CHAPTER

4 Atomic Structure

Chapter Highlights
Constituent of atoms, Thomson atomic model, Rutherford model, Electronic structutre of atom, Planck theory,
Spectrum, Bohr’s model, Hydrogen spectrum, Dual nature theory of matter, de Broglie relation. Uncertainty
principle, Quantum mechanical model, Shapes of orbitals, Quantum number and Aufbau, Pauli, Hund’s Law and
various levels of multiple-choice questions.

ATOM AND ITS CONSTITUENTS

ATOM AND ATOMIC THEORY • Atoms of same element also differ in properties
related to mass as in case of isotopes. While atoms
• Atom (Greek: atomos) means indivisible or uncuttable. of different elements have same properties in case of
• The words atom and atomic theory were introduced isotopes.
by Dalton in 1808 while explaning the atomic model.

Following are the main postulates of atomic theory as

Sub Atomic Particles
proposed by Dalton: Discussed below are the sub atomic particles or the con-
stituents of atoms.
• Atom is the smallest, indivisible fundamental particle.
• It can neither be created nor destroyed, however, it is Electrons (–1e0 or e–)
inter-convertible into another atom.
The electron was discovered by J. J. Thomson during the
• Atoms undergo chemical combination to form study of cathode rays (stream of electrons).
molecules but in a whole number ratio, for exam- The term electron was coined by J. L. Stoney.
ple, molecule is the smallest identity that exists
1
____
individually. 1. Mass: Its mass is 1837 of H-atom 0.00055 amu, 9.1 ×
• Atoms of the same element have same mass, size, 10
–31
kg.
properties etc., but atoms of different element differ 2. Location: It is present in the extra nuclear region of the
in these properties atom.
J. J. Thomson introduced significant modifications in 3. Charge: It is confirmed by Miliikan’s oil drop
the prevalent atomic model. His conclusions are the basis experiment and its value is 1.6 × 10–19 Q or – 4.8 ×
of the modern view of atomic theory, according to which: 10–10 esu.
• Atom is divisible into sub atomic particles.
Thomson gave the e/m ratio or specific charge ratio
• Atoms can also combine in non-whole number ratio in for an electron which equals to 1.76 × 108 C/g
non stoichiometric compounds, for example, Fe0.93O.
4.2 Chapter 4

• e/m ratio or specific charge ratio or Thomson ratio • It is the best projectile as it is chargeless.
follows the order mentioned: –1e– > , p1 > 2α4 > 0n1 • The H-atom has no neutron.
e/m ratio for a neutron is zero as it is a chargeless
particle. 1. Mass: Its mass is 1.674 × 10–27 kg or l .0086 amu.
• e/m ratio for cathode rays is constant and indepen- 2. Density: Its density is 1.5 × 1014 g/cc.
dent of the nature of gas in discharge tube and nature
of cathode or electrodes of tube, that is, electron is Meson or Pion
universal fundamental particle.
This subatomic particle was discovered by Yukawa in
• Mass of one mole of electron is 0.55 mg.
mrest cosmic rays (in 1935) (π+, π–).
• Mass of moving e– = _________
_________
√1 – (v / c)2 • These are present in the intermediate region between
• Electron can leave its orbit for a maximum duration 10–13 – 10–15cm of atom.
of 10–8 sec. • Mesons hold neutrons and protons together and
• Particle nature of electron is confirmed by scintilla- inter convert them. These are internuclear forces or
tion effect on ZnS screen. exchange forces.
• Photoelectric effect, emission of β-particle, thermal n p + π–
emission or heating of metal filament confirm the p n + π+
fundamental particle nature of electron. p p + π˚
n n + π˚
5. Density: Its density is 2.17 × 1017 g/cm3. • Neutral pions were discovered by Keemer.
• Now kaons (K+, K–, K0) and eta-meson have also
Proton (1H1 or p) been discovered.
The proton was discovered by Goldstein during the study • Mass of π = 270 × Mass of electron.
of anode rays or canal rays or +ve rays which originate in • π mesons are called pions.
the region between cathode and anode in a discharge tube.
The term proton was coined by Rutherford. Neutrino and antineutrinoz
• For anode rays e/m ratio depends upon nature of They are chargeless, very light particles and their exis-
gas taken in a discharge tube and It is maximum for tence was postulated by Fermi and Pauli. Neutrino has
hydrogen gas. an anticlockwise spin while anti-neutrino has a clockwise
spin.
1. Charge: It carries a charge of + l.6 × l0–19 C or + 4.8 ×
10–10esu. Quarks
2. Mass: Its mass is same as that of H-atom, that is, l .673 Electrons are made up of small particles called quarks.
× 10–27 kg or l.0072 amu. According to Murray Gellmann, quarks have fractional
• e/m ratio is 9.5 × 104C/g charges, colour and flavour. For example, upward and
downward quark etc.
1 amu =1/12 mass of C-atom
1 amu = 1.66 × 10–27 kg = 931.5 MeV
Positron or antielectron
Neutron (0n )1
(e+, β+ or +1e°) These are highly unstable and
The neutron was discovered by Chad-wick. generate γ-rays on combining with electrons. Positron was
discovered by Carl Anderson.
4
Be9 + 2He 6
C12 + 0n1
Neutron was discovered later because it is chargeless. Antiproton (p)
• It is heavier than an electron and a proton. It was discovered by Segree and Wei-gland by p–p and p–n
type of collisions.
• An isolated neutron is unstable and disintegrates as
follows: v-Particles
n1 e0 + 1p1 + υ
0 –l These were discovered by Rochester and Butler. These may
• It is stable inside the nucleus but unstable outside be v+, v– or v0.
it.
 Atomic Structure 4.3

Atomic Number (Z) • Heaviest isotopes are radioactive in nature, for

example, C-14, O-18 are radioactive isotopes of
Moseley postulated that the frequency of the X-rays was carbon and oxygen.
related to the charge present on the nucleus of the atom of
the element used as anticathode and found that Isobars
__
√υ= a(Z – b) Isobars are atoms of different elements with same mass
where υ is the frequency, z is the nuclear charge and a and number (A) but different atomic numbers (Z).
b are constants. • They have different number of protons and neutrons
a = Probability constant but the sum of their protons and neutrons is same.
b = A constant having same values for all lines of X-ray • They have different chemical properties but physi-
spectrum. cal properties related to mass are same, for example,
Ar40, 19K40, 20Ca40
The number of unit positive charges carried by the nucleus 18

of an atom is called the atomic number of the element.

Z = p = e– (for atoms) Isotones
Z = p (for ions) Isotones are species having different atomic number (Z)
and mass number (A) but same number of neutrons.
Some facts about atomic number (Z)
• It is always a whole number, and a permanent value
For example,
for each element.
• It is the serial number of elements in the periodic C14 N15 O16
6 7 8
table, that is, it determines their exact position.
No. of neutrous 14–6 15–7 16–8
• Periodic properties are related to the atomic number
=8 =8 =8
of elements.

NOTE Isoelectronics
Isoelectronics are species having same number of elec-
Atomic weight (A) = Mass number = n + p
trons, for example, Ne, Na+ O–2, CH4, NH +4 , all have 10
electrons.
Isotopes
Isoesters
• The concept of isotopes was formulated by Soddy.
Isoesters are species having same number of atoms as
• These are atoms of same element with same atomic well as same number of electrons, that is, all isoesters are
number (Z) but different mass numbers (A). iso-electronic species but all isoelectronic species may not
• They have same chemical properties. be isoesters.
• They have same number of protons.
• Rate of lighter isotopes > rate of heavy isotope
CN– N2 CO NO+
(isoto-pic effect).
• Isotopes are separated by fractional distillation, ther- Number of atoms 2 2 2 2
mal diffusion, gaseous diffusion methods. Number of e –
14 14 14 14
• Isotopes can be detected by Thomson Parabola method,
Aston’s mass spectrograph method, Dempster method.
• Some examples of isotopes: Isomorphs
Isomorphs are compounds that have same crystalline struc-
H1 H2 H3
1 1 1
tures. For example, all alums, green vitriol (FeSO4.7H2O),
C12 C14
blue vitriol (CuSO4.5H2O).
16
O O18
Cl35 Cl37
4.4 Chapter 4

Isodiaphers Density of nucleus is 1017 kg/m3or 1014 g/cm3 and vol-

ume of nucleus is 10–39 cm3.
Isodiaphers are atoms having same isotopic number or they
5. Centrifugal force develops between electrons and the
have same (n–Z) or (A–2Z) value.
nucleus so electrons revolve around the nucleus as
For example, planets move around the sun.

9
F19 19
K39 Largely deflected Slightly deflected
a-particles Nucleus
A = 19 A = 39 D-particles
Z=9 Z = 19
n = 10 n = 20
n–Z=1 n–Z=1
A – 2Z = 1 A – 2Z = 1 Undeflected
D-particles

THOMSON ATOMIC MODEL

Thomson atomic model was introduced by Thomson.
• According to this model, an atom occupies a spherical
Largely deflected Slightly deflected
shape with a radius of nearly 10–10 metre in which the D-particles
D-particles
positive charged is uniformly distributed and electrons Figure 4.1 The Rutherford Scattering Experiment
are embedded uniformly in this positively charged
sphere just like raisins are present in pudding.
• The important feature of this model is that the mass FA C T TO R E M E M B E R
of the atom is assumed to be uniformly distribute 1
_______
Scattering of α-particles α sin4 ( /2)
about the atom. θ
• The model explains the neutrality of an atom but fails
to explain the other aspects relating to the atomic
Strengths
structure.
• The Thomson atomic model was completely rejected • It explained the existence of a nucleus.
by the Rutherford and Mordson experiment. • It explains the movement of electrons as a circulatory
rotation of electron around the nucleus.

RUTHERFORD ATOMIC MODEL Limitations

During an experiment involving α-particle bombardment • It cannot explain the stability of an atom.
on a 10–4 mm thick gold foil, Rutherford observed that: • It cannot explain the number and velocity of electrons.
1. Most part of the atom is empty as most of the α-par- • According to this theory, atomic spectrum is
ticles pass straight through the foil without any continuous and non linear but in fact it is linear and
deflection discontinuous.
2. Electrons occupy position in this empty space (extra
nuclear region). ELECTRONIC STRUCTURE OF ATOMS
3. Centrally located, solid, compact, small part having all
positive charge and nearly the whole mass. It is called Wave theory
the nucleus (as only few α-particles get deflected up to
a maximum of 180°) 1 Crest
4. The value of radius (r) = 1.3 × 10–13 × A 3 cm a
Radius of atom = 10–10 m or 10–8 cm
a Trough
Radius of nucleus = 10 –l5 m or 10–13 cm
Atomic radius is greater than the nucleus radius by 105 O
times.
 Atomic Structure 4.5

Wave theory is described in brief as follows: Corpuscular Theory of Light

• All radiant energy propagates in terms of waves. • Corpuscular theory of light was first introduced by
• Radiant energy is a form of electromagnetic waves. Newton.
• Radiations are associated with electric and magnetic • According to this theory, light is propagated in the
fields, perpendicular to one another. form of small invisible particles.
• In the propagation of an electromagnetic radiation, there
is only propagation of wave but not of the medium. Quantum Theory
Wavelength Quantum theory was proposed by Max Planck and later
It is the distance between any two successive crests or two extended by Einstein.
successive troughs of a wave. • It states that a hot vibrating body does not emit
It is denoted by λ and it is measured in Å (Angstroms) or or absorb energy continuously but does so discon-
nm (nanometres). tinuously in the form of small energy packets or
bundles known as quanta or photons in case of
Frequency light energy.
It is the number of waves per second passing at a given • The energy of radiation (E) is directly proportional to
point. It is denoted by υ or f. The units of frequency are frequency of radiation (υ).
Hertz or cycles sec–1.
E∝υ
Velocity of light
E = hυ
It is the distance travelled by one wave in one second.
Here, h is Planck constant and its value is 6.6253 ×
• Velocity of light = frequency × wavelength
10–34 Js or kg m2 s–l.
c = υλ
• Absorption or emission of energy in the form of inte-
λ ∝ l/υ gral multiples of quantum is known as quantization
• Light and all the other electromagnetic radiations of energy, E = nhυ
travel in vacuum or air with same velocity. • A hollow sphere coated inside with platinum black
and having a small hole in its wall acts as a black
Wave number body. It is a perfect absorber and perfect emitter of
It is the number of waves spread in one centimetre and it is radiant energy.
_
denoted by v. It is increase of wavelength. • At a given temperature, the intensity of radiation
_ __ c increases with wavelength, approaches maximum
υ = __1λ as υ = __λ
_ and then starts decreasing.
So, υ = cυ • Planck’s quantum theory could explain only black
• Its units are cm or m .
–1 –1 body radiations, so Einstein extended the quantum
theory to all types of electromagnetic radiations.

