 1 corresponds to
minimum energy and subsequently n = 2, 3, 4, ..., are arranged in order of increasing
energy.
Higher is the value of n, greater is its distance from the nucleus, greater is its size and also
greater is its energy.
It also gives the total electrons that may be accommodated in each shell, the capacity of
each shell is given by the formula 2n 2 , where n : principal quantum number.
8.2 AZIMUTHAL QUANTUM NUMBER: (l)
This number determines the energy associated with the angular momentum of the electron
about the nucleus. It is also called as the angular momentum quantum number. It accounts
for the appearance of groups of closely packed spectral lines in electric field.
It can assume all integral values from 0 to n1. The possible values of l are :
0, 1, 2, 3, ..., n1.
Each value of l describes a particular sub-shell in the main energy level and determines the
shape of the electron cloud.
When n = 1, l = 0, i.e., its energy level contains one sub-shell which is called as a s-subshell. So for l = 0, the corresponding sub-shell is a s-sub-shell. Similarly when l = 1, 2, 3,
the sub-shells are called p, d, f sub-shells respectively.
As you known for n = 1, l = 0, there is only one sub-shell. It is represented by 1s. Now for n
= 2, l can take two values (the total number of values taken by l is equal to the value of n in
a particular energy level). The possible values of l are 0, 1. The two sub-shell representing
the IInd energy level are 2s, 2p. In the same manner, for n = 3, three sub-shells are
designated as 3s, 3p, 3d corresponding to l = 0, 1, 2, and for n = 4, four sub-shells are
designated as 4s, 4p, 4d, 4f corresponding to l = 0, 1, 2, 3.
h
.
The orbital Angular momentum of electron = A(A + 1)
2
Note that its value does not depend upon value of n.
8.3 MAGNETIC QUANTUM NUMBER (m)
An electron with angular momentum can be thought as an electric current circulating in a
loop. A magnetic field due to this current is observed. This induced magnetism is
determined by the magnetic quantum number. Under the influence of magnetic field, the
electrons in a given sub-energy level prefer to orient themselves in certain specific regions
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in space around the nucleus. The number of possible orientations for a sub-energy level is
determined by possible values of m corresponds to the number of orbitals in a given subenergy level).
m can have any integral values between l to +l including 0, i.e., m = l, 0 +, l, , 0, 1, 2,
3, 4, . . ., l1 + l. We can say that a total of (2l + 1) values of m are there for a given value of
l 2, 1, 0, 1, 2, 3.
In s sub-shell there is only one orbital [l = 0, m = (2l +1) = 1].
In p sub-shell there are three orbitals corresponding to three values of m : 1, 0 +1. [l = 1
m = (2l +1) = 3]. These three orbitals are represented as p x , p y , p z along X, Y, Z axes
perpendicular to each other.
In d sub-shell, there are five orbitals corresponding to 2, 1, 0 +1, +2, [l = 2
m = ( 2 2 + 1) = 5] . These five orbitals are represented as d xy , d yz , d zx , d x 2 y2 ,dz 2 .
In f sub-shell there are seven orbitals corresponding to 3, 2, 1, 0, +1, +2, +3 [l = 3
m = (2 3 + 1) = 7] .
8.4 SPIN QUANTUM NUMBER (s)
When an electron rotates around a nucleus it also spins about its axis. If the spin is
clockwise, its spin quantum number is +1/2 and is represented as . If the spin is anticlockwise, its value is 1/2 and is represented as . If the value of s is +1/2, then by
convention, we take that electron as the first electron in that orbital and if the value of s is
1/2, it is taken as second electron.
Illustration 15:
Solution:
Write down the values of quantum numbers of all the electrons present in
the outermost orbit of argon (At. No. 18)
1s 2 , 2s 2 2p 6 ,3s 2 3p 2x 3p 2y 3p z2
The electronic configuration of argon is
Values of quantum numbers are:
n
Illustration 16:
3s
3p 2x
+1/2, 1/2
+1/2, 1/2
3p 2y
+1/2, 1/2
3p 2z
+1/2, 1/2
Solution:
1
1
or
2
2
NARAYANA
EXERCISE 5
1.
2.
3.
4.
2p
3s
3p
3d
4s
4p
4d
5s
5p
5d
6s
6p
4f
7s
This order of orbitals is only a guidance and exceptions are known in few cases
of atoms.
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where N is the total number of possible exchanges of coordinates between sets of two
electrons of parallel spin and K is the average exchange energy per set of electrons of parallel
spin. For a system containing n electrons of parallel spin. For a system containing n electrons
of parallel spin, N is given by
N=
n!
2(n 2)!
The exchange energies for the two possible configurations of Cr are as follows:
3d4, 4s2
n = 5 E = 10K
1
n = 6 E = 15K
3d5, 4s
that is, the exchange energy stabilization of 3d5, 4s1 configuration is larger than 3d4, 4s2
configuration. Besides this, since the two electrons with parallel spins remain farther apart
than two electrons with opposed spins, the Columbic repulsion energy is also smaller in case
of two parallel spins. Thus the configuration 3d54s1, which contains more number of parallel
spins, is more stable than 3d54s2. The stability of the 3d104s1 configuration for the copper atom
may be explained in the same way.
Thus, it may be concluded that the unusual stability of electronic configurations involving
half-filled and completely filled orbitals is due to the larger exchange energy and lesser
columbic repulsion.
The simplified explanation of the above illustration is given below :
Exchange Energy : This stabilizing effect arises whenever two or more electrons with the
same spin are present in the degenerate orbitals of a subshell. These electrons tend to
exchange their positions and the energy released due to this exchange is called exchange
energy. The number of exchanges that can take place is maximum when the subshell is either
half filled or completely filled (Figure given below). As a result the exchange energy is
maximum and so is the stability.
