1 - SM - Atomic Structure (1-37) Cbs

Chapter
1 ATOMIC STRUCTURE
 Spectrum types of spectrum and Hydrogen spectrum
 Bohr’s model of an atom
 Radius, energy and velocity derivations
 De-Broglie equation
 Heisenberg uncertainty principle
 Quantum numbers
 Concept of orbital’s.
 Rules for filling of electrons in various orbitals.
 Electronic configuration
 SPECTRUM AND TYPES OF SPECTRA

Spectrum: It is the impression produced on a screen when radiations of particular
wavelengths are analysed through a prism or diffraction grating.
or
It is the image recorded when radiant energy is passed through a prism or grating. When
white light is passed through a prism it splits into seven different colors. This process is
called dispersion
These dispersed lines are arranged on a photographic plate according to increasing order
of their wavelengths or decreasing order of their frequencies is called a spectrum.
Spectrometer is the device used to record the spectrum.
Emission Spectrum: It is the spectrum of a radiation emitted by a substance in its excited

state.
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Substance is excited by –
(i) heating substances on a flame (or)
(ii) passing electric discharge through gases at low pressure (or)
(iii) passing electric current discharge through a thin filament of a high melting point metal.
V I B GY O R
VIBGYOR
Photographic Plate
Continuous spectrum
This spectrum consists of a limited no. of lines, each of which corresponds to a different ‘λ’
of light.
In this spectrum, violet merges into blue, blue in green, green into yellow and so on. i.e.
the spectrum is rainbow of colours (without a gap between them). i.e. It is continuous. This
type of spectrum is known as continuous spectrum.
VIBGYOR
Discontinuous spectrum
Line emission spectrum:
A discontinuous emission spectrum consisting of distinct and well defined lines with
dark areas in between is called line spectrum.
• It is also called as atomic spectrum as it is the characteristics of atoms.
Sodium Dark space

Vapour Bright lines
5890 A° 5896 A°
• Inert gases, metal vapours, non-metals in atomic state give line spectrum
• Each element has a unique emission line spectrum.
• The characteristic lines in atomic spectra can be used in chemical analysis to
identify the unknown atoms (as finger prints are used to identify people)
• Robert Bunsen was one of the first investigators to use line spectra to identify
elements.
Corporate Office: ICES House, 29–A, Kalu Sarai, Sarvapriya Vihar, New Delhi–16; Ph: 26515949, 26865182, 26569493, Fax: 26513942
FWS/SM/IX/CHE/ VOL-1/AS-3
• Thus, Cs, Rb, Tl, In, Ga & Sc were discovered when their minerals were
analysed by spectroscopic methods i.e by using their characteristic line spectra.
• Helium was discovered in the sun by spectroscopic method.
Band emission spectrum

Emission spectrum consisting of a series of very closely spaced lines is called band
spectrum.
• It is the characteristic of molecules
• It is due to vibrations and rotations of atoms present in a molecule.
• It is given by hot metals and molecular non-metals
Absorption spectrum: It is the spectrum produced by absorption of radiation.

• It contains dark lines on bright background.
• It corresponds to radiation absorbed in exciting an electron from lower to higher
levels.
• When white light is passed through unexcited atomic hydrogen and then through
slit and prism, the transmitted light is lacking in intensity at the same
wavelengths as are emitted in emission spectrum.
White light Dark line in the
V I BGYO R yellow region of
continuous
spectrum
NaCl Solution
Production of absorption spectrum
Sodium Bright background space

Vapour Dark lines
5890 A° 5896 A°
(a) Atomic emission. The light emitted by a sample of excited hydrogen atoms (or any
other element) can be passed through a prism and separated into certain discrete
wavelength. Thus an emission spectrum, which is a photographic recording of the
separated wavelengths, is called as line spectrum. Any sample of reasonable size
contains an enormous number of atoms. Although a single atom can be in only one
excited state at a time, the collection of atoms contains all possible excited states. The
light emitted as these atoms fall to lower energy states is responsible for the spectrum.
(b) Atomic absorption. When white light is passed through unexcited atomic hydrogen
and then through a slit and prism, the transmitted light is lacking in intensity at the same
wavelengths as are emitted in (a) the recorded absorption spectrum, is also a line
spectrum and the photographic negative of the emission spectrum.
Differences between Absorption spectrum and Emission spectrum

Absorption spectrum Emission spectrum
• It is produced by absorption of • It is produced by emission of radiation.

radiation. • It gives bright lines (coloured) on the
• It gives dark lines on a bright dark background
background • It corresponds to the radiation emitted
• It corresponds to the radiation absorbed when an excited electron returns back
in exciting an election from lower to the to the ground state.
higher energy levels. • It may be continuous or discontinuous.
• It is discontinuous.
Differences between Line spectrum and Band spectrum

Line spectrum Band spectrum
• It has sharp, distinct, well defined • It has many closed lines.

lines. • It is the characteristic of molecules.
• It is the characteristic of atoms. • It is also called as molecular
• It is also called as atomic spectrum. spectrum.
• It is due to transition of elections in an • It is due to vibrations and rotations of
atom. atoms in a molecule.
• It is given by inert gases, metal • It is given by hot metals and molecular
vapours and atomized non-metals non-metals.
Atomic Spectra of Hydrogen
(a) Hydrogen atom is simplest and contains only one electron. Due to monoelectronic
nature, in it only a few electronic transitions are possible and that is why it gives a
simple line spectra which is simplest to analyze. Each line of spectrum
characterizes a particular electronic transition.
(b) The groups of spectral lines observed in atomic spectra of hydrogen are given
specific names after their discoverer. Hydrogen spectrum is discontinuous line
spectrum.
There groups of spectral lines observed in atomic spectra of hydrogen are given
specific names after their discoverer.
There are six series which are as
(i) Lyman series (ii) Balmer series
(ii) Paschen series (iv) Brackett series
(v) Pfund series (vi) Humphery series
(c) These series lie in three regions of electromagnetic spectrum

(i) UV region - Lyman series
(ii) Visible region - Balmer series
(iii) IR region - Paschen, Brackett,
Pfund & Humphery series
(d) The wavelength of a spectral line is calculated by the following equation which
was theoretically derived by Rydberg.
1 1 1
= v = RH z 2  2 − 2 
λ  n1 n2 
Here,
λ = Wavelength (in cm), v = wave number ( incm−1 )
(
R H = Rydberg cons tan t 109677 cm −1 or 1.097 × 107 m −1 )
n1 = Orbit of lower energy
n2 = Orbit of the higher energy
z = Atomic number of element
Note:
1. For the first time, Balmer related wavelengths of different spectral lines lying in
Balmer region by using following relation.
1 1 1
v= = 109678  2 − 2  , n > 2 ( an int eger )
λ 2 n 
2. Although H-atom has only one electron, yet its spectrum consists of several lines. A
sample of H2 contains infinite number of molecules. On passing electric discharge
through H2 gas, molecules are dissociated into atoms. The electron of each H-atom is
excited to higher energy level. The life period of excited state is very low
(10−6 to 10−8 sec ) and therefore, electrons revert back to lower energy level and emit
out radiant energy falling into well-defined series.
(e) Important facts about different spectral series are summarized below.
Table Spectral line in H-spectrum