Table 4.1 Electronmagnetic Spectrum

Wave length Frequency
Photoelectric Effect
(in m) Name (cycles sec–1) Photoelectric effect was introduced by P. Lenard and
10–11 gamma rays 1019 explained by Einstein.
10–9 X-rays 1017 • It is the emission of electrons from a metal surface
10–8 ultra violet 1016 on exposing it to radiation of suitable frequency.
10–7 visible 1015 • It is readily shown by alkali metals like potassium
10–6 infrared 1014 and calcium, which have very low value of ionization
10–2 microwave 1010 energy.
1 TV 108 • When a photon strikes a metal surface, its energy
1
10 –10 2
radio 7
10 –10 6 is absorbed by the metal, consequently emission of
electrons takes place.
4.6 Chapter 4

A part of the energy of a photon is used to overcome • The spectrum of incandescent white light obtained
the attractive forces and the remaining energy is used in by heating a solid to very high temperature is a
increasing the kinetic energy of electron. continuous spectrum.
K.E. ( ½ mv2) = E – φ • When white light passes through a prism, it gives a
continuous spectrum of seven colours (VIBGYOR).
Here E = energy of radiation • In a continuous spectrum, each colour fades into the
φ = work function (minimum energy needed for next colour as in a rainbow.
electron emission)

K.E. = hυ – hυ0 Absorption Spectrum

υ0 = threshold frequency (minimum frequency of • The spectrum formed by the absorption of energy
light radiation needed for electron emission) in the form of light radiation is called absorption
spectrum.
• If v > v0 • It can be understood as the photographic negative
K.E. is positive, therefore, electrons are emitted. of an emission spectrum, that is, the missing wave-
length leaving the spaces in continuous spectrum. In
• If υ = υ0
this sense, absorption spectrum is just the opposite of
K.E. = 0, therefore no electron is emitted. the emission spectrum.
• If υ < υ0 • Absorption spectrum is formed due to the excitation
K.E. is negative, therefore, there is no emission of of atoms or molecules by absorbing energy.
electrons. • Absorption spectrum consists of dark lines or bands
• Photoelectric effect ∝ Frequency of light radiation on a bright background.
• Kinetic energy of electrons does not depend upon
intensity of light. However, number of ejected elec- Discontinuous or Line Spectrum
trons depends upon intensity of light.
1. The emission spectrum of atoms in gaseous phase
containing bright lines with sharp boundaries is called
SPECTRUM a line spectrum. It is a discontinuous spectrum having
Spectrum is the arrangement of components of electromag- emitted radiations of a particular wavelength.
netic radiations in the increasing order of wavelength or 2. The dark lines in the absorption spectrum and bright
decreasing order of frequency, when it is passed through a lines in the emission spectrum of a particular sub-
prism. The apparatus used to record the spectrum is called stance appear at the same places (same wavelengths).
a spectrometer or spectrograph.
3. Each element has its own characteristic line spectrum
Emission Spectrum like fingerprints by which it can be identified.

Emission spectrum is the spectrum of radiation emitted 4. The line spectrum of two element can never be identi-
by a substance after absorbing energy of a particular cal as
wavelength, or alternatively, the spectrum formed by the
emission of energy in the form of light radiation is called (a) They do not have same number of electrons.
emission spectrum. (b) They have different mass number.
(c) They have different energy level skill.
• Emission spectrum consists of bright lines or bands (d) They have different number of valence electron.
on a dark background.
• Emission spectrum is formed due to the emission of 5. Line spectrum is used in chemical analysis and iden-
light by the excited atoms or molecules. tification of unknown atoms. Rb, Cs, In, Ga, He are
identified by this method.
Continuous Spectrum 6. Line spectra are given by atoms so they are known as
atomic spectra whereas band spectra are given by mol-
• When no sharp boundaries are observed between
ecules so they are known as molecular spectra.
adjacent radiations, the spectrum is continuous.
 Atomic Structure 4.7

BOHR’S ATOMIC MODEL Spectral series for hydrogen atom

The atoms of hydrogen in a gas discharge tube, emit radia-
Bohr introduced circular orbit concept based on Planck’s
tions whose spectrum shows line characteristics (line spec-
quantum theory. According to Bohr’s model
tra) and lies in the infrared, visible and ultraviolet region of
• Around the nucleus there are circular regions called the electromagnetic spectrum.
orbits or shells. n=6
K L M N O..... n=5
n=1 2 3 4 5.....
n=4
Brackett n = 3
Energy and distance from nucleus increase from K Paschen n=2
onwards
Balmer n=1
• Every orbit has a fixed amount of energy so it is also
referrred to as an energy level. Lyman series

• An electron revolves around the nucleus without Figure 4.2

any loss of energy in a particular orbit of definite
energy. Table 4.2 The Type of Lines Obtained in a
• Angular momentum (mvr) in each orbit is quantized Hydrogen Spectrum
mvr = n __h
2π = nh
– n1 n2 Spectrum
Lyman 1 2....∝ uv
n→ 1 2 3 4
Balmer 2 3....∝ Visible
h h 3h 2h
mvr → Paschen 3 4....∝ Near IR
2π π 2π π
Brackett 4 5....∝ Far IR
Here h is Planck constant. Pfund 5 6....∝ Far IR
• When electron changes its orbit, energy change Humphries 6 7....∝ Far IR
occurs in quanta.
hc
∆E = E2 – E1 = hυ or __
λ • For radiations with the longest wavelength or least
energy, n2 must be nearest (next value) to n1.
Few Important Terms • For shortest wavelength and highest energy, n2 must
Quanta be infinite, that is, it must be close to the series limit.
It is a small bundle of any type of energy. Balmer series contains four important lines whose
wavelengths are 6563Å, 4862 Å, 4341 Å and 4102 Å.
Photon
These are called Hα, Hβ, Hγ, and Hδ lines respectively.
It is a small massless bundle of light energy and not a
material body.
To Find Total Number of Spectral Lines
Excited state Case I when an e– Jumps from nth orbit to Ground state
Here, electron jumps from a lower to a higher orbit or energy
n(n − 1)
level by absorbing energy in quanta. No. of lines =
2
De-excited state 4(4 − 1)
e.g., If n = 4, No. of lines = =6
Here, electron jumps from higher to lower energy level by 2
releasing energy in quanta. Case II when e– comes from n2 to n1
(n 2 − n1 ) (n 2 − n1 + 1)
Merits of Bohr’s Atomic Model No. of Lines =
2
It can explain linear nature of spectrum of hydrogen E.g., If n2 = 5, n1 = 2
like species (that is with one e”), for example H, He+,
Li +2 etc. (5 − 2)(5 − 2 + 1)
No. of Lines = =6
2
4.8 Chapter 4

Calculation of Energy, Wave Length Zeeman Effect

It is the splitting of main spectrum line into several lines
hc
__
∆E or λ =
π2Me4Z2 __
2________
n2
1
(–
1
__
n12 n22 ) in a strong magnetic field.

( )
_ __ 2 π2Me4Z2 __
v = 1λ = ________
n3c
1 1
– __
n12 n22
Stark Effect
It is the splitting of main spectrum line into several lines
( )
_ 1
v = __ 1
2 __ 1
__
λ = RHZ n12 – n22
in a strong electric field.
_
v Wave number, λ = Wavelength
• It cannot explain chemical bonding.
n1= Lower orbit, n2 = Higher orbit • It can explain only particle nature, that is, no expla-
RH = Rydberg constant = 109678 cm–1 or 1.1 × 107 m–1 nation of wave nature (against de Broglie’s, Heisen-
berg’s, Planck’s theory).
• In the calculation of radius of nth orbit
nh 2 2
rn = _________
4 π2mKze2
DE BROGLIE EQUATION AND DUAL
n2
__
NATURE THEORY
rn = 0.53 × Z Å
• De Broglie introduced dual nature theory for matter,
Here n = nth orbit that is for the subatomic particles (e–, p, n)
• According to this theory, matter has both particle as
• In the calculation of velocity of electron in nth orbit well as wave nature.
Z
vn = 2.165 × 106 × __ • Wave nature of electron was confirmed by Davis-
n m/sec
son and Germer by diffraction pattern experiment on
• In the calculation of energy of electron in nth nickel surface. The patterns obtained were found to
orbit be same as those predicted by Bragg for X-rays.
2 π2mZ2e2K2
En = – _________
n2h2
E = mc2 (i) for particle
313.52
E = hν
En = – _____ Z2 Kcal/mol hc
n2 E = __λ (ii) for wave
Z
En = –13.6 __
2

n2
eV/atom using (i) and (ii)
hc
__
Z
= –2.178 × 10–18 × __
2

λ = mc
2
n2
J/atom
Here K = l/4πε0 1_ ____
__ mc2
λ = hc
e = Charge on electron
m = Mass of electron
h
λ = ___
mc
h = Planck constant if c = v
Bohr value = value in 1st orbit of hydrogen atom
h
λ = ___
mv
Bohr radius = 0.53 Å λ = __hp (As p = mv)
Bohr velocity = 2.165 × 106m/s
Bohr energy = –13.6eV/atom λ ∝ __1p (At constant temperature)
Vn
_____ • If a particle has more mass or momentum it has less
• Number of revolutions = 2 π r wave nature.
n
e>p>>n
Shortcomings of Bohr’s Theory
• Heavy objects have less wavelength due to more
• It is not applicable for species having more than one mass.
electron like Li, He.
• Relation between wavelength and kinetic energy:
• It cannot explain fine spectrum of H, Li++ h
λ = ________
_______ h
= ________
_______
• It does not explain Zeeman and Stark effects. √ 2m K.E. √ 2m e.V.
 Atomic Structure 4.9

K.E = ½ mv2 = eV potential difference Here X, Y, Z are three coordinate axis.

½ mv2 = eV E is total energy.
eV
v = 2 ___
2
m V is potential energy (V = –Ze2/r)
____
eV
v = √ 2 ___
m
m is mass of electron wave.
—2
v ψ is Laplacian operator.
HEISENBERG’S UNCERTAINTY
PRINCIPLE Significance of ψ and ψ2
Heisenberg’s uncertainty principle is applicable only to ψ : It has no physical significance. It represents ampli-
subatomic particles. tude of electron-wave or boundary surface of an
orbital.
• According to this principle, it is impossible to mea-
sure simultaneously and accurately both change in ψ2: It is the probable electron density or it is the probabil-
position and change in momentum. If the value of ity of finding electrons in any region (3 dimen-
one is deter mined with certainty, the accuracy in sional space around the nucleus). If ψ2 is positive,
determining the other value is compromised. electrons are present and if ψ2 is zero electrons are
absent.
• It is also called principle of indeterm inancy.
• An orbital is represened by ψ ψ* or ψ2 for showing
h
∆x. ∆p ≥ ___
4π electron density.
h
∆x. m ∆v ≥ ___
4π • The probability of finding electron at a distance r
Here ∆x = Uncertainty in position from the nucleus in the region dr is given by 4 π r2
∆v = Uncertainty in velocity dr ψ*.
h
∆x. ∆v ≥ ____
4 πm
• In case where the energy of an atom or a molecule
does not change, another equation given by Schro-
h
∆E. ∆t ≥ ___
4π dinger becomes applicable.
Here ∆E = change in energy
Ĥ ψ = Ê ψ
∆t = change in time
Ĥ = T̂ + V̂
• If change in position is zero, change in momentum : (T + V)ψ = E ψ
will be infinite and vice versa. Here, H = Hamiltonion factor
• It applies when both ∆x and ∆p are along the same axis. V = Potential energy
T = Kinetic energy
Concept of Probability As according to this principle
E = Total energy
ox and op of an e– can not be find accurately at a particular
time so the idea of definite paths i.e., orbits as suggested
Orbital
by Bohr has no more significance. This leads to the concept
of probability. According to which it is possible to state or An orbital is a variedly shaped, three dimensional region
product the probability of locating an electron of a specific around the nucleus where the probability of finding elec-
energy in a given region of space around the nucleus at a trons is maximum.
given time. This leads to the concept of ‘orbital’ An orbital possesses the following features:
• It represents both the particle and wave nature of an
SCHRODINGER WAVE EQUATION electron.
Schrodinger wave equation explains three dimensional • The probability of finding an electron in an orbital is
wave nature of electron as follows: more than 90%.
δ____
Ψ δ 2Ψ δ 2Ψ • Except the s orbital, the rest are directional in nature.
+ ____
2
8ψ2m
δ Χ2
+ ____
δ Y2 δ Z2
+ ____
h2
[E – V] ψ = 0
• An orbital can accommodate a maximum of 2 elec-
8 ψ2m trons with opposite/antiparallel spins.
v ψ + _____
—2
h2
[E – V] ψ = 0
4.10 Chapter 4

Z Degenerate Orbital
Orbitals with same value of n and of same sub-shell are de-
X generate orbitals, for example, 2px, 2py 2pz 3dxy, 3dyz, 3dxz.
s
Y Radial Probability Distribution Function
Z Z Z • It is the probability of finding electrons in the region
between r and dr δr.
X
• It is given by 4 π r2 ψ2 δr. It is direction independent
y Here, r = radius or distance from nucleus
PX Y Py Y PZ
Z δr = thickness
Node It is zero electron density region.
ψ2 = 0
X
Radial node
y
d x2 — y 2 It is the region between two successive s orbitals.
dZ2
Z Z Z Nodal point
It is a point where two lobes join and the electron density
here is zero.

Nodal plane
y y y
dxy d xz d yz It is the plane which separates two lobes. Electron density
Figure 4.3 Shapes of Different Orbitals here is zero.
• No s orbital has a nodal plane or a point.
• px, py pz, dzorbitals have one nodal plane or point.
The solution of Schrodinger Wave Equation, for the • Rest of d orbitals (dxy dyz dxz dx2 – y2) have two nodal
single electron hydrogen atom, yields the wave function of
plane or points.
an atomic orbital, that is, ψ (r, θ, φ). It is a mathematical
function of r, θ and φ which are the three coordinates of
an electron. It can further be factorized into three separate Calculation of Nodes
parts, each of which is a function of only one coordinate. Node = n–1
ψ (r, θ, φ) = R(r) Θ (θ) Φ (φ)
Radial nodes or spherical nodes = n–l–l
Here, R(r) is the radial function which shows the
dependence of an orbital on the distance V of the electron Angular or non-spherical = l
from the nucleus. The radial function depends upon the For example, 1s: Node = 1–1 = 0
quantum numbers n and l. For example, 2s: Node = 2–1 = 1
Θ (θ) and Φ (φ) depict the angular dependence of the Angular node = 0
orbital on θ, and φ respectively. It is dependent on the
quantum numbers l and m. Radial node = 2–0–1 = 1
The total wave functions y can now be represented For example, 3s: Node = 3–1 = 2
as Angular node = 0
ψ (r, θ, φ) = Rnl (r) Θlm. (θ) Φm (φ) Radial node = 3–0–1 = 2
Radial Angular For example, 4d: Node = 4–1 = 3
part part Angular node = 0
Radial node = 4–0–1 = 3
 Atomic Structure 4.11

I II III

1s 1s 1s

4πr2R2
R2
R

r r r

2s 2s 2s

4πr2R2
2
R
R

Node
Node

r r r

2p 2p 2p

4πr2R2
2
R

r r r

The plots of (I) the redial wave function R; (II) the radial probability density R2 and (III) the radial density function
4π r2 R2 as a function of distance r of the electron from the nucleus for 1s, 2s and 2p orbitals.
Figure 4.4 Various Probability Curves