1
4 exchange by
electron 1
3 exchange by
electron 2
2 exchange by
electron 3
1 exchange by
electron 4
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filled and the maximum number of electrons in a shell, sub-shell or orbital. The configuration
so obtained can be represented in two ways. As an illustration, let us consider fluorine (Z = 9):
F (Z = 9) 1s2 2s2 2p 2x 2p 2y 2p 1z or
1s
2s
2px
2py
2pz
Importance of knowing the exact electronic configuration of an element lies in the fact that
the chemical properties of an element are dependent on the behaviour and relative
arrangement of its electrons.
Electronic configurations of heavier elements (beyond Z = 56) deviate a little from the order
mentioned previously. These are brief listed below
a) Lanthanides
La (Z = 57)
:
[Xe] 6s25d1 (not 4f1)
Ce (Z = 58)
:
[Xe] 6s25d14f1
Pr (Z = 59)
:
[Xe] 6s25d14f2
b) Actinides
Ac (Z = 89)
:
[Rn] 7s26d1 (not 5f1)
Th (Z = 90)
:
[Rn] 7s26d15f1
Pa (Z = 91)
:
[Rn] 7s26d15f2
c) Beyond Z = 103 Z = 104
:
[Rn] 5f146d27s2
Z = 105
:
[Rn] 5f146d37s2
Z = 106
:
[Rn] 5f146d47s2
Z = 112
:
[Rn] 5f146d107s2
EXERCISE 6
1. State the basic ideas that are violated by each of the following electronic configuration
and replace each by the correct configuration :
(a) B5 1s2 2s2
(b) Na11 1s2 2p6 2p6 2d1
(c) K19 [Ar] 3d1
(d) Ti22 [Ar] 4s2 4p2
(e) Hg80 [Xe] 4f10 5d10 6s2 6p2
2. Which of the following will be coloured ion ?
(a) Fe2+
(b) Cu+
(c) Sc3+
(d) Mn2+
Which has the maximum magnetic moment ?
3. Magnetic moment of X3+ ion of 3d series is 35 B.M. What is atomic number of X3+ ?
NARAYANA
2s
1s
x
nucleus
radial node
10.2 p ORBITALS
p - orbitals ( A = 1): These have a dumb - bell shape, having three possible mutually
perpendicular orientations. As they are not symmetrical, they have a directional character.
The two lobes of p-orbitals are separated by a nodal plane, where the probability of finding
electron is zero.
z
yz plane
y
xy plane
xz plane
x
px orbital
py orbital
pz orbital
10.3 d ORBITALS
d - orbitals ( A = 2): They have relatively complex geometry. Out of the five d-orbitals, the
first two d z2 & d x2 y2 lie along the axes, while the other three (dxy, dzx, dyz) project in
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x
dxy orbital
z
dyz orbital
dxz orbital
z
y
x
dx2 y 2 orbital
dz2 orbital
The five d orbitals
z
Nodal cone
y
Two nodal surface forming two nodal cones about z axis for d Z2 orbital.
xz - nodal plane
xy - nodal
plane
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yz - nodal plane
y
xy - nodal
plane
yz - nodal plane
z
y
xz - nodal
plane
x
Solution:
(a) n = 3, A = 2, m = 2
(b) n = 4, A = 0, m = 0
(c) n = 3, A = 1, m 1
(d) n = 2, A = 1, m = 1
(a) 3d x 2 y2
(b) 4s
(c) 3p x or 3p y
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Illustration 18 : (a) Find the orbital angular momentum of an electron in the following
orbital
(i) 3p
(ii) 3d
(iii) 3s
(a) =
A(A + 1)
h
=
2
A(A + 1) =
(i)
(ii)
For 3d , A = 2 A =
(iii)
For 3s, A = 0, l = 0
2(2 + 1)
h
= 6 =
2
(b) For the same value of n, higher the value of (n + A), higher is the energy.
(c) For the same value of n + A, higher the value of n, higher will be the
energy.
For (i) ( n + A) = 4 for 4s orbital
For (ii), (n+A) = 4, for 3d orbital
For (iii) ( n + A) = 4 for
For (iv), (n+A) = 3
3p orbital
3s orbital
Decreasing order of energy = (ii) > (i) > (iii) > (iv)
NARAYANA
z = r cos
and also,
x2 + y2 + z2 = r2
When Schrodinger equation is solved in polar coordinates, for hydrogen atom. It gives the
possible energy states and corresponding wave function [ (r, , )], called atomic orbitals.
The schrodinger equation cannot be exactly solved for a multi electron atom.
Atomic Orbitals and their Pictorial Representation : An atomic orbital is an electron wave
function, (r, , ) obtained from the solution of the schrodinger equation. Wave function
is a mathematical function of the three coordinates of electron (r, , ). This wave
function can be written into three separate parts each of which is a function of only one
coordinate.
= f(r, , )
(r, , ) = R(r), (), ()
R is function of r, is function of and is function of .
Where, R is radial function and and are angular function. The radial function depends
on quantum numbers n and A. The angular function depends on A and m.
Significance of Wave Function : The orbital wave function has no physical
significance. It is the square of the absolute value of wave function ||2, which has a
physical significance. It measure the electron probability density at a point in an atom.
If the variations of or ||2 with r, , are to be observed graphically. It would need a four
dimensional graph in space but on the plane of paper we can draw only two dimensional
graph to overcome this difficult.
We draw separate diagrams for
(i) Variation of radial function
(ii) Variation of Angular function
R is known as radial wave function
R2 is known as radial probability density and 42r2R2 is known as radial probability.
11.1 FUNCTION VARIATION OF RADIAL FUNCTION
(i) Plot of Radial Wave Function (R) vs r: In all cases R approaches zero as r
approaches infinity. There is a node (where the probability of finding electron is zero)
in 2s orbital radial function. At the node the value of radial function changes from
positive to negative for 2s orbital. In general ns orbitals have (n 1) nodes.
Node
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(ii) Radial Probability Density (R2)vs r: The square of radial wave function R2 for an
orbital gives the radial density. The radial density gives the probability density of
finding the electron at a point along a particular line.
Node
(iii) Radial Probability Functions (42r2R2) vs r: Radial probability function gives the
probability of finding the electron at a distance r from the nucleus regardless of
direction.