Name of series Wavelength n1 n2 Region
(Wave length range)
1) Lyman series 1 1 1 1 n>1 UV region
= Ru  2 − 2 
λ 1 n  1000A 0 − 3000A 0
2) Balmer series 1 1 1 2 n>2 Visible region
= RH  3 −
λ 2 n2  3800A 0 − 7000A 0
3) Paschen series 1 1 1 3 n>3 Near IR region
= RH  2 − 2
λ 3 n  7000A 0 − 10000A 0
4) Brackett series 1 1 1 4 n>4 Mid IR region
= RH  2 − 2
λ 4 n 
5) Pfund series 1 1 1 5 n>5 far IR region
= RH  2 − 2
λ 5 n 
6) Humphery series 1 1 1 6 n>6 far-far IR region
= RH  2 − 2
λ 6 n 
Note:
1. First spectral line in H-atom spectrum was observed by Balmer.
2. Spectral lines in hydrogen spectrum can be divided into
α (I line ) ,β (II liner ) , γ (III line ) , δ etc. for Hα line n2 = n1 + 1, for Hβ line n2 = n1 + 2
Hγ line n2 = n1 + 3 , for Hδ line n2 = n1 + 4
1
=0
In any series, for limiting line
n22
3. Ratio of wave lengths for mth and nth lines of a spectral series.
A) for Lyman Series:
1 1 1 
= RH  2 − 2

λm  1 ( m + 1) 
1 1 1 
= RH  2 − 2

λn 1 ( n + 1) 
2
λm  m + 1  ( n + 1) − 1 
2
=  
λn  n + 1   ( m + 1)2 − 1
 
B) Balmer Series:
1 1 1 
= RH  2 − 2

λm  2 (m + 1) 
1 1 1 
= RH  2 − 2

λn  2 ( n + 1) 
2
λm  m + 2   (n + 2 ) − 4 
2
=  
λn  n + 2   ( m + 2 )2 − 4 
 
4. For maximum energy and minimum wavelength of a spectral line n2 = ∞
5. For minimum energy and maximum wavelength n2 = n1 + 1
6. Number of fine spectral lines when an electron jumps from n2 to n1 =
 (n2 − n1 ) =  ( ∆n)
7. Number of spectral lines when an Electron jumps from Higher Energy level to the
n ( n − 1)
Ground level is
2
8. No. of spectral lines when an Electron jumps from two different energy levels is
N= 2
( n − n1 )(n2 − n1 + 1)
2
The energy corresponding to one of the lines in the Paschen series for H-atom
is 18.16 × 10−20 J . Find the orbit number for the transition which produced this line.
E = hc ν
E
ν=
hc
18.16 × 10 −20 J
ν= = 913710m−1
6.625 × 10 −34 J.s × 3 × 108 m.s−1
1  1 1
ν= = Rz 2  2 − 2 
λ  n1 n2 
 1 1 1
913710m−1 = 1.097 × 107 × 12  2 − 2   2 = 0.028  n2 = 6
 3 n2  n2
 BOHR’S ATOMIC MODEL

Bohr developed a model for hydrogen atom and hydrogen like one–electron species
(hydrogenic species – H, He+, Li2+, Be+3). He applied quantum theory in considering the
energy of an electron bound to the nucleus.
Important postulates
 An atom consists of a dense nucleus

situated at the centre with the electron
revolving around it in circular orbits
without emitting any energy. The force
of attraction between the nucleus and
an electron is equal to the centrifugal
force of the moving electron.
 Electron can revolve only in that orbit in which its angular momentum (mvr) is an
h
integral multiple of i.e, angular momentum is quantised. Thus
2π
h
Bohr’s equation is mvr = n (n is a whole number).
2π
 As long as an electron is revolving in an
orbit it neither loses nor gains energy.
Hence these orbits are called stationary
states.Each stationary state is associated
with a definite amount of energy and it is
also known as energy levels. The
greater the distance of the energy level
from the nucleus, the more is the energy
associated with it. The different energy
levels are numbered as 1,2,3,4, (from
nucleus onwards) or K, L, M, N etc.
 Ordinarily an electron continues to move in a particular stationary state without losing

energy. Such a stable state of the atom is called ground state or normal state.
 If energy is supplied to an electron, it may jump (excite) instantaneously from lower

energy (say 1) to higher energy level (say 2, 3, 4, etc.) by absorbing one or more
quanta of energy. This new state of electron is called as excited state. The quantum of
energy absorbed is equal to the difference in energies of the two concerned levels.
Since the excited state is less stable, electron will lose its energy and come back to the
ground state.
Energy absorbed or released in an electron jump, (∆E) is given by

∆E = E2 – E1 = h υ
Where E2 and E1 are the energies of the electron in the first and second energy
levels, and ν is the frequency of radiation absorbed or emitted.
Note: If the energy supplied to hydrogen atom is less than 13.6 ev, it will accept or absorb
only those quanta which can take it to a certain higher energy level i.e., all those photons
having energy less than or more than a particular energy level will not be absorbed by
hydrogen atom. But if energy supplied to hydrogen atom is more than 13.6 ev then all
photons are absorbed and excess energy appears as kinetic energy of emitted photo
electron
 RADIUS 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 Coulomb’s Law, the electrostatic force of attraction between the moving electron
KZe 2
and nucleus is Coulombic force = 2
r
1
K= (where ε 0 is permitivity of free space)
4πε0
K = 9 × 109 Nm 2 C –2
In C.G.S. units, value of K = 1 dyne cm2 (esu) –2
mv 2
The centrifugal force acting on the electron is
r
Since the electrostatic force balance the centrifugal force, for the stable electron
orbit.
mv2 KZe2
= 2 … (i)
r r
KZe 2
(or) v 2 = … (ii)
mr
According to Bohr’s postulate of angular momentum quantization, we have

nh
mvr =
2π
nh
v=
2πmr
n 2h 2
v2 = … (iii)
4π2 m 2 r 2
Equating (2) and (3)
KZe 2 n 2h 2
= 2 2 2
mr 4π m r
n2h2
Solving for r we get r =
4π2 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 .
n2h2 12 × (6.626 ×10 –34 )2

r0 = 2 2
= 2 –31 –19 2 9
= 5.29 ×10 –11 m
4π me K 4 × (3.14) × 9 ×10 × (1.6 ×10 ) × 9 ×10
r0 = 0.529Å
Radius of nth orbit for an atom with atomic number Z is simply written as
n2
rn = 0.529 × Å
Z
(i) If Z is a constant, then

r ∝ n2
Thus the radius of atom goes on increasing as the number(n) of energy levels in the
atom goes on increasing as shown below
r1 n12
=
r2 n22
(ii) If n is a constant, then