QUANTUM NUMBERS
nh
mvr = ___ –
2 π = nh
mvr = angular momentum in orbit.
Quantum numbers are set of four numbers used to address
an electron as follows h = Planck constant
1. To determine size, distance from nucleus and energy • Values of n = 1,2 ,3, 4 ............... ∝
of electron ins orbit. n ≠ 0, –ve, fractional
2. To decide shape, energy of electron in a sub-orbit.
3. To find number of orbitals and their directional posi- Azimuthal or Secondary or Angular
tion or orientation in space. Momentum Quantum Number
4. To find number of electrons and their spin.
• Angular momentum quantum number was intro-
duced by Sommerfield.
Principle Quantum Number
• It is denoted by `l’.
• Principle quantum number was introduced byBohr. • It determines shape of sub-orbit, energy in sub shell
• It is denoted by n. and angular momentum of an electron in any orbital.
It determines: h
mvr = ℓ( ℓ + 1) = ℓ( ℓ + 1) −
h
1. Size of orbit (shell) 2π
2. Distance of orbit from nucleus For any s orbital e– (mvr) = 0 (as ℓ = 0)
3. Energy of electron in an orbit
4. Maximum number of electron in any orbit For any p orbital e– mvr = ℓ( ℓ + 1) = 2 −
h
5. Angular momentum of electron in an orbit
4.12 Chapter 4

• This explains the existence of many closely packed AUFBAU PRINCIPLE

spectral lines in hydrogen spectrum.
• Values of l = 0 to n – 1 Aufbau is a German word which means ‘to build up’ so it
is also called building up rule.
n: 0 1 2 3 4
l: 0 0 0, 1 0, 1, 2 0, 1, 2, 3 (n + l) Rule
• l: 0 1 2 3 4 According to Aufbau principle electrons are filled in dif-
s p d f g ferent orbitais from lower (n + l) value orbital to higher
(n + l) value orbital as follows:
Magnetic Quantum Number 1 s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s <
• Magnetic quantum number was introduced by Land [Increasing order of (n + l) value or energy]
and Zeeman. In case (n + l) value is same, electron is filled first in
• It is denoted by m. orbital with lower value of n, for example,
It determines: 3p 4s
1. Number of orbitals n=3 n =4
m (total) value = n2 (when n is given) electrons first goes into 3p subshell.
= 2l + l when ’l’is given.
when n = 2 FA C T TO R E M E M B E R
m (total) = 22 = 4
when l = 2 1s < 2s < 2p < 3s
m (total) = 2 × 2 + 1 = 5 (n + l) 1+0 2+0 2+1 3+0
3p < 4s < 3d < 4p
2. Directional position of orbitais or orientation in shape
and Zeemann effect 3+1 4+0 3+2 4+1
3. Angular magnetic momentum
mvr = m ___h
2π= mh–
Electronic Configuration
Values of m = –l to + l including zero
• First fill electrons in orbital according to (n + l) rule
l=0 1 2 (initial configuration).
m = 0 –1, 0, +1 –2, –1, 0 + 1, +2 • If atomic number is >20, arrange the orbital in
increasing order of n-value (for final configuration).
Spin Quantum Number For example, 26Fe
• Spin quantum number was introduced by Uhlenbeck
and Goudsmit. 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6
• It is the intrinsic angular momentum measurement 1s2, 2s2, 2p6, 3s2, 3p6, 3d6, 4s2
which is used to differentiate between two electrons (final configuration)
in the same orbital. Violation of Aufba’ s Rule
• Schrodinger could not explain the spin of an electron.
• For each value of m, s has two different values + ½
and – ½.
+½ –½ As ns1. np4 Configuration is not possible.
α-spin β-spin
• + ½ and – ½ are just to mechanical spin states with Some Exceptional Configurations
no classical importance now as other spin states are Fully filled and half filled orbitals are more stable due to
also possible. greater number of exchanges, higher exchange energy and
• Total values of s or total number of electrons = 2m = symmetry.
2n2 = 2(l+ 1)
 Atomic Structure 4.13

Case I Some Other Exceptional Configurations

(n – l)d ns incomplete
4, 2
: (n – l)d , ns
5 1
41
Nb : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d4 5s1
d-orbital so d-orbital is both orbitals are half 42
Mo : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d5 5s1
less stable filled so more stable. 44
Ru : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d7 5s1

The number of exchanges that can take place in d4 config- or

uration are as follows: [Kr] 4d 5s7 1

45
Rh : [Kr] 4d8 5s1
46
Pd : [Kr] 4d10 5s0
1 2
47
Ag : [Kr] 4d10 5s1
57
La : [Xe] 4f0 5d1 6s2
3 EXCHANGES BY 2 EXCHANGES BY
58
Ce : [Xe] 4f2 5d0 6s2
ELECTRON 1 ELECTRON 2
61
Pm : [Xe] 4f5 5d0 6s2
78
Pt : [Xe] 4f14 5d9 6s1
3
79
Au : [Xe] 4f14 5d10 6s1

1 EXCHANGES BY PAULI’S EXCLUSION PRINCIPLE

ELECTRON 3

Total number of exchanges = 3 + 2 + 1 = 6 l. Any orbital can have a maximum of two electrons with
The number of exchange that can take place in d5 con- opposite or anti parallel spin.
figuration are as follows: or
2. No two electrons of an atom can have the same set of
all the four quantum numbers, for example, if n, l, m
1 2 are same, the value of s will be different.

4 EXCHANGES BY 3 EXCHANGES BY
Applications of Pauli Exclusion Principle
ELECTRON 1 ELECTRON 2
To find maximum number of electrons in:
1. Orbit: maximum number of electrons = 2n2
3 4
n = 1 for K e– = 2 × 12 = 2e–
n = 2 for L e– = 2 × 22 = 8e–
2 EXCHANGES BY 1 EXCHANGES BY
ELECTRON 3 ELECTRON 4 n = 3 for M e– = 2 × 32 = 18e–
2. Sub-orbit:
Total number of exchanges = 4 + 3 + 2 + 1 = 10 Sub-orbit: s p d f g
Example: Electrons 2 6 10 14 18
Cr: [18Ar] 3d4 4s2 [×]
24 3. Ans Orbital: has maximum two electrons
[18Ar] 3d5 4s1 [√]
Violation of Pauli’s Law
Case II
• When any orbital has two e– with parallel spin.
(n – 1) d9 ns2 : (n – 1) d10 ns–1
incompletely fully half
filled d orbital filled filled • When any orbit /sub-orbit/orbital has electrons more
[less stable] [more stable] than maximum limit.
Example: e.g., 1s7 is not possible
Cu: [18Ar] 3d9 4s2 [×]
29 as Ist orbit, and s–sub – orbit
29
Cu: [18Ar] 3d10 4s1 [√] Can have max. 2 e– only.
4.14 Chapter 4

HUND’S RULE OF MAXIMUM MULTIPLICITY SOLVED EXAMPLES

According to Hund’s rule, “In degenerate orbitals, elec-
trons are filled in such a way that maximum stability and
Wave Nature, Wavelength
multiplicity can be obtained for the former. First each de-
generate orbital is singly occupied then pairing of electron 1. 3 × 1018 photons of a certain light radiation produce
takes place.” 1.5 J of energy. Find out the wavelength of this radia-
The following would be a violation of Hund’s rule: tion (h = 6.626 × 10–34 Js).
Solution
paring empty orbital
E = hυ (for one photon)
Applications of Hund’s Rule E = Nhυ (for N photons)
Nhc
• To write correct and stable electronic configuration, E = ____
λ
for example, N hc 3 × 1018 × 6.62 × 10−34 × 3 × 108
λ = ____
E =
24
Cr: [Ar] 3d4 4s2 [×] 1.5
[Ar] 3d5 4s1 = 39.75 × 10–8 m = 3975 Å.
• To find number of unpaired electrons (n), for 2. Determine the wavelength of a photon of electromag-
example, netic radiation having energy 2.99 × 1012 erg mol–1
24
Cr: [Ar] 3d5 4s1 (h = 6.625 × 10–34Js).
Solution
3d5
4s 1
6.023 × 1023 × 6.625 × 10−34 × 3 × 108
N hc
n=6 λ = ____
E = 2.99 × 1012
• To find multiplicity (m) and spin (s) = 4000 Å.
m = (n + l) = (2s + l)
Example: Spectral Series and Rydberg Formula
24
Cr: [18Ar] 3d5 4sl 3. What transition in the hydrogen spectrum would have
m=6+1=7 the same wavelength as the Balmer transition n = 4 to
• Number of spins = n/2 = 6/2 = 3. n = 2 of He+ spectrum?
• To find magnetic nature and magnetic moment Solution
n = 0 diamagnetic For He+,
n = 1, 2 , 3 paramagnetic
n = 4, 5, 6 ferromagnetic or highly paramagnetic
1
__ 2 __1 __
λ = RHZ 22 – 42
1
( )
_______ For H,
magnetic moment (µ) = √ n(n + 2) B. M.
B. M. = Bohr magneton
1
__ 1 __
__
λ = RH n2 – n2
1
( 1 2
)
• To find colour Since λ is same
1. If n = 0 ion is colourless Z2 [l/22 – l/42] = [l/n12 – l/n22]
For example, Cu+ Zn+2, Cd+2 Z=2
2. If n = 1, 2, 3 ion is coloured [l/l2 – l/22] = [l/n12 – l/n22]
For example, Cu+2, Fe+2, Fe+3 n1 = 1 and n2 = 2

4. Find out the wavelength of Hα line of hydrogen spec-

trum in the Balmer series. (RH = 109676 cm–1).
Solution
1
__ 1 __
__
(1
λ = RH n21 – n22 )
 Atomic Structure 4.15

For Balmer series n1 = 2 and for H, Solution

n2 = 3 (first line of Balmer series) According to de Broglie equation,
λ = __ph
1
__ 1 __
__ 1
λ = 109676 22 – 32 ( )
= 109676 (1/4 – 1/9)
h
p = __
λ
5
= 109676 × __
36 cm
–1 6.62 × 10–34
= _________ = 3.31 × 10–24 kg ms–1
2 × 10–10
36
= ________
5 × 109676 cm 9. Show that the wavelength of a 150 g rubber ball mov-
= 65.65 × 10 cm –6 ing with a velocity 50 m sec–1 is short enough to be
= 6564 Å observed (h = 6.62 × 10–34 Js).
Solution
5. Find out the wavelength of radiations emitted produced in
a line in Lyman series, when an electron falls from fourth 6.62 × 10−34
h
λ = ___
mv = = 8.82 × 10–35 m
stationary state in hydrogen atom. (RH= 1.1 × 107 m–1) 0.150 × 50
Solution = 8.82 × 10–33 cm
The wavelength is short enough to be observed.
1
__
(
1 __
__ 1
λ = RH n21 – n22 ) 10. A cricket ball weighing 100 g is to be located within
For Lyman series n1 = 1, n2 = 4
0.1 Å. What is the uncertainty in its velocity?
1
__ 1 __
7 __ 1
λ = 1.1 × 10 12 – 42 ( ) Solution
= 0.9696 × 10–7 m h
∆x . m. ∆v = ___
4π
6. Calculate the wavelength for the shortest wave length ∆x = Location of ball= 0.l Å = 0.1 × 10–10 m
transition in the Balmer series of atomic hydrogen. m = Mass of ball = 100 g = 0.1 kg
Solution ∆v = Uncertainty in velocity
h = 6.626 × 10–34 Js
1
__
(
1 __
__ 1
λ = RH n21 – n22 ) 6.626 × 10−34
109677
= 109677 (1/4 – 0) = ______ 0.1 × 10–10 × 0.1 ∆v =
4 4 × 3.14
= 27419.25 cm–1 ∆v = 0.527 × 10–22 ms–1
7. Wavelength of high energy transition of H-atoms is 91.2 11. Calculate the minimum uncertainty in velocity of
nm. Calculate the corresponding wavelength of He+. a particle of mass 1.1 × 10–27 kg if uncertainty in its
Solution
position is 3 × 10–10 cm (h = 6.62 × 10–34 kg m2 s–1)
For H-atom Solution
h
∆x . m. ∆v = ___
1
__ 1 __
__
( 1
λ = RH n21 – n22 ) (i) 4π
h ____
∆v = ___ 1
4 π m ∆x
For He+ ion:
6.62 × 10–34
= ______________________
1
__
λ2
1 __
= RHZ2 __ (
– 1
n21 n22 ) (ii) 4 × 3.14 × 1.1 × 10–27 × 3 × 10–8
= 1.59 ms–1
By (i) and (ii),
λ2 __
__ 1 12. A bulb emits light of λ = 4500 Å. The bulb is rated as 150
λ1 = z2 watt and 8 % of the energy is emitted as light. How many
1
or λHe+ = λH × __
Z2
1
= 91.2 × __
22
= 22.8 nm photons are emitted by the bulb per second?
Solution
De Broglie Relation and Uncertainty Principle hc
Energy of one photon = __
λ
8. Calculate the momentum of a moving particle which 6.625 × 10–34 × 3 × 108 J
has a de Broglie wavelength of 2 Å. = _________________
4500 × 10–10
= 4.42 × 10–19 J
4.16 Chapter 4

8
Energy emitted by the bulb = 150 × ___
100 J = 1312 kJ [1/22 – 1/32]
8 = 1312 kJ (5/36)
n × 4.42 × 10–19 = 150 × ___
100 ∆E2 → 1 ____
_____ 3/4 3 __
__ 27
36 __
n = 27.2 × 1018 ∆E3 → 2 = 5/36 = 4 × 5 = 5

15. Find the ratio of the radii of the first three Bohr or
Miscellaneous
obits.
13. State the number of protons, neutrons and electrons in Cl2
and C14. Solution
Radius of the electron orbit in a particular state,
Solution
rn = n__
2