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SECTION - I
SUBJECTIVE TYPE PROBLEMS
Problem 1 :
Solution :
Problem 2 :
Solution :
= 2.55 eV
Now
A spectral line in the spectrum of H-atom has a wave number of 82200 cm1 .
What transition is responsible for this radiation? (Rydberg constant
RH=1.096 107 m-1).
= 1 / = 1/8220000
it lies in UV region or in Lyman series
Hence,
n1 = 1
Using the relation for wave umber for H-atom:
1
1
2
2
n1 n 2
v = 1/ = RH
1
1
82200 = 1.096 105 2 2
n1 n 2
Problem 3 :
Solution :
1
n 22
3
4
n2 = 2
Calculate the wavelength of light radiation that would be emitted, when an electron in
the fourth Bohrs orbit of He+ ion falls to the second Bohrs orbit. To what transition
does this light radiation correspond in the H-atom ?
Let us calculate E first.
1
Substituting
Now
E = 21.7 1019 Z2 n 2 n 2
2
1
n1 = 2 and n2 = 4, Z = 2 we get ; E = 1.632 108 J
=
hc
= 1.218 107 m = 1218
E
The value of = 1218 implies that, in H-atom this transition would lie in Lyman Series.
Hence our aim is now to find the transition : n2 1. (1st orbit)
n2 = 2
Hence the corresponding transition in H-atom is 2 1.
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Problem 4 :
Find the wavelength of radiation required to excite the electron in ground level of Li++
(Z = 3) to third energy level. Also find the ionisation energy of Li 2+ .
R = 1.097 107 m-1
1
1
= RZ2 2 2
n
n
2
1
Solution :
Putting the values :
We get
n 1 = 1, n2 = 3, Z = 3
= 8.77 107 m1
1
= 113.9
Ionisation energy is the energy required to remove the electron from ground state to infinity
i.e. corresponding transition responsible is 1
i.e.
Problem 5 :
Solution :
x =
h
6.63 10 34
=
4p 4 3.14 2 103
= 2.135 1032 m.
p = mv
= 9.1 1031 2 106
= 1.82 1024 Kgm/s
p = 0.1 % of p = 1.82 1027 Kgm/s
x =
Solution :
h
4
(a)
Problem 6 :
E = 13.6 32 2 2
1
E = 122.4 eV = 1.95 107 J = ionisation energy
h
6.63 10 34
=
4p 2 3.14 1.82 10 21
x = 2.89 108 m
Hydrogen when subjected to photo-dissociation, yields one normal atom and one atom
possessing 1.97 eV more energy than normal atom. The bond dissociation energy of
hydrogen molecule into normal atoms is 103 kcals mol1 . Compute the wave length of
effective photon for photo dissociation of hydrogen molecule in the given case.
H2 H + H*
where H is normal H-atom and H* is excited H-atom.
So the energy required to dissociate H2 in this matter will be greater than the usual bond
energy of H2 molecule.
E(absorbed) = dissociation energy of H2 + extra energy of excited atom
energy required to dissociate in normal manner = 103 103 cal (given)
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Find out the number of waves made by a Bohr electron in one complete revolution in
its 3rd orbit.
For an electron to be in a particular energy level of radius r, with de Bronglie wavelength :
2r = n
(where n = number of waves in one revolution)
=
h
2r mv
n=
mv
h
Problem 8 :
With what velocity should an particle travel towwards the nucleus of a copper atom
so as to arrive at a distance 1013 metre from the nucleus of the copper atom?
Solution :
To arrive at a distance d from the nuceleus, kinetic energy of - particle equals electrostatic
potential energy.
KE = PE
K ( q )(q cu )
1
m V2 =
2
d
q
q
m
K
V =
2 k q q cu
m d
Find the energy released (in ergs), when 2.0 gm atom of Hydrogen undergo transition
giving spectral line of lowest energy in visible region of its atomic spectrum.
Solution :
NARAYANA
Find the ratio of frequencies of violet light ( = 4.10 105) to that of red light
( = 6.56 10 5 cm). Also determine the ratio of energies carried by them.
C = ;
c : speed of light, : frequency & : wavelength
1
2
1
2
=
1
=
6.56 105
= 1.6
4.10 105
E1
E2
1
2
= = = 1.6
2
1
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SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1 :
A photon of wavelength 300 nm is absorbed by a gas and then reemitted as two photons.
One photon is red with wavelength of 760 nm. The wave number of the second photon will
be
(a) 2.02 106 m1
(b) 3.02 106 m1
6
1
(c) 1.02 10 m
(d) 2.2 106 m1
E =
Solution :
hc
...(i)
hc
E1 =
1
...(ii)
hc
E2 =
2
...(iii)
1
1
+
1 2
E = E1 + E2 = hc
1
1
-9
(300 10 )
1
2
= +
1
2
=
1
-9
(760 10 )
1
1
2
9
=
10
300 760
= (0.00333 0.00131) 109 = 2.02 106 m1
(a)
Problem 2 :
A certain laser transition emits 6.37 1015 quanta per second per square meter. The power
output in joules per square meter per second would be (l = 632.8 nm).
(a) 5 105 J m2 sec1
(b) 2 103 J m2 sec1
(c) 9.2 103 J m2 sec1
(d) none of the above
Solution :
= 2 103 J m2 sec1
(b)
Problem 3 :
The uncertainity in the location of circulating electron is equal to its de Broglie wavelength.
The minimum percent error in its measurement of velocity under this circumstance will be
approximately
(a) 4
(b) 8
(c) 18
(d) 22
Solution :
Let the electron be moving with momentum, p, its wavelength will be equal to h/p.
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x =
h
p
h
4
hp
4 h
p
1
p = 4
p
v
100
100
= p 100 =
=
= 7.96 8
v
4
4 3.14
(b)
Problem 4 :
A mono electronic species in energy level with energy X was provided with excess of energy
so that it jumps to higher energy level with energy Y. If it can emit 6 wavelenths originated
from all possible transition between these group levels, then which of the following relation is
correct?