1
r∝
z
r1 z 2
=
r2 z1
Energy of orbit:
• The energies are negative since the energy of the electron in the atom is less than
the energy of a free electron (i.e., the electron is at infinite distance from the
nucleus) which is taken as zero. The lowest energy level of the atom corresponds to
n=1, and as the quantum number increases, E becomes less negative.
• When n = ∞, E = 0, which corresponds to an ionized atom i.e., the electron and
nucleus are infinitely separated.
H → H+ + e– (ionisation).
• Stability will increase as the electron in an atom moves from infinity distance to a
distance ‘r’ from the nucleus, resulting in the value of potential energy becoming
negative. This is because of the fact that when two opposite charges attract each
KZe 2
other, there is a decrease in the potential energy, as attractive forces =
r2
• Potential energy of electron is negative while kinetic energy is positive.
• Total energy is negative and the negative value shows that attractive forces are
working between electron and nucleus. Therefore, work is to be done to remove the
electron from this equilibrium state.
• Energies are of two types:
Potential energy (EP): This is produced due to electrostatic forces of attraction
between electron and proton. Its value is negative.
If Z is the atomic number, e is the charge and r is the radius, then
− KZe 2
Potential energy =
r
Kinetic energy (EK): This is produced due to the velocity of electron.
If m is the mass, v is the velocity and r is the radius, then
1 2 1 KZe2
Kinetic energy of the electron = mv =
2 2 r
KE decreases, PE increases as we move away from the nucleus
• Total energy (ET):

Total energy = Potential energy + Kinetic energy
ET = EP + EK
− KZe 2 1 KZe2
ET = +
r 2 r
2
1 KZe
ET = −
2 r
EP = 2ET
EK = − ET
Calculation of Energy of an orbit:

The total energy, E of the electron is the sum of kinetic energy and potential energy.
1
Kinetic energy of the electron = mv2
2
− KZe 2
Potential energy =
r
1 K Ze 2
Total energy = mv2 – … (4)
2 r
From equation (1) we know that
mv 2 KZe2
= 2
r r
1 KZe2
∴ mv2 =
2 2r
Substituting this in equation (4)
KZe2 KZe2 KZe2
Total energy (E) = – = −
2r r 2r
Substituting for r, gives us
2π2mZ2e4K 2
E=-
n2h2
Where, n = 1, 2, 3……….
This expression shows that only certain energies are allowed to the electron.
Since this energy expression consists of so many fundamental constants, we are giving
you the following simplified expressions.
Z2 1erg = 10–7J
–12
E = –21.8 ×10 × erg per atom
n2 1erg = 6.2419 × 1011 eV
1eV = 23.06 kcal/mol
Z2 1eV = 1.602 ×10–12 erg

= –21.8 ×10–19 × J per atom
n2 1eV = 1.602 ×10–19J
Z2 1 cal = 4.184 J
= –13.6 × eV per atom
2
n 1 mol = 6.022 × 10 23
2
Z
= –313.6 × kcal / mole
n2
z2
= −1312 × kJ / mole
n2

1
E∝ 2
n
Therefore the energy of electron goes on increasing as the number of shells

increases.
E1 n22
−= 2
E2 n1
E ∝ −Z2
E1 Z12
−= 2
E2 Z2
Quantization of electronic energy levels

Separation Excitation
Quantum State Energy
Energy Energy
n=∝ 0 0 13.6
n=5 –13.6/52 = –0.54 0.54 13.05

n=4 –13.6/42 = –0.85 0.85 12.75
nd 2
n=3 2 Excited State –13.6/3 = 1.51 1.51 12.1
n=2 1st Excited State –13.6/22 = –3.4 3.4 10.2
Ground State –13.6 eV 13.6 eV 0 eV

n=1
Electronic energy levels of hydrogen atom
Total Energy increases as we more away from the nucleus .

Ground state
An atom in its lowest energy state or initial state is said to be in ground state. This is the
most stable state of an atom.
Excited State
The states of higher energy than the ground state are said to be in excited state. For
example, the electron of hydrogen atom in ground state is present in n = 1 shell.
(a) Electron in n = 2 shell is in first excited state
(b) Electron in n = 3 shell is in second excited state
(c) Electron in n = 4 shell is in third excited state
This means that the energy of n + 1 shell is in first excited state, of n + 2 shell in second
excited state and of n + 3 shell in third excited state, where n = the energy in ground state.
Excitation Potential
• The energy required to excite an electron from ground sate to any excited state is
known as excitation potential.
• Excitation potential has a positive value. For example,
First excitation potential of hydrogen atom = E2 − E1
Second excitation potential of hydrogen atom = E3 − E1
Third excitation potential of hydrogen atom = E4 − E1
Ionization Energy or Ionization Potential

The energy required to remove an electron from the outermost orbit of a gaseous atom in
ground state is called ionization energy or ionization potential. Its value is positive.
Separation Energy
The energy required to separate an electron from any excitation state of an atom is known
as separation energy.
For example, the first separation energy, i.e. the energy required to remove an electron
from the first excited state in hydrogen is + 3.4 eV.
Velocity of electron of Bohr’s orbit
We know that,
centrifugal force on electron = force of attraction between electron and nucleus
mv 2 KZe2
=
r r2 ……(1)
According to Bohr’s postulate of angular momentum quantization, we have
mvr = nh
2π ……(2)
Dividing equation (1) with (2),

2πKZe2
v=
nh
Here π, K, e and h are constants. Substituting their values in the above equation, we have
Z
v= × 2.188×108 cm s−1
n
1
v∝
n
Therefore, velocity goes on decreasing with increase in the number of shells.
Thus,
v 1 n2
=
v 2 n1

v∝Z
Therefore, velocity goes on increasing with increase in the atomic number.