Z (5.29 × 10 m)
–11
The atomic number of C12 is 6. So in it number of
electrons = 6 = n2 (5.29 × 10–11 m) for H atom
Number of protons =6 So, r1 : r2 : r3 = l2 : 22 : 32 = l : 4 : 9.
Number of neutrons = 12 – 6 = 6 16. A compound of vanadium has a magnetic moment of
In 6C14 1.73 B.M. Work out the electronic configuration of the
Number of electrons =6 vanadium ion in the compound.
Number of protons =6
Number of neutrons = 14 – 6 = 8. Solution
14. Find the ratio of the difference in energy between the Magnetic moment = 1.73 B.M. = √N(N+2) Here
first and the second Bohr orbit to that between the sec- N = number of unpaired electrons N=l
ond and the third Bohr orbit. It means that in the compound vanadium ion must
have one unpaired electrons.
Solution
V = 1s2, 2s2 2p6, 3s2 3p6 4s2 3d3
∆E = 1312 kj [(1/n2 initial) – (1/n2 final)] 23

V+4 = 1s2, 2s2 2p6, 3s2 3p6 3d1

∆E2 → 1 = En = 2 – En = 1

,
CONCEPTS AT A GLANCE
 The radius r, of the nucleus of an atom, is related to its mass
number (A) according to the equation r = R0 Al/3 1 Ze2
ET = −
where R0 is a constant having value = 1.4 × 10–15 m. 2 r
 The shapes of the seven f-orbtials are omplicated but their EK = –ET
designations are as follows.
 Total No. of electrons in any orbit is given as 2n2 or
f x3 ,f y3 ,f z3 ,f y z 2 y2 ,f y z 2 x2 ,f z y2 x2 ,f xyz
( ) ( ) ( ) ℓ =( n −1)

 The folllowing are not possible n ≠ 1, n < 1, m > 1. If any

∑ (2ℓ + 1)
ℓ=0
of these is not obeyed arrangement of quantum numbers  Exchange energy:
set is not permissible.
The electrons with parallel spins present in the degenerate
 Since ℓ cannot be equal to n so orbitals 1p, 2d, 3f, 4g do orbitals tend to exchange their position and during it the
not exist. energy released is known as exchange energy.
 In case of H-atom (Hydrogenic Species) energy depends  The two electrons in different orbitals are for apart so suf-
only upon n-value so fer less electronic repulsion than they are present in same
1s <2s ≃ 2p <3s ≃ 3p ≃ 3d< orbital with Anti parallel spins.
 Total Energy (ET) for any e– in any orbit:  The Limitation of de-Brogloe Concept is that it can be
applied only on objects having force free environment it
1 means not appli cable for any electron present in the atom.
ET = EK.E + EP.E = mv2 + EP.E
2

1 Ze2  Ze2 
= + 
2 r  r 
,
 Atomic Structure 4.17

,
TOOL BOX AND SUMMARY OF IMPORTANT RELTIONS
____
Nhc De Broglie Equation
 E = Nhυ = λ
When electron changes its orbit energy change occurs in quanta. h
___ h
___

λ = mc = mv
hc
∆E = E2 – E1 = hυ or (quanta)
λ h
n(n – 1)
λ=
______ 2m K.E.
 Number of spectrum lines = 2
Here, n is orbit from which electron jumps or higher energy K.E. = ½ mv2 = eV (Potential difference)
level. ½ mv2 = eV
eV
___
v2 = 2 m
Rydberg Formula _______
hc
__ 2 π2Me4Z2 __
_________ 1 1
__ v = √ 2eV / m
∆E or λ = n2 n12 (
– n2
2
) h
___
∆ x . m ∆v ≥ 4 π .
_ 2 π2Me4Z2
_________ 1
__ 1
__
v = 1/ λ =
_
n3c n12
– n2
2
( )  Here ∆x = Uncertainty in position,
1
__ 1
__ 1
__
1
(
v = λ = RHZ2 n 2 – n 2
2
) ∆v = Uncertainty in velocity.
h
____
_ ∆x . ∆v ≥ 4 πm
v = Wave number, λ = Wavelength
n1 = Lower orbit, n2 = Higher orbit Calculation of Nodes
RH = Rydberg constant
Node = n–1
RH= 109678 cm–1 or 1.1 × 107 m.
Radial nodes or spherical nodes = n–ℓ–l
 Calculation of radius of nth orbit
n2
__ Angular or non-spherical = ℓ
rn = 0.53 × Z Å
 Angular momentum of electron in any orbital.
Here, n = nth orbit
Calculation of velocity of electron in nth orbit: h

~- l ( l + l ) . or l ( l + l ) .ℏ
Z
__ 2π
vn = 2.165 × 10 × n m/sec
6

 Calculation of energy of electron in nth orbit:  K.E. (½ mv2) = E – ϕ

–313.52
______ 2 Here, E = Energy of radiation
En = n2
Z kcal/mol
__2
Z ϕ = Work function (minimum energy needed for electron
En = –13.6 n2 eV/atom
emission)
2
= –2.178 × 10–8 × Z J/atom K.E. = hυ – hυ0
n2 υ0 = Threshold frequency (minimum frequency of light
Vn
radiation needed for electron ejection).
 Number of revolutions =
2πrn

,
4.18 Chapter 4

EXERCISES

Single Option Correct Type

1. How many e– are present in p-sub-orbits in Zn-atom? 10. The correct set of quantum numbers is
(a) 2 (b) 6 (a) n = 2, l = l, m = –2, s = 0
(c) 12 (d) 18 (b) n = 2, l = –2, m = l, s = + ½
(c) n = 2, l= 2, m = –l, s = –½
2. Wavelength of spectral line emitted is inversely pro-
(d) n = 2, l = l, m = 0, s = + ½
portional to
(a) energy (b) velocity 11. The values of four quantum numbers of valence elec-
(c) radius (d) quantum number tron of an element are n = 4, l = 0, m = 0 and s = + ½.
The element is
3. The number of electrons, neutrons and protons in a
(a) Ti (b) K
species are equal to 10, 8 and 8 respectively. The
(c) Na (d) Sc
proper symbol of the species is
(a) 16O8 (b) 18O8 12. Set of isoelectronic species is
(c) Ne10
18
(d) 16O8–2 (a) H2, CO2, CN–, O–
(b) N, H2S, CO
4. Which set has same number of unpaired electrons?
(c) N2, CO, CN–, O2+2
(a) Fe2+, Mn+2 (b) Fe3+, Mn+2 (d) Ca, Mg, Cl
(c) Cr , Ni
+3 2+
(d) Zn2+ Cu2+
13. Number of orbitals in L energy level
5. Which one of the following forms a colourless solu-
(a) 1 (b) 2
tion in aqueous medium?
(c) 3 (d) 4
(a) V3+ (b) Cr3+
(c) Ti 3+
(d) Sc3+ 14. Ratio of radii of second and first Bohr orbits of H atom
Atomic number Sc = 21, Ti = 22, V = 23, Cr =24 is
(a) 2 (b) 4
6. The incorrect configuration is (c) 3 (d) 4
(a) K = [Ar] 4s1
15. If a source of power 4Kw produces 1020 photon
(b) Cr = [Ar] 3d5 4s1
Per second, the radiation belongs to a part of the spec-
(c) Cr = [Ar] 3d4 4s2
trum called
(d) Cu = [Ar] 3d10 4s1
(a) γ-Rays (b) U.V Rays
7. Which of the following elements has least number of (c) Microwaves (d) X-Rays
electrons in its M shell?
16. The outer most configuration of most electronegative
(a) Mn (b) Ni
element is
(c) K (d) Sc
(a) ns2 np5 (b) ns2 np6
8. In which orbital is the angular momentum of an elec- (c) ns np
2 4
(d) ns2 np6
tron zero?
17. Which one of the following expressions represent the
(a) 2p (b) 2s
electron probability function D?
(c) 3d (d) 4f
(a) 4πr dr ψ2 (b) 4πr2 dr ψ
9. Chromium is represented by the electronic (c) 4πr dr ψ
2 2
(d) 4πr dr ψ
configuration
18. If the electron of a hydrogen atom is present in the first
(a) [Ne] 3s2 3p6 3d1 4s2
orbit, the total energy of the electron is
(b) [Ne] 3s2 3p6 3d2 4s1
(c) [Ne] 3s2 3p6 3d5 4s1 (a) –e2/2r (b) –e2/r
(d) [Ne] 3s2 3p6 4s2 3d4 (c) –e /r
2 2
(d) –e2/2r2
 Atomic Structure 4.19

19. Quantum numbers of an atom can be defined on the 29. l = 3, then the values of magnetic quantum numbers
basis of are Å
(a) Aufbau’s principle (a) ± l, ± 2, ± 3 (b) 0, ± 1, ± 2, ± 3
(b) Heisenberg’s uncertainity principle (c) –1, –2, –3 (d) 0, + l, + 2, + 3
(c) Hund’s rule
30. Which one of the following pairs of ions have the same
(d) Pauli’s exclusion principle
electronic configuration?
20. Which of the following is isoelectronic? (a) Sr3+, Cr3+ (b) Fe3+, Mn2+
(a) CO2, NO2 (b) NO2–, CO2 (c) Fe , Co
3+ 3+
(d) Cr3+, Fe3+
(c) CN , CO
–
(d) SO2, CO2
31. The radius of hydrogen atom is 0.53 Å. The radius of
21. Which of the following do not travel with speed of Li2+ is of
light? (a) 1.27 Å (b) 0.17 Å
(a) De-Broglie waves (c) 0.57 Å (d) 0.99 Å
(b) X-rays
32. The atomic number of an element is 35. What is the
(c) Gamma rays
total number of electrons present in all the p-orbitals
(d) All of these
of the ground state atom of that element?
22. How many electrons can be accommodated in a (a) 17 (b) ll
p-orbital? (c) 23 (d) 6
(a) 6 electrons (b) 2 electrons
33. The atomic number of an element is 17. The number of
(c) 4 electrons (d) none of these
orbitals electron pairs in its valence shell is
23. The quantum number ‘m’ of a free gaseous atom is (a) 3 (b) 4
associated with (c) 6 (d) 8
(a) the effective volume of the orbital
34. The correct representation for d orbital is
(b) the shape of the orbital
(c) the spatial orientation of the orbital (a) (n – 1) d1–9 ns1
(d) the energy of the orbital in the absence of a mag- (b) (n – 1) d1–10 ns1–2
netic field (c) (n–1)d1–5
(d) (n–l) d1–10 ns2
24. In ground state, an element has 13 electrons in its M
shell. The element is 35. An element has 2 electrons in its K shell, 8 electrons
in L shell, 13 electrons in M shell and one electron in
(a) copper (b) iron
N shell. The element is
(c) nickel (d) chromium
(a) Cr (b) Fe
25. Which of the following pair of ions have same para (c) V (d) Ti
magnetic moment?
36. Effective magnetic moment of Sc3+ ion is
(a) Cu2+, Ti3+ (b) Ti3+, Ni2+
(c) Ti , Cu
4+ 2+
(d) Mn2+, Cu2+ (a) 0 (b) 1.73
(c) 2.83 (d) 3.87
26. The following quantum numbers are possible for how
many orbital? n = 3, l = 2, m = +2 37. Which of the following is not possible?
(a) 1 (b) 2 (a) n = 2, l = l, m = 0
(c) 3 (d) 4 (b) n = 2, l = 0, m = –l
(c) n = 3, l = 0, m = 0
27. The number of nodal planes in a px orbital is (d) n = 3, l = 1, m = –1
(a) 1 (b) 2
38. The most probable radius (in pm) for finding the elec-
(c) 3 (d) 0
tron in He+ is
28. How many d-electrons are present in Cr2+ ion? (a) 105.8 (b) 52.9
(a) 5 (b) 6 (c) 26.5 (d) 0.0
(c) 3 (d) 4
4.20 Chapter 4

39. In which of the following pairs are both the ions 46. Which one of the following is the standard for atomic
coloured in aqueous solution? mass?
(a) Sc3+, Co2+ (b) Ni2+, Cu+ (a) 1H1 (b) 6C12
(c) Ni , Ti
2+ 3+
(d) Sc3+, Ti3+ (c) 6C4 (d) 8O16
(At. no. Sc = 21, Ti = 22, Ni = 28,Cu = 29, Co = 27)
47. Which of the following relates to photons both as
40. When potassium metal is exposed to violet light wave motion and as a stream of particles?
(a) there is no effect
(a) interference (b) E = mc2
(b) ejection of electron takes place
(c) diffraction (d) E = hυ
(c) the absorption of electrons takes place
(d) ejection of some potassium atoms occurs 48. Electromagnetic radiation with maximum wavelength
is
41. The atomic number of Ni and Cu are 28 and 29 respec-
tively. The electronic configuration 1s2 2s2 2p6 3s2 3p6 (a) radiowave (b) X-ray
3d10 represents (c) infraredt (d) ultraviolet
(a) Cu+ (b) Cu2+ 49. When the e– of a H-atom moves from n = 4 to n = 1 the
(c) Ni 2+
(d) Ni number of spectral lines emitted is
42. Rutherford’s experiment, which established the nu- (a) 3 (b) 6
clear model of the atom, used a beam of (c) 9 (d) 15
(a) β-particles, which impinged on a metal foil and
50. Which set represents the quantum Numbers of 19th
got absorbed
electron in Cr–atom?
(b) γ-rays, which impinged on a metal foil and ejected
electrons (a) 4, 0, 0, ½ (b) 4, 1, 0, ½
(c) Helium atoms, which impinged on a metal foil and (c) 3, 2, 2, ½ (d) 3, 2, –2, ½
got scattered 51. The orbital diagram in which both the Pauli’s exclu-
(d) Helium nuclei, which impinged on a metal foil
sion principle and Hund’s rule are violated is
and got scatterd. ↑
(a) ↑ ↑↑ ↑
43. The quantum number + ½ and – ½ for the electron spin ↑ ↑ ↑ ↑
represent (b) ↑ ↑ ↑ ↑
(a) rotation of the electron in clockwise and anti- ↑ ↑ ↑
(c) ↑
clockwise direction respectively. ↑ ↑ ↑
(b) rotation of the electron in anti clockwise and (d) ↑ ↑ ↑ ↑
clockwise direction respectively. 52. The maximum number of 3d electrons having s = + ½
(c) magnetic moment of the electron pointing up and are
down respectively. (a) 10 (b) 5
(d) two quantum mechanical spin states which have (c) 14 (d) 7
no classical analogues.
53. The fourth electron of Be atom will have which of the
44. The electronic configuration of an element is 1s2 2s2
following quantum numbers?
2p6 3s2 3p6 3d5 4s1. This represents
(a) 1, 0, 0, ½ (b) 2, 0, 0, – ½
(a) excited state
(c) 2, l, 0, + ½ (d) 1, 1, 1, + ½
(b) ground state
(c) cationic form 54. The electron density between 1s and 2s orbital is
(d) anionic form (a) high (b) low
45. The angular momentum (L) of an electron in a Bohr (c) zero (d) none of these
orbit is given as 55. The Angular momentum of an e– can’t be
(a) L = nh/2π h 2h
(b) √[l(l + 1) h/2π (a) (b)
π 2π
(c) L = mg/2π
(d) L = h/4π 2.5h 0.5h
(c) (d)
2π π
 Atomic Structure 4.21