(a)
X
3
= 1+
Y
n
(b)
X n
=
Y 6
(c)
X
= (n -1)2
Y
(d)
X
3
= 1+
Y
n
If n is the principal quantum number of energy level corresponding to energy X, the principal
quantum number of energy level Y is (n + 3) as it emit 6 wavelengths.
X
(n + 3) 2
=
Y
n2
X
3
= 1+
Y
n
(a)
Problem 5 :
Solution :
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v = v0 + Vstop
h
So the given graph will be a straight line with slope equal to
e
h
1.6 1019
6.626 1034
= 2.4141014
(c)
Problem 6 :
The radius of hydrogen atom in its ground state is 5.3 1011 m. After collision with an
electron it is found to have a radius of 21.2 1011m. The principal quantum number of the
final state of the atom is
(a) 2
(b) 3
(c) 4
(d) 5
Solution :
n2
meters
z
21.2 1011
n =
11
5.310
=2
(a)
Problem 7 :
Suppose 1017 J of energy is needed by theinterior of human eye to see an object. How many
photons of green light (l = 550 nm) are needed to generate this minimum amount of energy?
(a) 14
(b) 28
(c) 39
(d) 42
Solution :
n=
1017 550 10 9
1017
=
= 27.6 28 photons
hc
6.626 1034 3 108
(b)
Problem 8 :
Which element has a hydrogen like spectrum whose lines have wavelength one fourth of
atomic hydrogen?
(a) He+
(b) Li2+
3+
(c) Be
(d) B4+
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Solution :
1
H
= R 12
1
X
= RZ2
n1
n 22
...(i)
1
1
n2 n2
1
2
...(ii)
x
Z = 2 (He+)
(a)
Problem 9 :
Solution :
Ionisation potential of hydrogen is 13.6 eV. Hydrogen atom in the ground state are excited
by monochromatic light of energy 12.1 eV. The spectral lines emitted by hydrogen according
to Bohrs theory
(a) One
(b) Two
(c) Three
(d) Four
The electron in H atom is excited to III shell after absorbing 12.1 eV. The possible transition
state = (3-1) = 3.
(c)
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SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1:
Solution :
Problem 2 :
Solution :
Problem 3:
In hydrogen like sample two different types of photons A and B are produced by electronic
transition. Photon B has its wavelength in the infrared region if photon A has more energy
than B, then the photon A may belong to the region
(a) ultraviolet
(b) visible
(c) infrared
(d) none
(a, b, c)
Since B is in infrared region and A has more energy than B hence it will have lesser wave
length i.e. ultra violet, visible or infrared region.
A hydrogen like atom in ground state absorbs n photons having the same energy and it
emits exactly n photons when electronic transition takes place. Then the energy of the
absorbed photon may be
(a) 91.8 eV
(b) 40.8 eV
(c) 48.4 eV
(d) 54.4 eV
(a, b)
Since it absorbs n photons and it also emits exactly n-photons therefore transition must
have taken place from 1 to 2.
Energy of photon = 10.2 Z2
where Z = 1, 2, 3, 4
Identify the correct statement(s)
(a) || is the probability of finding the electron in an orbital
(b) p-orbital is directional in nature
(c)
(d)
Solution :
(b, c)
It is obvious from the fact.
Problem 4 :
in velocity is : ! =
2
Solution :
(a)
1
!
2m
(b)
!
4m
(c)
1
!
4m
(d)
1
!
m
(d)
P.x
h
4
2x = P (given)
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P 2
h
2
4
m 2 ( V) 2
h
2
{ P = mV}
P 2
h
2
4
Problem 5 :
h
2m 2
1 h
m 2
or
1
!
m
In a hydrogen like sample electron is in 2nd excited state, the binding energy of 4th state of
this sample is 13.6 eV, then
(a) A 25 eV photon can set free the electron from the second excited state of this sample
(b) 3 different types of photon will be observed if electrons make transition up to ground
state from the second excited state
(c) If 23 eV photon is used then K.E. of the ejected electron is 1eV
Solution :
(d) 2nd line of Balmer series of this sample has same energy value as 1st excitation energy
of H-atoms
(a, b)
B.E. of
4th
state = 13.6
z2
n2
13.6
z2
= 13.6
42
z=4
sample is Be3+
energy of elecron in 3rd state
state = 1.5 42 = 24 eV
therefore 25 eV photon will cause ionisation.
Problem 6 :
Solution :
Problem 7 :
Solution :
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Problem 8 :
Solution :
Problem 9 :
The possible correct sets of quantum numbers for the unpaired electron of oxygen atom in
the orbitals of p-subshel are
(a) n = 2, l = 1, m = 0
(b) n = 2, l = 1, m = 1
(c) n = 2, l = 1, m = + 1
(d) n = 2, l = 1, m = 2
(a, b, c)
Option (d) is not possible because if l = 1, m has three values i.e. 1, 0, + 1.
The diagram illustrates a possible electronic configuration of which of the following species
Solution :
Problem 10 :
Solution :
(b) S atom
(d) P2 ion
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MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS
Write up I
In the Rutherfords experiment, -particles were bombarded towards the copper atoms so as to arrive
at a distance of 1013 metre from the nucleus of copper and then getting either deflected or traversing
back. The -particles did not move further closer.
Problem 1 :
Solution :
(b)
2
At the distance of closest approach v =
2Ze 2e 1
4 0 r0 m
Solution :
Which of the following metals can be used instead of gold in -scattering experiment
(a) Pt
(b) Na
(c) K
(d) Cs
(a)
It is because Pt is highly malleable and ductile and least ractive.
(b), (c) and (d) are soft metals and highly reactive, therefore, cannot be used.
Problem 3 :
N sin 4
(c)
1
sin / 2
4
(b) N
1
sin 4
(d) N = sin
1
sin ( / 2)
4
Hence, choice (c) is correct while choice (a), (b) and (d) are incorrect.