Thus,
v1 Z1
=
v 2 Z2
Time period:
Circumference
Time period(T) =
Velocity
2πr
=
v
2π × n2h2 nh n3h3
× = 2 2 4
4π2mZe2 2πZe2 4π mZ e
n3
T= ×1.5×10-16 s
2
Z
Orbital frequency:
It is the number of revolutions per second made by an electron.
1
Orbital frequency =
T
Velocity
=
Circumference
v
=
2πr
2πZe2 4π2mZe2 4π2mZ2e4
= × =
nh × 2π n2h2 n3h3
Z2
orbital frequencey= 3
× 6.66 × 1015 s −1
n
Drawbacks of Bohr’s Theory
(i) It failed to explain spectra of atoms having more than one electron.
(ii) It failed to explain Zeeman effect which is splitting of spectral lines in the presence
of magnetic field.
(iii) It failed to explain stark effect which is splitting of spectral lines in the presence of
external electrostatic field.
(iv) Although Bohr’s theory predicted with great accuracy the positions of spectral lines
of hydrogen atom and the singly ionized helium atom but refined spectroscopic
analysis has shown that these lines are not simple but have fine structure, i.e., they
consist of a number of component lines lying close together.
(v) It is difficult to find the effect of other electrons upon the energy state of any
particular electron.
(vi) The pictorial concept of electrons jumping from one orbit to another orbit is not
justified because of the uncertainty of their positions and velocities.
(vii) The main objection against Bohr theory is that it involves the use of two theories
which are essentially opposed to each other, the quantum theory involved to
account for existence of stationary orbits and for frequencies of the radiation while
motion of electrons in its orbit obeys the laws of classical mechanics.
(viii) It cannot explain the shapes of molecules formed by the combination of atoms.
(ix) No justification was provided for the principle of quantization of angular momentum,
h 2h 3h 1.5h 1.25
so why angular momentum is , , …etc. and why it can not be , etc
2π 2π 2π 2 π 2π
is explained here.
Dual Character (Particle and Wave Character of Matter and Radiation):

Although Bohr’s theory predicted with great accuracy the positions of spectral lines of
hydrogen atom and the singly ionized helium atom, shells, radius and energy of obit. But
refined spectroscopic analysis has shown that these lines are not simple but have fine
structure, i.e., they consist of a number of component lines lying close together. It is
difficult to find the effect of other electrons upon the energy state of any particular electron.
He fails to explain the quantum mechanical model of atom. In case of light some
phenomenon like diffraction and interference can be explained on the basis of its wave
character. However, the certain other phenomenon such as black body radiation and
photoelectric effect can be explained only on the basis of its particle nature. Thus, light is
said to have a dual character. Such studies on light were made by Einstein in 1905.
Louis de Broglie, in 1924 extended the idea of photons to material particles such as
electron and he proposed that matter also has a dual character-as wave and as particle.
Derivation of de-Broglie Equation

The wavelength of the wave associated with any material particle was calculated by
analogy with photon.
In case of photon, if it is assumed to have wave character, its energy is given by
E = hν ------------------ (i) (according to the Planck’s quantum theory)
Where ν the frequency of the wave and ‘h’ is is Planck’s constant
If the photon is supposed to have particle character, its energy is given by
E = mc2 ------------------ (ii) (according to Einstein’s equation)
Where ‘m’ is the mass of photon, ‘c’ is the velocity of light.
By equating (i) and (ii)
hν = mc2
But ν = c/λ
c
h = mc2
λ
(or) λ = h /mc
The above equation is applicable to material particle if the mass and velocity of photon is
replaced by the mass and velocity of material particle. Thus for any material particle like
electron.
h
λ = h/mv (or) λ=
p
Where mv = p is the momentum of the particle.
It may be mentioned here that wavelength of the de-Broglie wave can also be related to
the kinetic energy(E) of the particle
1
E = mv 2
2
1 2 2
mE = m v
2
mv = 2mE
Substituting this value of mv in de-Broglie equation we get
h
λ=
2mE
In case, a charged particle carrying charge Q coulomb is accelerated by applying a

potential difference of V volt then the kinetic energy of the particle is given by relation
E = Q × V joule
h h 12.3
λ= = =
2mE 2mQV V
The waves associated with material particles or objects in motion are called matter waves
or de-Broglie waves. These waves are distinctively different from the electromagnetic
waves.
DISTINCTION BETWEEN ELECTROMAGNETIC WAVES AND MATTER WAVES

Electromagnetic waves Matter waves
1. These waves are associated with electric 1. These waves are not associated with
and magnetic fields. electric and magnetic field
2. Electromagnetic waves can be emitted or 2. Matter waves are neither radiated into
radiated through the space space nor emitted by the particles. These
are simply associated with the particles.
3. All electromagnetic waves travel with the 3. Matter waves travel with the different
same velocity. velocities.
4. The velocity of all electromagnetic waves is 4. The velocity of matter waves are
equal to that of light. different from that of light.
5. The wavelength of electromagnetic waves 5. The wave length of matter waves is
is given by given by
c h h h
λ= = λ= =
ν mc mv p
Bohr’s theory versus de Broglie equation:
Bohr assumed electron as a particle and postulated that it can revolve only in that orbit in
h
which it s angular momentum (mνr) is an integral multiple of . Thus Bohr’s equation is
2π
h
mνr = n (n is a whole number). According to de Broglie, an electron behaves as a
2π
standing or stationary wave which extends round the nucleus in a circular orbit.
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. That means there is constructive interference of
electron waves and the electron motion has a character of standing wave or non-energy
radiating motion. This is shown in the following figure (a). Always it is a necessary
condition to get an electron-wave in phase such that the circumference of the Bohr’s orbit
(= 2πr) is equal to the whole number multiple of the wavelength (λ) of the electron-wave.
(a) (b)
nλ = 2πr
2πr
λ = Where n is a whole number.
n
h
According to de Broglie’s theory λ =
mν
On comparing the two equations given above we can write
2πr h
=
n mν
h
or mνr = n.
2π
This is Bohr’s equation which stipulates that angular momentum of an electron moving
h
round the nucleus is an integral multiple of . In other words, de Broglie’s theory and
2π
Bohr’s theory are in agreement with each other. In case the circumference of the Bohr’s
orbit (2πr) is bigger or smaller than nλ, the electron-wave is said to be out to phase as
shown in the above figure (b). Then destructive interference of waves occurs causing
radiation of energy. Such an orbit cannot possibly exist.
 HEISENBERG’S UNCERTAINTY PRINCIPLE