56. If the wavelength of an electromagnetic radiation is 64. An electron is moving in Bohr’s fourth orbit, its
2000 Å. What is the energy in ergs? de-Broglie wavelength is X. What is the circumference
(a) 9.92 × 10–19 (b) 9.94 × 10–12 of the fourth orbit?
(c) 4.97 × 10 –12
(d) 4.97 × 10–19 (a) 2λ (b) 2/λ
(c) 3λ (d) 4λ
57. The de Broglie wavelength of the electron in the
ground state of hydrogen atom is [K.E.= 13.6 eV]; 65. The correct order of number of unpaired electrons in
1eV = 1.602 × 10–19 J the ion Cu2+ Ni2+, Fe3+ and Cr3+ is
(a) 33.28 nm (b) 3.328 nm (a) Cu2+ > Ni2+ > Cr3+ > Fe3+
(b) Ni2+ > Cu2+ > Fe3+ > Cr3+
(c) 0.3328 nm (d) 0.0332 nm
(c) Fe3+ > Cr3+ > Ni2+ > Cu2+
58. The value of Planck constant is 6.63 × 10–34 Js. he (d) Fe3+ > Cr3+ > Cu2+ > Ni2+
velocity of light is 3.0 × 108 m s–1. which value is clos- 66. Find the magnetic moment of a divalent ion in aqueous
est to the wavelength in nanometres of a quantum of solution if its atomic number is 25.
light with frequency of 8 × 1015 s–1?
(a) 6.9 B.M. (b) 5.9 B.M.
(a) 4 × 101 (b) 3 × l07 (c) 4.9 B.M. (d) 3.0 B.M.
(c) 2 × 10 –25
(d) 5 × 10–18
67. The magnetic moment of Cu2+ ion is
59. The total number of electrons present in all the s or- (a) 2.6 (b) 2.76
bitals, all the p orbitals and all the d orbitals of cesium (c) 1.73 (d) 0
ion are respectively
68. Given: the mass of electron is 9.11 × 10–31 kg Planck
(a) 12, 20, 22 (b) 8, 22, 24
constant is 6.626 × 10–34 Js, the uncertainty involved in
(c) 10, 24, 20 (d) 8, 26, 10 the measurement of velocity within a distance of 0.1 Å
60. The frequency of radiation emitted when the electron is
falls from n = 4 to n = 1 in a hydrogen atom will be (a) 5.79 × 108 ms–1 (b) 5.79 × 105 ms–1
(Given ionization energy of H = 2.18 × 1018 J atom–1 (c) 5.79 × 106 ms–1 (d) 5.79 × 107 ms–1
and h = 6.625 × 10–34 Js) 69. The energy ratio of a photon of wavelength 3000Å and
(a) 1.54 × 10l5 s–1 (b) 1.03 × 10l5 s–1 6000Å is
(c) 3.08 × 10 s
l5 –1
(d) 2.00 × l0l5 s–1 (a) 1 : 1 (b) 2 : 1
61. Among the following series of transition metal (c) 1 : 2 (d) 1 : 4
ions, the one where all metal ion have 3d2 electronic 70. The energy of second Bohr orbit of the hydrogen atom
configuration is is –328 kJ mol–1, hence the energy of fourth bohr orbit
(a) Ti3+, V2+, Cr3+, Mn4+ would be
(b) Ti+, V4+, Cr6+, Mn7+ (a) –164 kJ mol–1 (b) –41 kJ mol–1
(c) Ti4+, V3+, Cr2+, Mn3+ (c) –82 kJ mol –1
(d) –1312 kJ mol–1
(d) Ti2+, V3+, Cr4+, Mn5+ 71. The de Broglie wavelength associated with a particle
(At. wt Ti = 22, V = 23, Cr = 24, Mn = 25 ) of mass 10–6 kg moving with a velocity of 10 ms–1 is
62. The relationship between energy E, of the radiation (a) 6.63 × 10–7 m (b) 6.63 × 10–16 m
with a wavelength 8000 Å and the energy of the ra dia- (c) 6.63 × 10 m
–21
(d) 6.63 × 10–29 m
tion with a wavelength 16000 Å is 72. In hydrogen atom, energy of first excited state is –3.4
(a) E1 = 2E2 (b) E1 = 4E2 eV. The kinetic energy of the same orbit of hydrogen
(c) E1 = 6E2 (d) E1 = E2 atom would be
(a) + 3.4 eV (b) + 6.8 eV
63. The atomic numbers of elements X, Y, Z are 19.21
(c) –13.6eV (d) +13.6eV
and 25 respectively. The number of electrons present
in the ‘M’ shells of these elements follow the order 73. The velocity of an electron in the second shell of
(a) Z > Y > X (b) X > Y > Z hydrogen atom is
(c) Z > X > Y (d) Y > Z > X (a) 10.94 × 106 ms–1 (b) 18.88 × 106 ms–1
(c) 1.888 × 106 ms–1 (d) 1.094 × 106 ms–1
4.22 Chapter 4

74. Electron energy of a photon is given as: ∆E/atom (4) the oxidation state of nitrogen in HN, is –3
= 3.03 × 10–19 J atom–1 then, the wavelength of the (a) 1, 2, 3 (b) 2, 3, 4
photon is (c) 3, 4 (d) 1, 2, 4
(a) 6.56 nm (b) 65.6 nm
81. For a d-electron, the orbital angular momentum is
(c) 656 nm (d) 0.656 nm
(a) √6h (b) √2h
Given, h (Planck constant) = 6.63 × 10–34 Js c (velocity
(c) h (d) 2h
of light) = 3.00 × 108 ms–1
82. The orbital angular momentum of an electron in 2s
75. If the nitrogen atom has electronic configuration 1s7, orbital is
it would have energy lower than that of the normal h
(a) + __21 . __
2π (b) zero
ground state configuration 1s2 2s2 2p3 , because the
electrons would be closer to the nucleus. Yet 1s7 is h
(c) __
2π
h
(d) √2 __
2π
not observed because it violates
83. The mass of an electron is m. Its charge is e and it is
(a) Heisenberg uncertainty principle accelerated from rest through a potential difference V.
(b) Hund’s rule The velocity acquired by the electron will be
(c) Pauli’s exclusion principle
(a) √V/m (b) √eV/m
(d) Bohr postulates of stationary orbits
(c) √2e V/m (d) none
76. Radial nodes present in 3s and 2p orbitals are
respectively 84. An atom A has the electronic configuration of 1s2 2s2
2p1. Atom B has the electronic configuration of 1s2
(a) 0, 2 (b) 2, 0
2s2 2p1. The empirical formula of the compound
(c) 2, 1 (d) 1,2
obtained from the reaction of A and B is
77. The radius of which of the following orbits is same as (a) AB (b) AB3
that of the first Bohr’s orbit of hydrogen atom? (c) A3B3 (d) A2 B6
(a) He+ (n = 2) (b) Li2+ (n = 2)
85. A 600 W mercury lamp emits monochromatic radia-
(c) Li (n = 3)
2+
(d) Be3+ (n = 2)
tion of wavelength 331.3 nm. How many photons are
78. The wavelength associated with a golf ball weighing emitted from the lamp per second?
200 g and moving at a speed of 5 m/h is of the order
(h = 6.626 × 10–34 Js; velocity of light = 3 × 108 ms–1
(a) 10–10 m (b) 10–20 m
(c) 10 m
–30
(d) 10–40 m (a) 1 × 1019 (b) 1 × 1020
(c) 1 × 1021 (d) 1 × 1023
79. Ground state electronic configuration of nitrogen atom
can be represented by 86. The shortest wavelength in hydrogen spectrum of
Lyman series when RH = 109678 cm–1 is
(1)
(a) 1002.7 Å (b) 1215.67 Å
(2) (c) 1127.30 Å (d) 911.7 Å

(3) 87. Which electronic level would allow the hydrogen atom
to absorb a photon but not to emit a photon?
(4) (a) 1s (b) 2s
(a) 1 only (b) 1, 2 (c) 2p (d) 3s
(c) l, 4 (d) 2, 3
88. Correct set of four quantum numbers for the valence
80. Which of the following statement(s) are correct? (outermost) electron of rubidium (Z = 37) is
(1) the electronic configuration of Cr is [Ar] 3d5 4s1 (a) 5, 0, 0 , ± ½ (b) 6, 0, 0 , + ½
(atomic number of Cr = 24) (c) 5, 1, l, ± ½ (d) 5, l, 0, ± ½
(2) the magnetic quantum number may have a nega-
89. The increasing order (lowest first) for the values of
tive value
e/m (charge/mass) for electron (e), proton (p), neutron
(3) in silver atom, 23 electrons have a spin of one
(n) and alpha particle (a) is
type and 24 of the opposite type (atomic number
(a) n, p, a , e (b) n, p, e, a
of Ag = 47)
(c) n, a, p, e (d) e, p, n, a
 Atomic Structure 4.23

90. The ionization energy of hydrogen atom is 13.6 eV. 97. For n = 2 the correct set of ℓ, m are
What will be the ionization energy of He+? (a) ℓ = 2, m = –2,–1, 0 +1, +2
(a) 13.6 eV (b) 54.4 eV (b) ℓ = 1 m = –2,–1, 0 +1, +2
(c) l22.4 eV (d) zero (c) ℓ = 1 m = –1, 0, +1
91. If S, be the specific charge (e/m) of cathode rays and S2 (d) ℓ = o m = –1, 0, +1
be that of positive rays then which is true?
98. Probability of finding the electron ψ2 of s orbital
(a) S1 = S2 (b) S1 < S2
doesn’t depend upon
(c) S1 > S2 (d) None of these
(a) azimuthal quantum number.
92. Predict the total spin in Ni2+ ion (b) energy of s orbital
(a) ±5/2 (b) ±3/2 (c) principal quantum number
(c) ± l/2 (d) ± l (d) distance from nucleus (r)
93. The orbital diagram in which Aufbau principle is 99. The charge cloud of a single electron in a 2px atomic
violated is orbital has two lobes of electron density. This means
↑ ↑ (a) there is a high probability of locating the electron
(a) ↑ ↑ ↑
↑ in a 2px atomic orbital at values of x > 0
(b) ↑ ↑ ↑ ↑ (b) there is a great probability of finding a p electron
↑
(c) ↑ ↑ ↑ ↑ right at the nucleus
↑ ↑ ↑ (c) there is a high probability of locating it values of
(d) ↑ ↑ ↑ ↑
x < 0 but no probability at alloy locating if any
94. Wave function vs distance from nucleus graph of an where in the yz plane along which x = 0.
orbital is given below: (d) both (a) and (c)
+ 100. The wavelength of the de Broglie wave of the elec-
tron revolving in the fifth orbit of the hydrogen atom
is (r0 is the Bohr’s radius = 0.529 Å)
Ψ -
r (a) 20 r0
(b) (10 π) r0
The number of nodal sphere of this orbital is (c) 5 π r0
(a) 1 (b) 2 (d) 15 π r0
(c) 3 (d) 4
101. A monoenergetic electron beam with a de Broglie
95. For the electronic transition from n = 2 → n = 1, wavelength of x Å is accelerated till its wavelength is
which of the following will produce shortest wave halved. By what factor is its kinetic energy changed?
length? (a) 8 (b) 6
(a) Li2+ ion (b) D atom (c) 4 (d) 3
(c) He+ ion (d) H atom 102. The de Broglie wavelength associated with a ball of
mass 1 kg having a kinetic energy 0.5 J is
96. Which of the following curves may represent the
speed of the electron in a hydrogen atom as a func (a) 6.626 × 10–34 m
tion of the principal quantum number n? (b) 13.2 × 10–34 m
(c) 10.38 × 10–21 m
a
d
(d) 6.626 Å
b
103. The size of a microscopic particle is one micron
v c and its mass is 6 × 10–13 gm. If its position may be
measured to within 0.1% of its size, the uncertainty in
n velocity, in cm s–1, is approximately
(a) d (b) c (a) 10–6/3 π (b) 10–7/2 π
(c) b (d) a (c) 10–5/4 π (d) 10–7/4 π
4.24 Chapter 4