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Write up II
The branch of science which deals with dual behaviour of mater is said to be quantum mechanics. The
fundamental equation of quantum mechanics is Schrodinger wave equation. The important features of
quantum mechanics are
(i) The energy of electron is quantized as a result of wave like properties of electrons.
(ii) The position and momentum of an electron cannot be determined simultaneously. The path of
electron cannot be determined. We can only talk of probability of finding electron.
(iii) An atomic orbitals is represented by wave function for an electron. R is radial wave function
whose value varies with distance from the nucleus 2 determines total probability (angular and
radial) whereas R2 is called raidal probability. All information about electron in an atom is stored in
orbital wave function . R is radial wave function.
(iv) R can be +ve or ve but R2 is always +ve. Similarly, can be +ve or ve but 2 is always +ve 2
can be equal to zero.
Problem 4 :
Solution :
Problem 5 :
Solution :
Problem 6 :
(a)
(b) R2
(c)
(d) R2
r
Solution :
(b)
It is because 2s orbital has one node where R2 = 0.
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Sol.
Column (I)
Column (II)
(a)
(p)
infrared region
(b)
(q)
3.4 eV
(c)
(r)
13.6 eV
(d)
(s)
(a)
13.6 22
n2
n = 1, 2, 3 .....
Hence it can be 13.6 eV, 3.4 eV both
(b)
In 7 3 transition n = 7 3 = 4
Maximum no. of spectral line observed =
4(4 + 1)
= 10
2
5 1 : 10 lines
(d)
Series limit of Balmer series is the last line i.e. 3.4 eV energy.
(a) (q, r)
(b) (p, s)
(c) (s)
(d) (q)
NARAYANA
INSTITUTE OF CORRESPONDENCE COURSES
10.Assertion : Electronic configurations of Fe3+ (containing 23 electrons) is not same as that of Vanadium
(Z = 23), i.e. isoelectronic species do not have the same electronic configuration.
Reason :
Solution :
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ASSIGNMENTS
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1.
2.
The electromagnetic radiation of wave length 3186 is just sufficient to ionise the outermost electron
of a gaseous Cs atom. Calculate the ionization energy of Cs in kJ/mole.
3.
Calculate the energy emitted when electrons 1 g atom of hydrogen undergo transition giving spectral
lines of lowest energy in the visible region of its atomic spectrum.
4.
Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic hydrogen.
5.
Calculate the de Broglie wavelength of the electron in the ground state of hydrogen atom, given that its
kinetic energy is 13.6 eV. (1eV = 1.602 1019 J).
6.
With what velocity must an electron travel so that its momentum is equal to that of a photon of wavelength
560 nm?
7.
A laser emits monochromatic radiation of wavelength 663 nm. If it emits 1015 quanta per second per
square metre, calculate the power output of the laser in joule per square metre per second.
8.
If astronomical observations, signals observed from the distant starts are generally weak. If the photon
detector receives a total of 3.15 108 J from the radiations of 600 nm, calculate the number of photons
received by the detector.
9.
The energy of an -particle is 6.8 1018 J. What will be the wavelength associated with it?
10.
The ionization energy of hydrogen in excited state is + 0.85 eV. What will be the energy of the photon
emited when it returns to the ground state?
LEVEL - II
1.
Electromagnetic radiation of wavelength 242 MM is just sufficient to ionise the sodium atom. Calculate
the ionisation energy in kJ mol1.
2.
Find the number of quanta of radiations of frequency 4.67 1013 s1 that must be absorbed in order to
melt 5g of ice. The energy required to melt 1 g of ice is 333 J.
3.
Calculate the wavelength and energy of radiation emitted for the electronic transition from infinite to
stationary state of hydrogen atom.
4.
If the energy difference between two electronic states is 46.12 kcal mol1, what will be the frequency
of the light emitted when the electrons drop from higher to lower states?
5.
Calculate the ratio of the velocity of light and the velocity of electron in the first orbit of a hydrogen
atom.
6.
The wavelength of a certain line in Balmer series is observed to be 4341 . To what value of n does
this correspond?
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7.
The uncertainty in position and velocity of a particle are 1010 m and 5.27 1024 m s1 respectively.
Calculate the mass of the particle.
8.
Calculate the momentum of a particle which has a de Broglie wavelength of 2.5 1010 m.
9.
Find the number of waves made by a Bohr electron in one complete revolution in the 3rd orbit.
10.
The ionisation energy of hydrogen atom is 13.6 eV. What will be the ionisation energy of He+.
LEVEL - III
1.
Helium can be excited to 1s1 2p1 configuration by supplying 33.12 1019 J of energy. The lowest excited
singlet state 1s1 2s1 lies 5000 cm-1 below 1s1 2p1 state. What should be the average HeX bond energy
so that HeX2 could form non-endothermically ? Assume the compound would be formed from lowest
excited singlet state of He+. Heat of atomization of X = 200 kJ mol1 .
2.
A uranyl actinometer containing oxalic acid is irradiated with light of wavelength 4350 for 15 minutes.
At the end of this time, it was found that oxalic acid equivalent to 12 ml of 0.001 M KMnO4 solution has
been decomposed by light. At this wavelength, the quantum efficiency of actinometer is 0.58. Find the
power of radiation source in 104 watt assuming that one photon decomposes only one molecule of
oxalic acid.
3.
The reaction between H2 and Br2 to form HBr in the presence of light is initiated by the photodecompostion
of Br2 into free bromine atoms (free radicals) by absorption of light. The bond dissociation energy of
Br2 is 192 kJ/mole. What is the longest wavelength of the photon that would inititate the reaction?
4.
A hydrogen like atom (described by the Bohrs model) is observed to emit six wavelength, originating
from all possible transitions between a group of levels. These levels have energies between 0.85 eV
and 0.544 eV including both these values).
(a)
(b)
5.
Electrons in hydrogen like atom (Z = 3) make transition from the fifth to the fourth orbit and from the
fourth to the third orbit. The resulting radiations are incident normally on a metal plate and ejects photoelectrons. The stopping potential for the photo-electrons ejected by the shorter wavelength is 3.95 eV.