All moving objects that we see around us e.g., a car, a ball thrown in the air etc., move
along definite paths. Hence their position and velocity can be measured accurately at any
instant of time. Is it possible for subatomic particle also?
As a consequence of dual nature of matter, Heisenberg, in 1927 gave a principle about the
uncertainties in simultaneous measurement of position and momentum (mass × velocity)
of small particles.
This principle states “It is impossible to measure simultaneously the position and
momentum of a small microscopic moving particle with absolute accuracy or certainty” i.e.,
if an attempt is made to measure any one of these two quantities with higher accuracy, the
other becomes less accurate.
The product of the uncertainty in position (∆x) and the uncertainty in the momentum (∆p =
m. ∆v where m is the mass of the particle and ∆v is the uncertainty in velocity) is equal to
or greater than h/4π where h is the Planck’s constant.
Thus, the mathematical expression for the Heisenberg’s uncertainty principle is simply
written as
h
∆x ×∆P ≥
4π
But momentum (P) = mass(M) × velocity(V)
∆ P = m ∆V
Then
h
∆x × m∆V ≥
4π
h
∆x × ∆V ≥
4π m
Explanation of Heisenberg’s 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 is disturbed. The accuracy with which
the position of the particle can be measured depends upon the wavelength of the light
used. The uncertainty in position is ±λ. The shorter the wavelength, the greater is the
accuracy. But shorter wavelength means higher frequency and hence higher energy. This
high energy photon on striking the electron changes its speed as well as direction. But this
is not true for macroscopic moving particle. Hence
Heisenberg’s uncertainty principle is not applicable to macroscopic particles.
Exercise-3:
1. Find the momentum of a particle whose de-Broglie wavelength is 12 pm.
2. Describe de Broglie’s theory of electron and give the need for such a theory. Obtain
the relevant equation. How is this theory an improvement over Bohr’s theory?
3. The wavelength associated with a proton is equal to the wavelength associated
with an electron. Find the relationship between the velocities of both the
microscopic particles.
Mass of proton = 1.6726 x 10-24 g
Mass of electron = 9.11 x 10-31 kg.
4. Write briefly about Heisenberg’s uncertainity principle.
5. The uncertainty in the position of a moving bullet of mass 0.02 kg is 5.0 × 106m.
Calculate the uncertaintyin its velocity.
6. Find the uncertainty in the position of a microscopic body if uncertainty in its velocity
is i) 0.005 % ii) Zero
Given that mass of electron = 9.11× 10 −31kg and velocity of electron = 300 m/s.
7. An aircraft moving at a speed of 200 m/sec has a de-Broglie wavelength of 5 × 10–4.
Calculate the mass of the aircraft.
8. Find de-Broglie wave length of an electron that has been accelerated by a potential
difference of 1 kv ?
9. Describe de Broglie’s theory of electron and give the need for such a theory.
Obtain the relevant equation. How is this theory an improvement over Bohr’s
theory.
10. Find the uncertainty in the position of an electron, if uncertainty in its velocity
is 5 × 10 5 m / s ? h = 6.626 x 10-34 J.s, mass of electron = 9.11 x 10-31 kg
QUANTUM NUMBERS:
An atom contains large number of shells and subshells. These are distinguished from one
another on the basis of their size, shape and orientation (direction) in space. The
parameters are expressed in terms of different numbers called quantum numbers.
Quantum numbers may be defined as a set of four numbers with the help of which we can
get complete information about all the electrons in an atom. It tells us the address of the
electron i.e., location, energy, the type of orbital occupied and orientation of that orbital.
Note: only 3 quantum numbers are obtained from schrodinger wave equation
1. Principal quantum number (n):

 It is given by Niels Bohr.
 It accounts for the formation of line spectrum in the H – atom.
 It indicates the main shell or energy level or orbit in which the electron resides,
which are designated as K, L, M, N…etc from the nucleus.
 It gives the information about the;
• approximate distance of the electron from the nucleus in an atom
• size or radius of orbit or shell(as n increases size of orbit also increases)
• energy of an electron (as n increases energy also increases)
• velocity of an electron (as n increases velocity decreases)
 It also tells the maximum number of electrons a shell can accommodate, which
is given by 2n2, where n is the principal quantum number. This is Bohr-Bury
rule.
Shell K L M N O
Principal quantum number (n) 1 2 3 4 5
Maximum number of electrons 2 8 18 32 50
Note: 1. Outer most shell is called as valence shell

2. Last but one shell is called as penultimate shell
2. Azimuthal quantum number or angular momentum quantum number or orbital

Quantum number or subsidiary quantum number ( l ):
 It was proposed by sommerfeld and denoted by “ l ”
 It determines the number of subshells or sublevels to which the electron
belongs.
 It tells about the shape of subshells.
 “ l ” can have any value from 0, 1,2 to (n—1) for each value of n

Value of 0 1 2 3
“l”
Name of s p d f
subshell
Shape of Spherical Dumbbell Double Complex
subshell dumbbell
h
 It represent the orbital angular momentum, which is equal to l ( l + 1)
2π
 The number of orbitals in any suborbit is determined by the expression 2 l + 1
and the number of electrons is determined by the expression 2(2 l + 1).
Number of sub
Designation Total no. of
‘n’ ‘ l ’ (= 0 to n–1) Symbol shells in a given
of sub shell electrons in ‘n’
orbit i.e. ‘n’
1 0 s One 1s 2
0 s Two 2s 2
2 =8
1 p 2p 6
0 s Three 3s 2 

3 1 p 3p 6  18
2 d 3d 10 
0 s Four 4s 2 
1 p 4p 6 
4  32
2 d 4d 10 
3 f 4f 14 
In the above table the letters s, p, d and f are named as sharp, principal, diffuse and
fundamental respectively.
n=1 n=2 n=3 n=4
K L M N
s sp s pd s pd f
3. The magnetic quantum number (m or ml ):
 The magnetic quantum number was introduced by Lande.
 According to lande, the presence of more lines in the spectrum in a magnetic
field in an electric field indicates that the energy levels are further subdivided
by the field and an additional quantum number called magnetic quantum
number, m is required to specify these energy sub-levels.
 This quantum number explains about the splitting of spectral lines in
presence of magnetic field (Zeeman effect) or in presence of an electric field
(stark effet)
 It determines the number of preferred orientations of the electron (orbitals)
present in a subshell.
 The value of m varies from − l to + l through zero.
 For a given value of “ l ” the total value of ‘m’ is equal to ( 2l + 1)
• For s sub-shell, l = 0. Thus, m = 2 × 0 + 1 = 1

∴s sub-shell consists of only one orbital called s orbital with m = 0.
• For p sub-shell, l = 1. Thus, m = 2 × 1 + 1 = 3

∴p sub-shell consists of three orbitals called px, py and pz orbitals with
m = -1, +1, 0.
• For d sub-shell, l = 2. Thus, m = 2 × 2 + 1 = 5
∴d sub-shell consists of five orbitals called dxy, dyz, dz2, dxz and
dx2−y2orbitals with m = -2, -1, 0, +1, +2.
 The total number of orbitals present in an energy level is determined by the

formula n2 where n is principal quantum number.
l Name of sub shell ‘m’ values (orbitals) Name of orbitals

0 s – sub shell 0 (one) s – orbital
−1 p x orbital
 
1 p – sub shell +1 ( three ) p y orbital p − orbitals
0  
p2 orbital 
+2  dxy
−1 dyz

2 d – sub shell +1 ( five ) dzx
−2  dx2-y2

0  d z2
−3 
−2 
−1 

3 f – sub shell 0  ( seven )
+1 

+2 

+3 
 The set of orbitals present in a given sub shell possess same energies and
hence are called degenerate orbitals. For example: px, py and pZ are degenerate
orbitals.
• The number of degenerate orbitals of s subshell = 0.
• The number of degenerate orbitals of p subshell = 3 (px, py and pZ).