104. The electrons, identified by quantum numbers n and l 111. An electron in a hydrogen atom in its ground state
(i) n = 4. l = 1 (ii) n = 4, l = 0 (iii) n = 3, l = 2 (iv) n absorbs 1: 50 times as much energy as the minimum
= 3, l = 1 can be placed in order of increasing energy required for it to escape from the atom. What is the
from the lowest to highest as wavelength of the emitted electron?
(a) (iv) < (ii) < (iii) < (i) (a) 4.7 Å (b) 4.70 pm
(b) (ii) < (iv) < (i) < (iii) (c) 6.3 Å (d) 8.4 Å
(c) (i) < (iii) < (ii) < (iv)
(d) (iii) < (i) < (iv) < (ii) 112. If the radius of the first Bohr orbit is ‘a’, then de
Broglie wavelength of electron in 3rd orbit is nearly
105. What is the wavelength of the radiation emitted pro-
duced in a line in the Lyman series when an electron (a) 2π a (b) 6π a
falls from fourth stationary state in hydrogen atom? (c) 3a (d) a/3
(RH = 1.1 × 107 m–1)
113. If the shortest wavelength of H atom in Lyman series is
(a) 96.97 nm (b) 969.7 nm ‘a’, then longest wavelength in Balmer series of He+ is
(c) 9.697 nm (d) none
(a) a/4 (b) 5a/9
106. Rearrange the following (I to IV) in the order of (c) 4a/9 (d) 9a/5
in creasing masses and choose the correct answer
from (a), (b), (c), (d). (atomic masses: N =14, O = 114. In hydrogen atom, an orbit has a diameter of about
16, Cu = 63). 16.92 A. What is the maximum number of electrons
I. 1 molecule of oxygen that can be accommodated?
II. 1 atom of nitrogen (a) 32 (b) 16
III. 1 × 1010 g molecular weight of oxygen (c) 48 (d) 72
IV. 1 × 10–18 g atomic weight of copper
(a) II < I < IV < III (b) IV < III < II < I 115. Energy levels A, B, C of a certain atom corresponds
(c) II < III < I < IV (d) III < IV < I < II to increasing values of energy, i.e., EA < EB < Ec. If
X1, X2 and X3 are the wavelengths of radiations cor-
107. The ionization energy of He+ is 19.6 × 10–18 J atom–1.
Calculate the energy of the first stationary state of Li2+. responding to the transitions C to B, B to A and C to
A respectively, which of the following statement is
(a) 19.6 × 10–18 J atom–1
(b) 4.41 × 10–18 J atom–1 correct?
X1 C
(c) 19.6 × 10–19 J atom–1 B
(d) 4.41 × 10–17 J atom–1
X2 X3
108. The masses of photons corresponding to the first A
lines of the Lyman and the Balmer series of the (a) X1 + X2 + X3 = 0 (b) X3 = X1 + X2
atomic spectrum of hydrogen are in the ratio of X X
(a) 4 : 1 (b) 27 : 5 (c) X32 = X12 + X22 (d) X3 = ______
1
X +X
2

1 2
(c) 1 : 4 (d) 5 : 27
116. A 1000 watt radio transmitter operates at a frequen cy
109. An X-ray tube is operated at 50,000 volts. The of 880 kc/sec. How many photons per sec does it emit?
short-wavelength limit of the X-rays produced is [h = 6.626 × 10–34 Js]
(a) 0.1245 Å (a) 2.51 × 1030 (b) 2.27 × l028
(b) 0.3485 Å (c) 1.72 × 1030 (d) 1.77 × 1027
(c) 0.2485 Å
(d) 0.03456 Å 117. How many moles of electrons weigh one kilogram?
(mass of electron = 9.108 × 10–31 kg, Avogadro number
110. The ratio of the difference between 2nd and 3rd = 6.023 × 1023)
Bohr’s orbit energy to that between 3rd and 4th orbit (a) 6.023 × 1023 (b) 1/9.108 × 1031
energy is
6.023
(a) 7/20 (b) 20/7 (c) _____
9.108 × 10
54 1
(d) __________
9.108 × 6.023
× 108
(c) 27/9 (d) 9/27
 Atomic Structure 4.25

118. Calculate the wavelength and energy of the radiation (a) 2.18 × 10–21 kJ (b) 3.18 × 10–22 kJ
emitted for the electronic transition from infinity (c) 1.18 × 10–23 kJ (d) 2.18 × l0–31 kJ
(∞) to stationary state first of the hydrogen atom.
(RH = 1.09678 × 107 m–1, h = 6.6256 × 10–34 Js)

More than One Option Correct Type

119. Some of the following sets of quantum numbers are 123. Energy of level 1, 2, 3 of a certain atom corresponds
correct for a 4d electron. Which are correct sets ? to increasing value of energy E1 < E2 < E3. If λ1, λ2 and
1 λ3 are the wavelength of radiation corresponding to
(a) 4 , 3, 2 ,+ transition 3 → 2, 2 → 1 and 3 → 1 respectively. Which
2
of following statement is/are correct?
(b) 4, 2, 1, 0
1 1 1
1 (a) = + .
(c) 4, 2, −2, + λ 2 λ1 λ 3
2
λ1 λ 3
1 (b) λ 2 = .
(d) 4, 2, 1, − λ1 + λ 2
2
1 1 1
120. [Cr(H2O)6] Cl3 (Cr = 24) has a magnetic moment of (c) = + .
λ 3 λ1 λ 2
3.83 B.M. The incorrect distribution of 3d electrons in
the chromium of the complex is [2010] λ1 λ 2
(d) λ 3 = .
λ1 + λ 2
(a) 3d1xy 3d1yz 3d1xz
(b) 3d1xy 3d1yz 3d1z2 124. For radial probability distribution curves, which of the
following is /are correct?
(c) 3d12d1 x2 – y2 3d1z2 3d1xz
(a) the number of spherical or radial nodes is equal to
(d) 3d1xy 3d1x2 – y2 3d1yz (n – l – 1).
121. Which of the following statement (s) is /are incorrect ? (b) the number of maxima in 2s orbital is two
(c) the number of angular nodes is ‘l’.
(a) 3 s orbital has 2 radical nodes.
(d) 3d z 2 has two spherical nodes.
(b) Electronic configuration of Co3+ is 4s2 3d4.
125. In which of the orbital/orbitals radial node and angular
(c) 2 p orbital has 1 radial node. nodes are same?
(a) 3p (b) 4p
(d) Node is a region around the nucleus of an atom
(c) 6f (d) 5d
where probability of finding electron is maximum.
126. Four different set of quantum numbers for 4 electrons
122. Which of the following factors induce larger angle of
are given below :
deflection in Rutherford’s scattering experiment?
(a) The initial kinetic energy of striking α-particles e1 = 4, 0, 0 – 1/2; e2 = 3, 1, 1 – 1/2
must be large e3 = 3, 2, 2 + 1/2 ; e4 = 3 ,0, 0, + 1/2
(b) The initial kinetic energy of striking α-particles Then which of the following order of energies of e1, e2,
must be small e3 and e4 are against the quantum rules ?
(c) The nucleus to which the α-particles are striking
(a) e1 > e2 > e3 > e4
must have small atomic number
(d) The nucleus to which the α-particles are striking (b) e4 > e3 > e2 > e1
must have high atomic number (c) e3 > e1 > e2 > e4
(d) e2 > e3 > e4 > e1
4.26 Chapter 4

127. Pick out the wrong statements. (c) The azimuthal quantum number may have a nega-
(a) Fe3+ ion is more stable than Fe2+ ion in the gaseous tive value.
state. (d) The electronic configuration of Cr is [Ar] 3d5 4s1
(b) For an electron in a 4p-orbital, the quantum num- (atomic number of Cr = 24)
bers are n = 4, l = 1, m = 2, s = +1/2 129. Which of the following statements is /are correct?
(c) Angular momentum of 3s electron is one. (a) The energy of an electron is largely determined by
(d) (n + l) rule is followed for determining the orbital its principal quantum number.
of the lowest energy state. (b) The energy of electron in an orbital in the hydro-
gen atom depends upon the value of principal
128. Which of the following statement is/ are correct? quantum number only.
(a) The number of unpaired electrons in both Fe2+ and (c) The value of principal quantum number for 24th
Mn2+ are five. electron is 3.
(b) In silver atom, 23 electrons have a spin of one type (d) The principal quantum number is a measure of
and 24 of the opposite (atomic number of Ag = the most probable distance of finding the electron
47). around the nucleus

Passage Based Questions

Passage-1 (a) 1.6 Å (b) 16 Å
(c) 4.0 Å (d) 6.25 Å
According to de Broglie concept, all material particles
posses wave character as well as particle character. Passage-2
The wave associated with a moving particle is called
matter wave. The wavelength of the matter wave is The substances which contain atoms with unpaired
given by the equation electrons in their orbitals behave as paramagnetic sub-
h h stances. Such substances are weakly attracted by the
λ= = where p is the momentum of the particle, magnetic field. The paramagnetism is expressed in
p mv
terms of magnetic moment. The magnetic moment is
‘m’ is the mass of the particle and 'v' is the velocity of related to the number of unpaired electrons according
the particle. ‘h’ is called Planck’s constant. to the following relation.
130. The wavelength associated with an electron (mass = Magnetic moment, μ = n ( n + 2 ) BM
9.11 × 10–31 kg) moving with a velocity of 106 m s–1 is Where, n – number of unpaired electrons.
(h = 6.625 × 10–34 J s) BM stands for Bohr Magneton, a unit of magnetic
(a) 0.727 nm (b) 7.27 nm moment.
(c) 727 nm (d) 7.27 m
133. Which of the following ions has the highest magnetic
131. The de Broglie wave length of a moving particle of moment?
mass 1 g is 6.625 × 10–23 m. The velocity of the particle (a) Fe2+ (b) Mn2+
is (c) Cr3+ (d) V3+
(a) 100 cm s–1
134. Which of the following ions has magnetic moment
(b) 100 m s–1
equal to that of Ti3+
(c) 10 m s–1
(a) Ni2+ (b) Co2+
(d) 1000 m s–1
(c) Fe2+ (d) Cu2+
132. Particle A moving with a certain velocity has de
135. An ion of a d-block element has magnetic moment
Broglie wavelength of 1 Å. If the particle B has mass
5.92 BM select the ion among the following:
20% and velocity 80% of that of A, the de Broglie
wavelength of B will be (a) Sc3+ (b) Zn2+
(c) Mn2+ (d) Cr3+
 Atomic Structure 4.27

Match the Column Type

136. Match List I with List II and select the correct answer (c) 2p3 is and

⇀
using the codes given below the lists:
Not

⇀
List-I List-II
(Metal ions) (Magnetic moment) (d) Principal quantum no. n
l. Cr 3+
(i) √35
Column-II
2. Fe2+ (ii) √30
3. Ni2+ (iii) √24 (p) Bohr
4. Mn2+ (iv) √15 (q) Hund’s rule
(v) √8
The correct matching is: (r) Pauli’s exclusion principle

1 2 3 4 (s) Aufbau principle

(a) (i) (iii) (v) (iv) (t) Size of orbit
(b) (ii) (iii) (v) (i)
(c) (iv) (iii) (v) (i) 139. Match the following
(d) (iv) (v) (iii) (i)
Column-I
(e) (v) (i) (ii) (iii)
(a) 2s (b) 2p
137. Match the following:
List-I List-II (c) 3s (d) 3p

1. Number of values of ’l’ for an (i) 0, 1, 2 Column-II

energy level ............(n – 1) (p) sum of (n +1) is 3
2. Actual values of ‘l’ for a (ii) + l .........+ 2,
(q) total number of nodes are two
particular type of orbital + 1, 0, –l
3. Number of ‘m’ values (iii) –2 .... –l (r) Only one node

4. Actual values of ‘n’ for a (iv) n (s) No radial node

particular type of orbital (t) No angular node
The correct matching is:
140. Match the following
1 2 3 4
(a) (iv) (iii) (i) (ii) Column-I
(b) (iv) (i) (iii) (ii) (a) [Ar] 3d84s2 (b) [Ar] 3d10
(c) (i) (ii) (iv) (iii)
(d) (ii) (iii) (i) (iv) (c) [Ar]3d1 (d) [Ar]3d9

138. Match the following Column-II

(p) Cu2+
Column-I
(q) Zn2+
(a) 2s, 3s, 4s, 4d (r) Ti+3
(order of increasing energy) (s) Cu+
(t) Ni
(b) Quantum numbers of 2s2 electrons
n l m s
2 0 0 +1/2
2 0 0 –1/2
4.28 Chapter 4

Integer Type

141. An electron absorbs a photon of light of frequency 147. Atomic No. of Fe = 26; Number of electrons present in
7.312 × 1014 s–1 in the first excited state of hydrogen 3d orbital in Fe2+ ion is ____
and jumps from there to nth excited state. The value of
n is ________. 148. Hydrogen atoms in the ground state are excited by
means of monochromatic radiation of wavelength
142. The ground state electronic wave function of hydrogen 970.6 Å. How many different lines are possible in the
atom is proportional to e − r/a 0 where r is the distance resulting emission spectrum?
from the nucleus and a0 is a constant.
149. Due to transition between different energy levels in
Calculate the relative probability of finding the elec- H–atom, the de–Broglie wavelength of electron is
tron inside a region of volume 1.0 pm3, located at the decreased from 16.5 Å to 6.6 Å. Maximum number of
nucleus to a distance of a0 from the nucleus. Report spectral lines that can be observed for these transitions
your answer in single digit ignoring any fraction are ____
involved . (Given: ln 0.14 = –2 )
150. Total number of isoelectronic species among the
143. The maximum number of 4f electrons having spin following is _______.
quantum number –1/2 is ____ . [2010]
N3−, Fe3+, Al3+, Mg2+, Ca2+, Zn2+, F−, Be, Na+, Ne
144. What is the difference in the angular momentum of an
electron present in 2p and that present in 4p orbital? 151. How many electrons are present in Si atom corre-
sponding to l = 1 ?
145. Find out the number of waves made by a Bohr electron
in one complete revolution in its 3rd orbit? 152. An ion Mna+ has the magnetic moment equal to 4.9
B.M. Find the value of a
146. Calculate the number of nodal planes in the dxy orbital.