Calculate the work function of the metal and stopping potential for the photo-electrons jected by the
longer wavelength. (RH = 1.094 107 ms1).
6.
A particle of charge equal to that of an electron and mass 208 times the mass of electron
(i.e., mu-meson) moves in a circular orbit around a nucleus of charge + 3e. (Take the mass of the
nucleus to be infinite). Assuming that the Bohr model of the atom is applicable to this system.
(RH = 1.097 107 m1).
(i)
(ii)
Find the value of n for which the radius of the orbital is approximately the same as that of the first
Bohr orbit for H-atom.
(iii)
Find the wavelength of the radiation emitted when the mu-meson jumps from the third orbit to the
first orbit.
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7.
Estimate the difference in energy between 1st and 2nd Bohrs orbit for a H 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 l = 3.0 108 m? Which hydrogen atom like species does this atomic number corresponds
to?
8.
A series of lines in the spectrum of atomic H lies at wavelengths 656.46 , 480.27 , 434.17 , 410.29 nm.
What is the wavelength of next line in this series?
9.
When a beam of 10.6 eV photons of intensity 2.0 W/m 2 falls on a platinum surface of
area 1 10 -4 m2 and work function 5.6 eV , 0.53 % of the incident photons eject photo electrons. Find
the number of photo electrons emitted per second and their mimimum energies in (eV). Take
1 eV = 1.6 10 -19 J .
10.
Assume that the de Broglie wave associated with an electron can form a standing wave between the
atoms arranged in a one dimensional array with nodes at each of the atomic sites . It is found that one
such standing wave is formed if the distance d between the atoms of the array is 2 . A similiar
standing wave is again formed if d is increased to 2.5 but not for any intermediate value of d . Find
the energy of the electrons in electron volts and the least value of d for which the standing wave of the
type described can be formed .
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SECTION - II
SINGLE CHOICE QUESTIONS
1.
2.
3.
If the speed of electron in the Bohrs first orbit of hydrogen atom be x, then speed of the electron in the
3rd orbit is
(a) x/9
(b) x/3
(c) 3x
(d) 9x
Which one of the following set of quantum numbers is not possible for 4p electron?
(a) n = 4, l = 1, m = 1, ms = + 1/2
(b) n = 4, l = 1, m = 0, ms = + 1/2
(c) n = 4, l = 1, m = 2, ms = + 1/2
(d) n = 4, l = 1, m = 1, ms = 1/2
1 h
(a) +
2 2
(c)
4.
5.
6.
7.
8.
9.
(b) zero
h
2
(d)
h
2
The uncertainity in the momentum of an electron is 1.0 105 kg ms1. The uncertainity in its position
will be (h = 6.62 1034 kg m2 s1)
(a) 1.05 1028 m
Naturally occuring boron is 20% 5B10 and 80% 5B11. The atomic weight of boron is
(a) 10.50
(b) 11.0
(c) 10.80
(d) 10.20
A particle A moving with a certain velocity has a de Broglie wavelength of 1 . If particle B has mass
25% of that A and velocity 75% of that of A, the de Broglie wavelength of B will be approximately
(a) 1
(b) 5.3
(c) 3
(d) 0.2
What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition,
n = 4 to n = 2 in the He+ spectrum.
(a) n = 4 to n = 1
(b) n = 3 to n = 2
(c) n = 3 to n = 1
(d) n = 2 to n = 1
(c)
(b)
(d)
(d) in he z-direction
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10.
11.
12.
13.
14.
15.
16.
(d)
l (l + 1)
3e2
(b)
40 r
2e 2
e 2
(d)
40 r
40 r 2
The energy of an electron in the second Bohr orbit of H-atom is E. The energy of the electron in the
Bohrs first orbit is
(a) E/4
(b) 4E
(c) 4E
(d) 2 E
The wave number of the shortest wavelength of absorption spectrum of H-atom is (Rydberg
constant = 109700 cm1)
(a) 109700 cm1
(b) 3/4 109700 cm1
(c) 1/2 109700 cm1
(d) 9 10 109700 cm1
In the Bohrs orbit, what is the ratio of total kinetic energy and total energy of the electron?
(a) 1
(b) 2
(c) + 1
(d) + 2
In two H atoms A and B the electrons move around the nucleus in circular orbits of radius r and 4r
respectively. The ratio of the times taken by them to complete one revolution is
(a) 1 : 4
(b) 1 : 2
(c) 1 : 8
(d) 2 : 1
(c)
17.
18.
19.
20.
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SECTION - III
MULTIPLE CHOICE QUESTIONS
1.
2.
(b) n = 2, l = 2, m = 1
(c) n = 3, l = 0, m = 1
(d) n = 5, l = 2, m = 1
For radial probability distribution curves, which of the following is/are correct.
(a) The number of maxima in 2s orbital are two
(b) The number of spherical or radical nodes is equal to n l 1
(c) The number of angular nodes are l
(d) 3dz2 has two angular nodes.
4.
5.
g orbital is possible if
(a) n = 5, l = 4
Which of the following transitions are allowed in the normal electronic emission spectrum of an atom?
(a) 2s 1s
(b) 2p 1s
(c) 3d 2p
(d) 5p 3s
1
n
1
n4
(c) S =
7.
1
n3
h
2
(b) S = s
h
2
1 h
(d) S =
2 2
3 h
2 2
(b)
(c)
(d)
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8.
Which of the following statements relating to the spectrum of hydrogen atom are false?
(a) The lines can be defined by quantum number
(b) The line of longest wavelength in the Balmer series corresponds to the transition between n = 3 and
n = 2 levels
(c) The spectral lines are closer together at long wavelengths
(d) A continuum occurs at n =
9.
10.
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MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS
Write up - I
The wave numbers of the spectral lines of Lyman Series may be calculated using the equation given
below as derived by Niels Bohr for an atom or ion free from electron-electron repulsion.