• The number of degenerate orbitals of d subshell = 5 (dxY, dyz, dzx, dz2 , dx2 − y2 , )
 The maximum number of electrons that can be accommodated in an orbital is
not more than2.
 Numbering of electrons in orbitals is shown below.
4 5 6 7 8 9 10
6
1 2 2 1 2 3 4 5
1 2
s – orbital p – orbitals d – orbitals
2 m=–1
1 2
2
m=0
m=1
K L M N
(a)
s sp s pd s pd f
(b)
1 13 1 3 5 13 5 7
Division of sub–stationary states into groups of states in the presence of
(a) No magnetic field (b) Magnetic field
4. The spin quantum number (s or ms ):
 It was proposed by Goudsmit & Uhlenbeck and denoted by the symbol of ‘s’.
 The value of ‘s’ is + ½ & − ½, Which is signified the spin or rotation or direction of
electron on it’s axis during the movement.
 The spin may be clockwise & anticlockwise.
h
 It represents the value of spin angular momentum is equal to s ( s + 1) .
2π
 Maximum spin of an atom = ½ x number of unpaired electron.
 Total spin = (2s+1)
QUESTIONS ON QUANTUM NUMBERS

1. The maximum number of atomic orbitals associated with a principal quantum
number 5 is
(A) 9 (B) 12 (C) 16 (D) 25
Sol: The number of orbitals in a principle shell is n2 = 52 = 25.
2. Beryllium’s fourth electron will have the four quantum numbers:

n l m s n l m s
(A) 1 0 0 1/2 (B) 1 1 1 1/2
(C) 2 0 0 −1/2 (D) 2 1 0 +1/2
Sol. It is 2s2 Ans: C
3. To give designation to an orbital, we need

(A) Principal and azimuthal quantum number
(B) Principal and magnetic quantum number
(C) Azimuthal and magnetic quantum number
(D) Principal, azimuthal and magnetic quantum numbers. Ans: D
4. If n = 3, l = 0 and m = 0, then atomic number is

(A) 12 or 13 (B) 13 or 14 (C) 10 or 11 (D) 11 or 12
Ans: D
5. The values of 4 quantum numbers of valence electron of an element are n = 4,
1
l = 0, m = 0 and s = + the element is
2
(A) K (B) Ti (C) Na (D) Sc
Ans: A
Exercise-4:
1. Explain spin quantum number
2. Write a note on (a) Principal quantum number and (b) Azimuthal quantum number
3. Find the total number of electrons having the following quantum numbers ?
1
a) n=4, l = 0 b) n=5 , ms = +
2
Ans: 25
4. What are quantum numbers? Name the various quantum numbers. Explain their
significance
 CONCEPT OF ATOMIC ORBITALS

As we have studied that each in the previous section we learnt that each stationary state is
split into sub–stationary states. These sub–stationary states are the regions in space
where the electron is revolving around the nucleus. These states are referred to as “atomic
orbitals”. Thus the atomic orbital is defined as the region in space where there is a finite
probability of finding the electron. In the previous section, we discussed atomic orbitals
such as s,p,d,f etc., present in each shell (K,L,M,N….) we now discuss the shapes of
these atomic orbitals. It should be noted that the atomic orbital is plotted by drawing the
boundaries of the region where the electron is likely to move around the nucleus.
Shapes and Size of Orbitals

An orbital is the region of space around the nucleus within which the probability of finding
an electron of given energy is maximum (90–95%). The shape of this region (electron
cloud) gives the shape of the orbital. It is basically determined by the azimuthal quantum
number l, while the orientation of orbital depends on the magnetic quantum number (m).
Differences between orbit and orbital
Orbit Orbital
1. Orbit is a well defined circular path 1. It represents the region in space
around the nucleus in which an around the nucleus in which the
electron revolves. probability of finding the electron is
maximum.
2. It represents the planar motion of an 2. It represents the three-dimensional

electron. motion of an electron around the
nucleus.
3. It gives a definite path of an electron 3. It does not specify definite path and
and is not in accordance with the is in accordance with the uncertainty
uncertainty principle. principle. According to this concept,
electron may be anywhere in this
region.
4. All orbits are circular. 4. Orbitals have different shapes.
5. Orbits do not have directional 5. Except s-orbital, all other orbitals

character. have directional characteristics.
6. An orbit can accommodate electrons 6. An orbital cannot accommodate

equal to 2n2. more than two electrons.
Let us now see the shapes of orbitals in the various subshells.
 s–Orbital:
s orbital is spherical as shown in figure . A better way of representing ‘s’ orbital is
shown in figure in the previous section, we learnt the various types of orbitals
present in each shell. They are summarized below.
Shell Types of orbitals present in the shell

K (n=1 s
L (n=2) s and p
M (n=3) s, p and d
N (n=4) s, p, d and f
O (n=5) s, p, d, f and g
The size of the orbital depends upon the value of principal quantum number (n). Greater
the value of n, larger is the size of the orbital. Therefore, 2s–orbital is larger than 1s orbital
but both of them are non-directional and spherically symmetrical in shape.
 p –Orbital:
The p orbitals correspond to l=1. There are no ‘p’ orbitals in K – shell (i.e., 1p does
not exist). The p orbitals are present from n=2 (i.e. L shell) onwards.
The probability of finding the p–electron is maximum in two lobes on the opposite
sides of the nucleus. This gives rise to a dumb–bell shape for the p–orbital. For p–
orbital l = 1. Hence, m = –1, 0, +1. Thus, p–orbital have three different orientations.
These are designated as px, py&pz depending upon whether the density of electron
is maximum along the x y and z axis respectively. The px ,py and pz orbitals are
shown in Figure .
 d-Orbital:
The d orbitals correspond to l=2. these present from M(n=3) shell onwards. A total
of five ‘d’ orbitals are present in each of the shell from n=3 onwards (see Table 1.2).
these five ‘d’ orbitals are designated as dxy, dxz, dyz, d x 2 − y 2 and d z2 . The first three
orbitals viz., dxy, dxz anddyz lie in the xy, yz and zx planes respectively. The orbital
d x 2 − y 2 lies along x–and y–axes. The d z2 orbital lies along z–axis. The orientations of
these orbitals are shown in Figure .
There are two nodal planes in each orbital.
Z X
Y
d z2
d x2 − y2
Dough–nut shape or Baby soother shape Clover leaf shape

X X Y
Y Z Z
dxz dyz
dxy
Similarly f-subshell has 7 orbitals.
Node and nodal plane
i) Node represents the region where probability of finding an electron is zero. Similarly,
nodal plane represents the plane having zero probability of finding electron
ii) Nodes are of two types

a) Radial or Spherical nodes b) Angular nodes or nodal plane
iii) Calculation of number of nodes:

Radial nodes = n-l-1
Angular nodes = l
Total nodes = n-1
Where, n and l are principal and azimuthal quantum numbers.