Previous Years' Questions

153. Energy of H-atom in the ground state is –3.6 eV, 157. The de Broglie wavelength of a tennins ball of mass
hence energy in the second excited state is [2002] 60 g moving with a velocity of 10 metres per second
(a) –6.8 eV (b) –3.4eV is approximately [2003]
(c) –1.51 eV (d) –4.53 eV (Planck constant h = 6.63 × 10–31 Js)
(a) 10–33 m (b) 10–31m
154. Uncertainty in position of a particle of 25 g in space (c) 10–16 m (d) 10–25 m
is 10–5 m. Hence uncertainty in velocity (ms–1) is
(Planck constant h = 6.6 × 10–34 Js) [2002] 158. The orbital angular momentum for an electron re
(a) 2.1 × 10 –28
(b) 2.1 × 10 –34 volving in an orbit is given by ℓ /(l + 1) h/2π. This
(c) 0.5 × 10–34 (d) 5.0 × 10–24 momentum for an s electron will be given by [2003]
(a) + ½.h/2 π
155. Which of the following ions has the maximum (b) zero
magnetic moment? [2002] (c) h/2 π
(a) Mn2+ (b) Fe2+ (d) √2.h/2 π
(c) Ti2+ (d) Cr2+
159. Which one of the following grouping represents a
156. In Bohr series of lines of hydrogen spectrum, the third collection of isoelectronic species? (At. numbers
line from the red end corresponds to which one of the Cs-55, Br-35) [2003]
following inter-orbit jumps of the electron for Bohr (a) Na+, Ca2+, Mg2+
orbits in an atom of hydrogen? [2003] (b) N3–, F–, Na+
(a) 3 2 (b) 5 2 (c) Be, Al3+, Cl–
(c) 4 1 (d) 2 5 (d) Ca2+, Cs+, Br
 Atomic Structure 4.29

160. The number of d electrons retained in Fe2+ (At. number 167. Of the following sets which one does not contain iso
of Fe = 26) ions is [2003] electronic species? [2005]
(a) 3 (b) 4 (a) PO43–, SO42–, ClO4– (b) CN–, N2, C22–
(c) 5 (d) 6 (c) SO32–, CO32–, NO3– (d) BO33–, CO32–, NO3–
161. Which of the following sets of quantum numbers is 168. According to Bohr theory, the angular momentum of
correct for an electron in 4f orbital? [2004] an electron in 5th orbit is [2006]
(a) n = 4, l = 3, m = +4, s = + ½ (a) 25h/π (b) 1.0 h/π
(b) n = 4, l = 4, m = –4, s = –½ (c) 10 h/π (d) 2.5 h/π
(c) n = 4, l = 3, m = + l, s = + ½
(d) n = 3, l = 2, m = –2, s = + ½ 169. Which one of the following sets of ions represents a
collection of isoelectronic species? [2006]
162. Consider the ground state of Cr atom (Z = 24). The (a) K+, Cl–, Ca2+, Sc3+ (b) Ba2+, Sr2+, K+, Ca2+
numbers of electrons with the azimuthal quantum (c) N3–, O2–, F–, S2– (d) Li+, Na+, Mg2+ Ca2+
numbers, l =1 and 2 are, respectively [2004]
(a) 12 and 4 (b) 12 and 5 170. Which of the following sets of quantum numbers
(c) 16 and 4 (d) 16 and 5 represents the highest energy of an atom? [2007]
(a) n = 3, l = 2, m= l,s = + 1/2
163. The wavelength of the radiation emitted, when in a
(b) n = 4, l = 0, m = 0, s = +1/2
hydrogen atom electron falls from infinity to station
(c) n = 3, l = 0, m = 0, s = + 1/2
ary state 1, would be (Rydberg constant = 1.097 × 107
(d) n = 3, l = l,m= l,s = + 1/2
m–1) [2004]
(a) 91nm (b) 192nm 171. Which one of the following constitutes a group of the
(c) 406nm (d) 9.1 × 10–8 nm isoelectronic species? [2008]
(a) C2 , O2 , CO, NO
2– –

164. Which one of the following sets of ions represents the (b) NO+, C22–, CN–, N2
collection of isoelectronic species? [2004] (c) CN–, N2, O22–, C22–
(a) K+ Ca , Sc , Cl
2+ 3+ –
(b) Na , Ca , Sc3+, F–
+ 2+
(d) N2, O2–, NO+, CO
(c) K , Cl , Mg , Sc
+ – 2+ 3+
(d) Na+ Mg2+, Al3+, Cl–
172. In an atom, an electron is moving with a speed of
165. In a multielectron atom, which of the following or- 600 m/s with an accuracy of 0.005%. Certainity with
bitals described by the three quantum numbers will which the position of the electron can be located is
have the same energy in the absence of magnetic field (h = 6.6 × 10–34 kg m2 s–1, mass of electron, em = 9.1 ×
and electric fields? [2005] 10–31 kg): [2009]
(a) n= l, l = 0, m = 0 (a) 5.10 × 10 m
–3
(b) 1.92 × 10 m
–3

(b) n = 2, l = 0, m = 0 (c) 3.84 × 10–3 m (d) 1.52 × 10–3 m

(c) n = 3, l = l,m=l
(d) n = 3, l =2, m=l 173. Calculate the wavelength (in monometer) associated
(e) n = 3, l = 2, m = 0 with a proton moving at 1.0 × 103 ms–1 (Mass of proton
(a) b and c (b) d and e = 1.67 × 10–27 kg and h = 6.63 × 10–34 Js): [2009]
(c) c and d (d) a and b (a) 0.40 nm (b) 2.5 nm
(c) 14.0 nm (d) 0.032 nm
166. Which of the following statements in relation to the
hydrogen atom is correct? [2005] 174. Ionization energy of. He+ is 19.6 × 10–18 J atom–1. The
energy of the first stationary state (n = 1) of Li2+ is
(a) 3s and 3p orbitals are of lower energy than 3d
[2010]
orbital
(b) 3p orbital is lower in energy than 3d orbital (a) 4.41 × 10 J atom
–16 –1

(c) 3s orbital is lower in energy than 3p orbital (b) –4.41 × 10–17 J atom–1
(d) 3s, 3p and 3d orbitals all have the same energy (c) –2.2 × 10–15 J atom–1
(d) 8.82 × 10–17 J atom–1
4.30 Chapter 4

175. The energy required to break one mole of C1 – C1 (a) 6.500 × 10–7 m (b) 8.500 × 10–7 m
bonds in C12 is 242 kJ mol–1. the longest wavelength (c) 1.214 × 10–7 m (d) 2.816 × 10–7 m
of light capable of breaking a single C1 – C1 bond is
179. The correct set of four quantum numbers for the
(c = 3 × 108 ms–1 and NA = 6.02 × 1023 mol–1 [2010]
valence electrons of rubidium atom (Z = 37) is:[2014]
(a) 594 nm (b) 640 nm
(c) 700 nm (d) 494 nm 1 1
(a) 5, 1, 1, (b) 5, 0, 1,
2 2
176. A gas adsorbs a photon of 355 nm and emits at two
1 1
wavelengths. If one of the emissions is at 680 nm, the (c) 5, 0, 0, (d) 5, 1, 0,
other is at: [2011] 2 2
(a) 743 nm (b) 376 nm 180. Which of the following is the energy of a possible
(c) 453 nm (d) 581 nm excited state of hydrogen? [2015]

177. The electrons identified by quantum numbers n and l (a) +13.6 eV (b) –6.8 eV
[2012]
(c) –3.4 eV (d) +6.8 eV
(1) n = 4, l = 0
(2) n = 4, l = 1 181. A stream of electrons from a heated filament was
(3) n = 3, l = 1 passed between two charged plates kept at a potential
(4) n = 3, l = 2 difference V esu. If e and m are charge and mass of an
can be placed in order of increasing energy as electron, respectively, then the value of h/λ (where λ is
(a) 4 < 2 < 3 < 1 (b) 2 < 4 < 1 < 3 wavelength associated with electron wave) is given by:
(c) 1 < 3 < 2 < 4 (d) 3 < 4 < 2 < 1 [2016]
178. Energy of an electron is given by, [2013] (a) 2meV (b) meV
 Z2 
E = –2.178 × 10–18  2  (c) 2meV (d) meV
n 
Wavelength of light required to excite an electron in
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)

ANSWER KEYS
Single Option Correct Type
1. (c) 2. (a) 3. (d) 4. (b) 5. (d) 6. (c) 7. (c) 8. (b) 9. (c)
10. (d) 11. (b) 12. (c) 13. (d) 14. (b) 15. (d) 16. (a) 17. (c) 18. (a)
19. (d) 20. (c) 21. (a) 22. (b) 23. (c) 24. (d) 25. (a) 26. (b) 27. (a)
28. (d) 29. (b) 30. (b) 31. (b) 32. (a) 33. (a) 34. (b) 35. (a) 36. (a)
37. (b) 38. (c) 39. (c) 40. (b) 41. (a) 42. (d) 43. (d) 44. (b) 45. (a)
46. (b) 47. (d) 48. (a) 49. (b) 50. (a) 51. (a) 52. (b) 53. (b) 54. (c)
55. (c) 56. (b) 57. (c) 58. (a) 59. (c) 60. (c) 61. (d) 62. (a) 63. (a)
64. (d) 65. (c) 66. (b) 67. (c) 68. (c) 69. (b) 70. (c) 71. (d) 72. (a)
73. (d) 74. (c) 75. (c) 76. (b) 77. (d) 78. (c) 79. (c) 80. (a) 81. (a)
82. (b) 83. (c) 84. (a) 85. (c) 86. (d) 87. (a) 88. (a) 89. (c) 90. (b)
91. (c) 92. (d) 93. (b) 94. (a) 95. (a) 96. (b) 97. (c) 98. (a) 99. (d)
100. (b) 101. (c) 102. (a) 103. (d) 104. (a) 105. (a) 106. (a) 107. (d) 108. (b)
109. (c) 110. (b) 111. (a) 112. (b) 113. (d) 114. (a) 115. (d) 116. (c) 117. (d)
118 (a)
 Atomic Structure 4.31

More than One Option Correct Type

119. (c) and (d) 120. (b), (c) and (d) 121. (b), (c) and (d) 122. (b), and (d)
123. (c) and (d) 124. (a), (b) and (c) 125. (a) and (d) 126. (a), (b) and (d)
127. (b), and (c) 128. (b) and (d) 129. (a), (b), (c) and (d)

Passage Based Questions

130. (a) 131. (b) 132. (d) 133. (b) 134. (d) 135. (c)

Match the Column Type

136. (c) 137. (b)
138. a → (s); b → (r); c → (q); d → (p, t) 139. a → (r, t); b → (p, r, s); c → (p, q, t); d → (q)
140. a → (t); b → (q, s); c → (r); d → (p)

Integer Type
141. (5) 142. (7) 143. (7) 144. (0) 145. (3) 146. (2) 147. (6) 148. (6) 149. (6)
150. (6) 151. (8) 152. (3)

Previous Years' Questions

153. (c) 154. (a) 155. (a) 156. (b) 157. (a) 158. (b) 159. (b) 160. (d) 161. (c) 162. (b)
163. (a) 164. (a) 165. (b) 166. (d) 167. (c) 168. (d) 169. (a) 170. (a) 171. (b) 172. (b)
173. (a) 174. (b) 175. (d) 176. (a) 177. (a) 178. (c) 179. (c) 180. (c) 181. (c)
4.32 Chapter 4

HINTS AND SOLUTIONS

Single Option Correct Type

4. Both Mn+2 and Fe3+ have 5 un-paired electrons. 3 ×108
_______
58. v = c/λ = 8 × 1015 = 37.5 × 10–9 m
5. As Sc3+ has no unpaired electron so it is colour less. = 37.5 nm ≈ 4 × 101 nm
12. All have 14 electrons. 59. Cs+ : 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6
14. As rn α n2. So r2 = 4 r1 No. of electrons in s orbitals = 5 × 2 = 10
nhe No. of electrons in p orbitals = 4 × 6 = 24
15. Power (P) = No. of electrons in d orbitals = 10 × 2 = 20
λ
63. As Z has 13 electrons, Y has 9 electrons and X has 8 electrons
nhe 10 20 6.62 × 10 −34 × 3 × 108 in M shell.
λ= =
p 4 × 10 3 64. As circumference = nλ = 4λ
= 4.965 × 10–9 m = 49.65 A° 65. As they have 5, 3, 2, 1 number of unpaired electrons
respectively.
16. As halogens are most electronegative so the configu-
66. It is Mn2+ having five unpaired electrons so its magnetic
ration is ns2 np5.
moment is
20. As both have 14 electrons. µ = √5 (5 + 2) = 5.9 B.M.
24. As 24Cr = 2, 8, 13, 1 i.e., M shell has 13 electrons. 67. As it has only one unpaired electron so magnetic
moment is
25. As n = 1.
√l (l + 2) = 1.73 B.M.
30. Both Fe3+ and Mn2+ have [Ar] 3d5 configuration.
68. ∆v = h/4π m × ∆x
n2 0.53
__ × I2
_______
31. rn = 0.53 × Z = 3
= 0.17 Å 6.626 x 10–34
________________________
= 4 x 3.14 x 9.1 x 10–31 x 0.1 x 10–10
32. (Z = 35) : 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
No. of electron in all the p orbitals = 5.8 × 106 ms–1
= 6 × 2 + 5 = 17 69. E1/E2 = λ2/λ1 = 6000/3000 = 2 : 1
36. As it has no unpaired electrons. 70. As En ∞ 1/n2
37. As values of m is from –1 to +1 including zero. 71. Use the relation; λ = h/mv
Z
__ 1
__
39. As Ni2+, Ti3+ has 2, 1 unpaired electrons respectively so both 73. vn = 2.188 × 106 × n = 2.188 × 106 × 2
are coloured. = 1.094 × 10 ms
6 –1

41. It represent the configuration of Cu+.

74. Use the relation ∆E = hc/λ
43. These represent two quantum mechanical spin states which
75. As maximum number of electrons in any orbit, sub-orbit or
have no classical analogues.
orbital is decided by Pauli’s law.
n(n – 1) 4(4 − 1) 6.626 × 10–34
___________
49. No. of lines = = =6 78. λ = h/mv = 200 × 10–3 × 5
2 2
= 6.626 ×_________
10–32
50. 24
Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5 81. As mvr = √ 2l(l + 1) h
The 19th e– is in 4s1
1 Here l = 2 so mvr = 6 –h
hence n, ℓ, m, s are 4,0, respectively. 82. Here l = 0 so mvr = 0.
2
h 84. Both A and B have the valencies 3
55. Angular momentom = n as 2.5 is not an intiger so So, the formula is AB.
2π
h Energy nhc
2.5 is not possible. 85. Power = =
2π Time λ×t

56. E = hc/λ =
6.626 × 10–27 × 3 × 106
________________ n × 6.626 × 10 −34 × 3 × 108
2000 × 10–8 600 =
331.3 × 10 −9 × 1
= 9.94 × 10–12 ergs
 Atomic Structure 4.33