= R H Z2 1 2 where n = 2, 3, 4 5.
n
where
22 m e k 2 e 4
= Rydberg constant
Ch 3
me is the mass of electron but for actual calculation we will have to consider the nuclear motion and then
me will have to be replaced by reduced mass (m) where
RH =
m N me
m N + m e , mN = mass of nucleus
2.
3.
If proton in the nucleus of hydrogen atom is replaced by positron (+1e0) having the charge of proton but
mass that of electron, the wave number of the lowest energy transition in the Lyman series of the
above designated H-atom considering the nuclear motion will be equal to
(a)
3
RH
4
(b)
3
RH
8
(c)
RH
2
(d)
3
RH
2
What will be the ratio of the wave number of the 1st line to that of the 5th line of Lyman series of
He+ ion?
(a)
25
32
(b)
27
35
(c)
100
32
(d)
108
35
NARAYANA
Write up - II
2
2
h 2 2
+
+
+V
82 m x 2 y 2 z 2
4 r 2 2 (r )
1s
4 r 2 2 (r )
2s
r
The wave functions of 1s and 2s orbitals of hydrogenic atom or ion are given below:
1/ 2
1s =
Z
2
a0
e Zr / a 0
1/ 2
Z
Zr Zr / 2a 0
2s =
2 e
a0
2a 0
In 2s-orbital there occurs a point at the radius at which curve touches X-axis. Here the probability of
finding the electron is zero. This is called radial node.
On the basis of the above write-up, answer the following questions :
4.
An electron moves along x-axis and restricted to move only between x = 0 and x = L. Hence
L
2
(a) dx = 1
(b)
dx > 1
(d)
0
L
(c)
dx = 0
0
L
dx < 1
2
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5.
The value of r at which radial node of 2s-electron of H-atom will appear is:
(a) r = a0
(b) r = 2a0
(c) r =
6.
a0
2
(d) r =
a0
3
The value of r at which the maxima of the probability distribution curve of 1s orbital electron of H-atom
will occur is
(a) r = a0
(b) r = 2a0
(c) r =
a0
3
(d) r =
a0
2
Column I
Column II
(d) Velocity
8.
Column I
(a) Visible, infrared, ultraviolet
Column II
(p) increases
wavelength of light
(b) Lyman, Balmer, Paschen
(q) decreases
If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b)
If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c)
(d)
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Assertion : In Rutherfords gold foil experiment, very few -particles are deflected back.
9.
10.
11.
12.
13.
14.
15.
Reason :
Assertion :
Reason :
Assertion :
Reason :
Assertion :
Reason :
Assertion :
Reason :
Hunds rule demands that the configuration should display maximum multiplicity.
Assertion :
The plots of radial probability density and radial probability function versus distance r
from the nucleus for any particular orbital are identical
Reason :
Radial probability density (R2) is along the radial distance where as radial probability
function (4r2R2) is the probability in a shell of thickness dr.
Assertion :
The 19th elecron in potassium atom enters into 4s-orbital and not the 3d-orbital.
Reason :
(n + l) rule is followed for determining the orbital of the lowest energy state.
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SECTION - V
(PROBLEMS ASKED IN IIT-JEE)
A.
1.
The energy of an electron in the first Bohr orbital of H atom is 13.6 eV. The possible energy values(s)
of the excited state(s) for electrons in Bohr orbitals of hydrogen is (are) :
2.
(a) 3.4 eV
(b) 4.2 eV
(c) 6.8 eV
(d) + 6.8 eV
(1998)
The electrons, identified by quantum numbers n and l, (i) n = 4, l = 1, (ii n = 4, l = 0, (iii) n = 3, l = 2 and
(iv) n = 3, l = 1 can be placed in order of increasing energy, from the lowest to highest, as :
(1999)
3.
4.
5.
6.
The electronic configuration of an element is 1s2, 2s2, 2p6, 3s2, 3p6, 3d5 4s1. This represents its :
(a) excited state
(2000)
(2001)
(a) one
(b) two
(c) three
(d) zero
The wavelength associated with a golf ball weighing 200g and moving at a speed of 5 m/h is of the
order:
(2001)
(a) 1010 m
(b) 1020 m
(c) 1030 m
(d) 1040 m
1
1
The quantum numbers + and for the electron spin represents :
2
2
(2001)
8.
If the nitrogen atom had electronic configuration 1s7, it would have energy lower than that of the normal
ground state of configuration 1s2 2s2 2p3, because the electrons would be closer to the nucleus, yet 1s7
is not observed because it violates :
(2002)
(a) Heisenberg uncertainty principle
Rutherfords experiment, which established the nuclear model of the atom, used a beam of :
(a) particles, which impinged on a metal foil and got absorbed
(2002)
NARAYANA
9.
Which hydrogen like species will have same radius as that of Bohr orbit of hydrogen atom?
(a) n = 2, Li2+
(b) n = 2, Be3+
(c) n = 2, He+
(d) n = 3, Li2+
10.
B.
1.
An isotone of
2.
(b)
77
33 As
(c)
77
34 Se
(d)
78
34 Se
When alpha particles are sent through a thin metal foil, most of them go straight through the foil
because :
(1984)
alpha particles are much heavier than electrons
alpha particles are positively charged
most part of the atom is empty space
alpha particle move with high velocity
The sum of the number of neutrons and proton in the isotope of hydrogen is :
(1988)
(b) neutrons
(d) photons
The energy of an electron in the first Bohr orbit of H atom is 13.6 eV. The possible energy value (s)
of the excited state (s) for electrons in Bohr orbits of hydrogen is (are) :
(1998)
(a) 3.4 eV
(c) 6.8 eV
7.
(1986)
(b) 5
(d) 3
(a) protons
(c) electrons
6.
(1984)
(a) 6
(c) 4
5.
(2005)
(1984)
77
32 Ge
(a)
(b)
(c)
(d)
4.
is :
(a)
(a)
(b)
(c)
(d)
3.
76
32 Ge
(2004)
(b) 4.2 eV
(d) + 6.8 eV
(1998)
4s1,
64
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NARAYANA
8.