Example: Number of radial nodes for 3px orbital =1
Number of angular nodes for 3px orbital =1
Total number of nodes for 3px orbital =2
Note: 1. Each p−orbital is separated by 900

2. For Px orbital, zy is the nodal plane
3. For Py orbital, zx is the nodal plane
4. For Pz orbital, xy is the nodal plane
Orbitals Nodal planes

dxy xz, yz
dxz xy, yz
dyz xy, xz
dx 2 − y 2 dxy, zaxis
dz 2 0 (no nodal plane)
Electronic Configuration and Magnetic Properties
 RULES FOR FILLING OF ELECTRONS IN VARIOUS ORBITALS

 Aufbau Principle:
• It is a German word, meaning building up’
• According to this principle, “In the ground state the atomic orbitals are filled
in order of increasing energies”. i.e. in the ground state the electrons
occupy the lowest orbitals available to them.
 ( n + l ) Rule: This rule states that electrons are filled in orbitals according to their
increasing values of (n + l ) . When ( n + l ) is same for sub energy levels, the
electrons first occupy the sublevels with lowest “n” value.
Thus, order of filling up of orbitals is as follows: is < 2s < 2p < 3s < 3p <4s< 3d < 4p
<5s< 4d < 5p < 6s < 4f< 5d.
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d
6s 6p
7s
Example of (n + l ) rule:
Type of Values of (n+
Value of n Values of l Relative energy
orbitals l)
1s 1 0 1+0=1 Lowest energy
Higher energy than
2s 2 0 2+0=2
1s orbital
2p 2 1 2+1=3 2p orbital (n=2) have
lower energy than 3s
3s 3 0 3+0=3
orbital (n=3)
 Pauli’s Exclusion Principle

• According to this principle, “No two electrons in an atom can have all the four
quantum numbers n, l , m and s identical.
• In an atom, any two electrons may have three quantum numbers identical but
fourth quantum number must be different.
• Since this principle excludes certain possible combinations of quantum numbers
for any two electrons in an atom, it was given the name exclusion principle,
• Its results are as follows
(i) The maximum capacity of a main energy shell is equal to 2n2 electron
(ii) The maximum capacity of a subshell is equal to 2(2 l + 1). Electrons
(iii) According to this principle an orbital can accommodate the most two
electrons with their spins opposite to each other.
(iv) It means that an orbital can have 0, 1, or 2 electrons
(low energy) (high energy)

 Hund’s Rule of Maximum Multiplicity:
(a) This rule governs the filling up of degenerate orbitals of the same sub-shell
(b) According to this rule “Electron filling will not take place in orbitals of same
energy until all the available orbital of a given subshell contain one electron
each with parallel spin.”
(c) This implies that electron pairing begins with fourth, sixth and eighth electron
in p. d and f orbitals of the same sub-shell respectively.
(d) The reason behind this rule is related to repulsion between identical charged
electron present in the same orbital
(e) They can minimize the repulsive forces between them selves by occupying
different orbitals.
(f) Moreover, according to this principle, the e − entering the different orbitals of
subshell have parallel spins. This keeps them farther apart and lowers the
energy through electron exchange or resonance.
(g)The term maximum multiplicity means that the total spin of unpaired e − is
maximum in case of correct filling of orbitals as per this rule.
Maximum multiplicity = unpaired e− + 1
 EXTRA STABILITY OF HALF FILLED AND COMPLETELY FILLED ORBITALS

Half-filled and completely filled sub-shells have extra stability due to the following
reasons.
• Symmetry of orbitals
(a) It is a well known fact that symmetry leads to stability.
(b) Thus, if the shifting of an electron from one orbital to another orbital differing
slightly in energy results in the symmetrical electronic configuration. it
becomes more stable
(c) For example p3, d5, f7 configurations are more stable than their near ones
• Exchange Energy
(a) The e − in various subshells can exchange their positions, since e − in the
same subshell have equal energies.
(b) The energy is released during the exchange process with in the same
subshell.
(c) In case of half filled and completely filled orbitals, the exchange energy is
maximum and is greater then the loss of orbital energy due to the transfer of
electron from a higher to a lower sublevel e.g. from 4s to 3d orbitals in case
of Cu and Cr
(d) The greater the number of possible exchanges between the electrons of
parallel spins present in the degenerate orbitals, the higher would be the
amount of energy released and more will be the stability
(e) Let us count the number of exchange that are possible in d4 and d5
configuration among electrons with parallel spins
Note: Increasing order of stability d5 < p3 < d10 < p6
 ELECTRONIC CONFIGURATION OF ELEMENTS
Electronic configuration is the distribution of electrons into different shells, sub

shells and orbital’s of an atom Keeping in view the above mentioned rules.
Electronic configuration of an element is defined as “The systematic

arrangement of electrons into various atomic orbitals according to increasing order
of their energies” is called electronic configuration.
Electronic configuration of any orbital can be simply represented by the notation.
Number of electrons in the

subshell
x
nl
Principal quantum number Symbol of subshell or
orbitals (s,p,d,f)
Alternatively;
Orbital can be represented by a box and an electron with its direction of spin by
arrow. To write the electronic configuration, just we need to know
(i) the atomic number
(ii) the order in which orbitals are to be filled
(iii) maximum number of electrons in a shell, sub–shell or orbital.
a) Each orbital can accommodate two electrons

b) The number of electrons to be accommodated in a subshell is 2 ×No. of
degenerate orbitals.
Sub-shell Maximum number of electrons

s 2
p 6
d 10
f 14
c) The maximum number of electron in each shell (K, L, M, N…) is given by

2n2. Where n is the principal quantum number.
Electronic configurations of elements from 1 to 30