0.1
___
600 × 331.3 × 10 −9 ∆ x = 100 × 10–4 cm = 10–7 cm
⇒ n= = 10 × 10 21
1
___ 6.626 × 10–27
___________
6.626 × 10 −34 × 3 × 108 ∆v = 4 π × 6 × 10–13 × 10–7 cm s–1
86. The shortest wavelength in hydrogen spectrum of Lyman 1
__ 10–7
___
= 4 π × 1.1 × 10–7 cm s–1 = 4 π cm s–1
series cab be given : as follows
105. n1= 1 , n2 = 4
1 RH RH 109678 Now 1/ λ = RH [l/n12 – 1/n22] = 1.1 × 10–7 [l/l2 – l/42]
= = =
λ n
2
1
2
1 After solving
λ = 96.9 nm.
⇒ λ = 9.117 × 10 −6 cm
107. I.E. of He+ = E × 22 (as Z for He = 2)
I.E. of Li2+ = E × 32 (as Z for Li = 3)
= 911.7 × 10 −10 m = 911.7 Å.
I.E. (He+) __
_______ 4
Hence, =
87. It is the 1s level, the ground state, where the H-atom can only I.E. (Li2+) 9
9
__
absorb a photon and go to higher excited states. Therefore, I.E. (Li2+) = × I.E. (He+)
4
9
__
88. Rb has the configuration, 1s2 2s2 2p2 3s2 3p6 3d10 4s2 4p6 5s1 ; = × 19.6 × 10–18 = 4.41 × 10–17 J atom–1
4
so n = 5, l = 0, m = 0 and s = ½
108. ∆E = mc2.
90. I.E. of He+ = 13.6 eV × Z2 For Lymann series, m1c2 α (l/l2 – 1/22)
For Balmer series, m2c2 α (1/22 – 1/32)
= 13.6 eV × 4 = 54.4 eV m1/m2 = 3 × 36/4 × 5
m, : m2 = 27 : 5
91. Mass of positively charged ions in positive rays is more than
mass of electrons. 109. Energy of electrons striking the anti-cathode

92. No. of unpaired electrons in Ni2+ is two. = 50000 × 1.6 × 10–19 J

= 8.0 × 10–15 J
Total spin = ± ½ × No. of unpaired electrons
c
__ 6.626 × 10–34 × 3 × 108
________________
hλ= λ
93. s-subshell should be filled first as it possesses lower energy 19.88 × 10
−26

level than p-subshell. = J

λ
95. Li2+ ion has shortest wavelength. 19.88 × 10–26
__________
λ= 8 × 10–15
m = 2.485 × 10–11 m

100. Radius of the 5th orbit = 52r0 = 25 r0 = 0.2485 Å.

Circumference = 2 π (25 r0) = 50 πr0 = 5 λ, 110. As ∆E3 – 2 = –1312[(1/n22) – (1/n12)
= –1312 (1/9 – 1/4)
n λ.= 2π rn
–1312 × –5
________
λ = (10 π) rn = 36
h
______ Similarly,
101. λ =
√ 2mE ∆E4 – 3 = –1312 (1/16 – 1/9)
λE½ = constant. –1312 × –7
________
=
So λ1 √E1 = λ2 √E2 16 × 9
∆E3 – 2 __
_____ 20
= 7
λl/ λ1 = √(E2/E1) = 2 ∆E4 – 3

Therefore, E2/E1 = 4 111. As 13.6 eV is needed for ionization, 20.4 eV (13.6 × 1.5)
must have been absorbed. Of this, 6.8 eV is converted to
102. λ = h/√2m E kinetic energy.
6.626 × 10–34
__________ h
_________
= _________ = 6.626 × 10–34 m λ=
√ 2 × 1 × 0.5 √(2 m K.E.)
6.626 × 10–34 Js
_____________________________
103. ∆p. ∆x = h / 2π =
√(2 × 9.1 × 10–31 × 6.8 × 1.6 × 10–19 J)
m. ∆v. ∆x = h/2π
1
___ h
_____ = 4.70 × 10–10 m = 4.70 Å
∆ v = 4 π × m. ∆x
112. rn = r1 × n2
m = 6 × 10–13 g.
r3 = 32a = 9a
4.34 Chapter 4

3h
___
mvr3 = n = 4 (N – shell)
2π
3h
______ h
____
Number of electrons = 2n2 = 2 × 42 = 32
mv = = 116. Frequency = 880 kc/sec
2 π . 9a 6 πa
h
___ h.6 π a
_____ = 880 × 103 cycles/sec
λ = mv = = 6 π a.
h h = 6.626 × 10–34Js
113. For shortest λ of Lyman series of H n2 = ∝ hυ = [6.626 × 10–34] × 880 × 103 J
1
___ 1 ___
__ 1
= RH I2 – ∝2 = 583.1 × 10–30 J
λL
For longest λ of Balmer series of He+ n2 = 3 Power transmitted = 1000 watts = 1000 J/s
Number of photons emitted per sec
1
___ 1 __
__ 1
λB
= Z2 RH 22 – 32 1000
________
= 583 × 10–30 = 1.72 × 1030
λ
___ 1_____
× 36
So, λ B = 5 × 4 117. As mass of one electron = 9.108 × 10–31 kg So, 1 kg of
A
electrons = 1/9.108 × 10–31
Hence, λB = 9 λA /5 = 9a/5. 1031
_______________
= 9.108 × 6.022 × 1023
mol
6.92
____
114. r = 2 = 8.46 Å 10
__________
31–23
108
___________
rn = r1 . n2 = 9.108 × 6.022
mol = 9.108 × 6.022
mol
r__
n 8.46 Å
______
n2 = r = = 16
1 0.529 Å

More than One Option Correct Type

119. For n = 4, the value of l may be 0, 1, 2, and 3. For ‘d’ eletrons In Fe3+ ion all the five 3d orbitals are half filled while they are
l = 2. The value of may be ±2, ±1 or 0. The spin quantum not in Fe2+. So. Fe3+ is more stable than Fe2+.
number of electron is. For s orbital l = 0. Hence angular momentum
120. Cr3+ 1s2 2s2 2p6 3s2 3p6 3d3.
3d1xy 3d1xz 3d1yz has lower energy h h
=
2π
( )
l l +1 =
2π
0 ( 0 + 1) = 0
124. Number of nodes = n − 1. Number of maxima = n
i.e., one more than the number of nodes. and not one.
For ‘2s’ orbital, the number of maxima = 2 129. For one electron system energy of electron depends only on
Also, 3d z does not have any spherical node.
2
principal quantum number while for many electron system it
126. Energy order, n = 3 < n = 4 depends on value of (n +1)
l =0 < l =1 < l = 2 24th electron enters in 3d orbital. Hence, its principal quan-
127. For a 4p electron, the correct quantum numbers are n = 4 tum number is 3.
1 1
l = 1, m = − 1, 0, +1 and s = + or −
2 2

Passage Based Questions

h
130. λ =
6.625 × 10 34
−
mv
h
131. λ = =
−34
mv 1 × 10 −3 × v
6.625 × 10
= meter = 6.625 × 10–33m
−31 6
9.11 × 10 × 10
6.625 × 10 −34 1
6.625 v= ms −
= × 10 −9 meter 1 × 10 −3 × 6.625 × 10 −33
9.11 34
= 0.727 × 10–9 metre 6.625 × 10 − 1
= = 100ms −
= 0.727 nm 6.625 × 10 −36
h
132. For particle A, λA =
m A .v A
 Atomic Structure 4.35

h 1×1×1 1
For particle B, λB =
mB vB
= 1× ( 0.2 × 0.2 ) =
0.16
λB h m v 100
= × A A λB = = 6.26 Å
λA mBvB h 16
So, de Broglie wavelength of B = 6.25 Å
 mA   vA  135. n ( n + 2 ) = 5.92
λB = λA 
 m B   v B  n(n + 2) = 35
n = 5, Mn2+ contains 5 unpaired electrons.
mA
= 1×
0.20 m A

Match The Column Type

136. As Cr3+ Fe2+ Ni2+, Mn2+ have 3, 4. 2, 5 unpaired electron respectively.

Integer Type
ν h
141. v = 7.312 × 1014 s−1 → υ = = 2437200 m−1 λ= [by de-Broglie’s equation]
c mv
υ in cm−1 = 24372 cm−1 2π r × mv
No. of waves =
For Ist excited state n = 2 h

1 1  nh
24372 = 109677  − 2  mvr =
2π
 4 n2 
n2 = 6, i.e., 5th excited state nh
mv =
142. dv = 1.0 pm3 2π r
P ∝ ψ2 dv , where ψ2 α e(
−2γ /a 0 )
2π r nh
No. of waves = × =n
At nucleus, r = 0 h 2π r
Pr = 0 ∝ e0. (1 pm)3 = 1(pm)3 For 3rd orbit n = 3.
At a distance r = a0, 147. Fe(26) = 3d6 4s2
Pγ = a 0 ∝ e–2 (1.0 pm3) = 0.14 × 1 pm3 Fe2+(24 e) = 3d6 4s0
No. of electrons in 3d orbital in Fe2+ ion = 6
Pr = 0 1
= = 7.1 = 7 148. Six different lines
Pγ = a o
0.14
1 1 1 
= 109678 × 1  − 2 
143. Total number of electrons in f shell = 14 970.6 × 10 −8
 1 n2 
Number of electrons having spin quantum number
−6
–1/2 is 7. 9.1176 × 10 1 1
= 1− ; = 0.0606
970.6 × 10 −8
n 22 n 22
⇀

n2 = 4
144. Zero, because angular momentum of an electron
( 4 − 1)( 4 )
h Number of lines = =6
=
2π
( )
1 1 + 1 for 2p and 4p, the value of 1 is same, i.e., 2
h 2π r
one. 149. λ = =
mv n
145. Number of waves in an orbit = circumference of orbit per
n1 = 5 and n2 = 2
unit wavelength
Number of spectral lines = 6
2πr 151. Electronic configuration of Si is 1s2 2s2 2p6 3s2 3p2
λ
4.36 Chapter 4

Thus, electronic configuration of Mna+ having 4 unpaired electron

152. Magnetic moment = n ( n + 2 ) where n is no. of unpaired
electron 25
Mn3+ 1s2, 2s2, 2p6, 3s2 3p6, 3d4

4.9 = n ( n + 2 ) or n = 4

Previous Years’ Questions

1
__ 1
___
153. n1 = 1, n2 = ∝ = 1.097 × 107 12 – ∝2
1
__ 1
___ 1
___ 1
________
= RH 2 – 2 λ = 1.097 × 107 m = 9.11 × 10–8 m
λ n1 n2
= 91.1 × 10–9 m
1
__ 1 1
λ
= 1.09678 × 107 2 − 2 = 91.1 nm. (1 nm = 10–9 m)
1 ∝
λ = 9.11 × 10–8 m 164. As these have 18 electrons.
E = hv = h × c/λ
165. Orbitals having same (n + l) value in the absence of electric
(c = 3 × 108 m sec–1) and magnetic field will have same energy.
6.6256 × 10–34 × 108
______________
= 9.11 × 10–8
= 2.18 × 10–18 J 166. They do not have same energy as they have different n +
= 2.18 × 10–21 kj l values and for hydrogen the energy order of orbital is
13.6
____ 1 s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f.
En = n2 ev
For second excited state n = 3, 167. Number of electron in SO32– =16 + 8 × 3 + 2 = 42
No. of e– in CO = 6 + 8 × 3 + 2 = 32
–3

13.6
____ 2

E3 = – 9 = –1.51 eV No. of e– in NO = 7 + 8 × 3 + 1 = 32
–

h
_____
3

154. ∆x. ∆v ≥ π These are not isoelectronic species as number of electrons

4 m
155. Here, Mn2+ has 5 unpaired electrons so it has maximum are not same.
magnetic moment.
168. As mvr = nh/2π = 5h/2 π = 2.5h/π
156. The lines at the red end suggest Balmer series. These are
obtained for the jumps n = 2 from n = 3 and second line from 169. As all of these have 18 electrons.
n = 4 and third line from n = 5, that is, 5 2.
170. NO+, C2–2
, CN– and N2 all are isoelectronic as all have four-
157. λ = h/mv teen electrons.
6.626 × 10–34
__________
λ = 60 × 10–3 × 10 = 10–33 m (nearly) h
171. ∆x ⋅ m ⋅ ∆v =
4π
158. As for s orbital, l = 0 h
∆x =
159. As N–3, F– and Na+ has 10 electrons. 4π m∆v
0.005
161. Any sub-orbit is represented as nl such that n is the principle ∆v = 600 × = 0.03
quantum number (in the form of values) and l is the azi- 100
muthal quantum number (its name). 6.626 × 10 −34
∆x =
Value of l < n, l 0 1 2 3 4 4 × 3.14 × 9.1 × 10 −31 × 0.03
−3
s p d f g = 1.92 × 10 m
value of m: – l, .0, + l
value of s: + ½ or – ½ h 6.63 × 10 −34
172. Ż = =
thus for 4f: n = 4, l = 3, m = any value between –3 to + 3. mv 1.67 × 10 −27 × 10 3
= 0.40 nm
162. E.C of Cr (Z = 24) is 1s2 2s2 2p6 3s2 3p6 3d5 4s1 so electrons
173. Ionization energy of He+ = E∞ – E1 = 0 – E1
with l = 1 (p), are 12 with l = 2 (d), are 5
E1 (He+) = –19.6 × 10–18 J atm-1
1
__ 1
___ 1
___
163. λ = vH = RH n 2 – n 2
1 2
 Atomic Structure 4.37

kZ 2 hc
En = 176. E 2 − E1 = ∞
N 2
Ż
− k × 22  1 6.6 × 10 −34 × 3 × 108
−18
−19.6 × 10 = +2.178 × 10 −8 1 − =
12  4 Ż
K= 4.9 × 10 −18 6.6 × 4
= × 10 −8
−18 2.178
4.9 × 10 ×9
E1 (Li 2 + ) = − 2 = 12.12 × 10 −8
1
= – 44.1 × 10–18 J atom–1 = 1.212 × 10 −7 m

= – 4.41 × 10–17 J atom–1 h

181. λ =
mv
242 × 10 3 hc
174. E = = h
6.023 × 10 23 Ż =
2m(KE)
6.626 × 10 −34 × 3 × 108
= J molecule h
Ż ∴ = 2meV
λ
6.626 × 3 × 6.023 × 10 −3
Ż=
242 × 10 3
= 0.4947 × 10 −6 m
Ż = 494.7 mm.

1 1 1 1 1 1
175. = + ; = +
Ż1 Ż1 Ż 2 355 680 Ż2
Ż 2 = 743 nm.