9.
(1998)
(b) beta emission
(d) electron capture
(b)
(c)
(d)
(1999)
SUBJECTIVE QUESTIONS
1.
Estimate the difference in energy between 1st & 2nd Bohrs orbit for a H 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
l = 3.0 10 -8 m ? Which hydrogen atom like species does this atomic number corresponds to?
[JEE 1993]
2.
What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition
n = 4 to n = 2 of He+ spectrum ?
[JEE 1993]
Find out the number of waves made by a Bohr electron in one complete revolution in its3rd
3.
orbit.
[JEE 1994]
4.
Iodine molecule dissociates into atoms after absorbing light of 4500 . If one quantum of radiation is
absorbed by each molecule , calculate the kinetic energy of iodine atoms . (Bond energy of
[JEE 1995]
I2 = 240 k J mol -1).
5.
A bulb emits light of l = 4500 . The bulb is rated as 150 watt and 8 % of the energy is emitted as light.
How many photons are emitted by the bulb per second.
[JEE 1995]
6.
Consider the hydrogen atom to be a proton embedded in a cavity of radius a0 (Bohrs radius) whose
charge is neutralized by the addition of an electron to the cavity in vacuum infinitely slowly .
(a) Estimate the average of total energy of an electron in its ground state in a hydrogen atom as the
work done in the above neutralization process . Also if the magnitude of the average kinetic energy
is half the magnitude of the average potential energy , find the average potential energy.
(b) Also derive the wavelength of the electron when it is a0 from the proton . How the wavelength of
an electron in the ground . State Bohrs orbit .
[JEE 1996]
7.
An electron beam can undergo diffraction by crystals . Through what potential should a beam of
electrons be accelerated so that its wavelength becomes equal to 1.54 .
[JEE 1997]
8.
A compound of vanadium has a magnetic moment of 1.73 BM . Work out the electronic configuration
of the vanadium ion in the compound .
[JEE 1997]
9.
Calculate the energy requird to excite one litre of hydrogen gas at 1 atm and 398 k to the first excited
state of atomic hydrogen . The energy for the dissociation of H - H bond is 436 k J mol -1 Also
calculate the minimum frequency of photon to break this bond.
[JEE 2000]
65
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NARAYANA
ANSWERS
EXERCISE - 1
12
1.
3.312 10
erg
3.
2.
2.01 1018
EXERCISE - 2
1.
r1 = 0.1763 ; r2 = 0.7053
2.
(IE) He+ = 54.4 eV (IE) ; (IE) Li2+ = 122.4 eV ; (IE) Be3+ = 217.6 eV
3.
EXERCISE - 3
1.
32.77 eV
3.
2.5 108 m
2.
6.63 1033 m
2.
V =
EXERCISE - 4
1.
1.893 10-34 m
3.
1 h
2m
EXERCISE - 5
1.
(a) ml = 0
(b) l = 1
(c) n = 2
2.
3.
4.
(a) 2p
(b) 4d(c) 5s
EXERCISE - 6
1.
2.
3.
(a)
(b)
(c)
(d)
(e)
(a)
(b)
(c)
(d)
Z = 26
66
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NARAYANA
SECTION - I
(Subjective Questions)
LEVEL - I
1.
26
2.
375.25 kJ / mol
3.
182.5 kJ
4.
27419.25 cm1
5.
0.3328 nm
6.
1300 ms1
7.
3 104 Jm2 s1
8.
9.51
10.
12.75 eV
9.
2.31
1016
LEVEL - II
1.
493.6 kJ mol1
2.
5.38 1022
3.
4.
5.
c/v = 137
6.
n=5
7.
0.099 kg
8.
9.
10.
54.5 eV
1.
1167.5 kJ mol1
2.
158
3.
6235
4.
Li2+, 4060 nm
5.
6.
(i)
(ii)
n = 25
LEVEL - III
r = n2 1014 m
8.
397.2 nm
9.
6.25 1011
10.
d = 0.5 , E = 150.8eV.
SECTION - II
(Single Choice Questions)
1.
3.
5.
7.
9.
11.
13.
15.
17.
19.
(b)
(b)
(c)
(d)
(a)
(c)
(d)
(b)
(b)
(a)
2.
4.
6.
8.
10.
12.
14.
16.
18.
20.
(c)
(c)
(b)
(b)
(b)
(a)
(b)
(a)
(a)
(c)
67
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NARAYANA
SECTION - III
(Multiple Choice Questions)
1.
3.
5.
7.
9.
(b, c)
(a, b, c)
(b, c, d)
(a, c)
(b, c, d)
2.
4.
6.
8.
10.
(a, b, c)
(a, b, d)
(a, b, d)
(a, d)
(b, c, d)
SECTION - IV
(Comprehension Type Questions)
1.
3.
5.
(b)
(a)
(b)
2.
4.
6.
(b)
(a)
(a)
(a)
(c)
(a)
(c)
(p)
(p, q)
(r)
(p)
(b)
(d)
(b)
(d)
(q, s)
(q, s)
(p)
(q)
(b)
(b)
(c)
(a)
10.
12.
14.
(a)
(b)
(d)
SECTION - V
(Problems asked in IIT-JEE)
OBJECTIVE QUESTIONS
A.
Only one
1.
3.
5.
7.
9.
B.
option is correct
(a)
(b)
(c)
(c)
(b)
2.
4.
6.
8.
10.
(a)
(a)
(d)
(d)
(a)
2.
4.
6.
8.
(a, c)
(d)
(a)
(a)
2.
4.
7.
9.
n1 = 1 , n2 = 2
0.216 10 -19 J
63.3 volt
98.19 k J , 10.93 1014 Hz
(b, d)
(a, c)
(a, b)
(a, b, c)
(a, d)
SUBJECTIVE QUESTIONS
1.
3.
5.
8.
10.2 eV , z = 2 , He+
3
27.2 1018
1 s2 , 2 s2 , 2 p6 , 3 s2 3 p6 3 d1
68
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