Element Symbol Atomic Number Electronic configuration
Hydrogen H 1 1s1
Helium He 2 1s2
Lithium Li 3 1s2 2s1
Beryllium Be 4 1s2 2s2
Boron B 5 1s2 2s2 2p1
Carbon C 6 1s2 2s2 2p2
Nitrogen N 7 1s2 2s2 2p3
Oxygen O 8 1s2 2s2 2p4
Fluorine F 9 1s2 2s2 2p5
Neon Ne 10 1s2 2s2 2p6
Sodium Na 11 1s2 2s2 2p6 3s1
Magnesium Mg 12 1s2 2s2 2p6 3s2
Aluminium Al 13 1s2 2s2 2p6 3s2 3p1
Silicon Si 14 1s2 2s2 2p6 3s2 3p2
Phosphorus P 15 1s2 2s2 2p6 3s2 3p3
Sulphur S 16 1s2 2s2 2p6 3s2 3p4
Chlorine Cl 17 1s2 2s2 2p6 3s2 3p5
Argon Ar 18 1s2 2s2 2p6 3s2 3p6
Potassium K 19 [Ar] 4s1
Calcium Ca 20 [Ar] 4s2
Scandium Sc 21 [Ar] 4s23d1
Titanium Ti 22 [Ar] 4s2 3d2
Vanadium V 23 [Ar] 4s2 3d3
Chromium Cr 24 [Ar] 4s1 3d5
Manganese Mn 25 [Ar] 4s2 3d5
Iron Fe 26 [Ar] 4s2 3d6
Cobalt Co 27 [Ar] 4s2 3d7
Nickel Ni 28 [Ar] 4s2 3d8
Copper Cu 29 [Ar] 4s1 3d10
Zinc Zn 30 [Ar] 4s2 3d10
Due to greater stability of half-filled and fully-filled orbitals, the configurations d5 ns1 and
d10 ns1 are written in place of d4 ns2 and d9 ns2 respectively.
Explanation:
Cu has 29 electrons. Its expected electronic configuration is 1s22s22p63s23p64s23d9
But a shift of one electron from lower energy 4s orbital to higher energy 3d orbital will
make the distribution of electron symmetrical and hence will impart more stability.
Thus the electronic configuration of Cu is 1s2 2s22p63s23p64s13d10
Fully filled and half filled orbitals are more stable.
 Electron configuration of some important elements
Element Symbol Z Electron configuration

Palladium Pd 46 [Kr ] 4d10 5s0
Gadolinium Gd 64 [ Xe] 4f 7 5d16s2
Dubnium Db 104 [Rn] 5f 14 6d3 7s2
 Configuration of ions:
First of all, the configuration of the atom is written. Then, appropriate number of electrons
is deducted from the outermost shell for the configuration of the cation. Similarly,
appropriate number of electrons is added to the outermost shell for the configuration of the
anion. Eg: Na atom. Electronic configuration = 1s22s2 2p63s1; Electronic configuration of
Na+ = 1s22s22p6.
Fe - [ Ar ] 4s2 3d6 ; Fe3 + − [ Ar ] 3d5 4so
 MAGNETIC PROPERTIES OF ELEMENTS:

• Para magnetism: If in the electronic configuration of an element, any unpaired
electron is present, then it is attracted by external magnetic field. This property is
called paramagnetic.
Eg: Fe+3
• Diamagnetism: If in the electronic configuration of an element, all the electrons
present are paired, then the element will be repelled by external magnetic field.
This property is called diamagnetism.
Eg: Zn+2
• Since the spinning electrons in an orbital, behave as a micro magnet, they have
magnetic moment. When the electrons are paired in any orbital, they cancel the
magnetic moments of each other. But in case of paramagnetic substances, there is a
net magnetic moment. The magnetic moment may be calculated by the formula given
below :
µ = n(n + 2) BM
µ=Magnetic moment
n = number of unpaired electrons.
B.M = Unit of magnetic moment (Bohr magneton)
1 B.M = 9.273 x 10-24 Joule / Tesla
No. of unpaired electrons Magnetic moment (BM)

1 1.73
2 2.82
3 3.87
4 4.89
5 5.91
QUESTIONS ON ELECTRONIC CONFIGURATION

1. For a given value of n (principal quantum number), the energy of different subshells
can be arranged in the order of.
(A) f > d > p > s (B) s > p < d > f (C) f > p > d > s (D) s > f > p > d
Sol. It is the rule Ans. (A)
2. Correct set of four quantum numbers for the outermost electron of rubidium (Z = 37)
is
(A) 5, 0, 0, 1/2 (B) 5, 1, 0, 1/2 (C) 5, 1, 1, 1/2 (D) 6, 0, 0, 1/2
Sol. Its configuration is 5s 1 Ans. (A)
3. The order of increasing energies of the orbitals follows:
(A) 3s, 3p, 4s, 3d, 4p (B) 3s, 3p, 3d, 4s, 4p
(C) 3s, 3p, 4s, 4p, 3d (D) 3s, 3p, 3d, 4p, 4s
Sol. Follow ( n + l ) rule Ans. (A)
4. The total spin resulting from a d7 configuration is

(A) 3/2 (B) 1/2 (C) 2 (D) 1
1 3
Sol. For d7, three unpaired electrons, spin = 3 × =
2 2
Exercise-5:
1. State Hund’s rule. How to arrange three electrons in p orbitals?
2. If the principal quantum number n has a value of 3, what are permitted values of the
quantum numbers ‘l’ and ‘m’?
3. The configuration of potassium (19) is 1s22s22p63s24s1 and not 1s22s22p63s23p63d1.
Why?
4. Find out the number of unpaired electrons in (a) Co2+; (b) Ni2+
Ans: Co+2 is 3 Ni+2 is 2
5. a) Name the orbitals corresponding to given set of quantum numbers
(i) n = 3, l = 2, m = ± 2 (ii) n = 4, l = 0, m = 0
(ii) n = 3, l = 1, m ± 1 (iv) n = 2, l = 1, m = 1
Ans: (i) 3d (ii) 4s (iii) 3p (iv) 2p
Important Points
 Number of sub-shells in the shell = n
 Number of orbitals in the shell = n2
 Number of orbitals in the sub-shell = 2 l + 1
 Number of electrons in the shell = 2n2
 Number of electrons in the sub-shell = 2(2 l + 1)
 Number of electrons in an orbital= 2
 Number of elliptical orbits according to Sommerfeld = n −1
 A part of an atom up to penultimate shell is a kernel or atomic core.
 Number of electrons present in cation = Number of protons – charge on the ion.
 Number of electrons present in anion = Number of protons + charge on the ion.
 Electrons are present in shells except valence shell are called core electrons.
 The last shell of an atom is called ultimate shell or valence shell and is represented
by the symbol ‘n’. For example in sodium, the valence shell is M−shell.
 The last but one shell of an atom is called penultimate shell (n− −1). In chlorine L−shell
is the penultimate shell.
 The shell just before the penultimate shell is called antipenultimate shell.
 Electron(s) that are present in the valence shell are called valence electrons.
 Substances which have same number of electron and atoms called Isosteres.
hc
 E = hν = = hc ν
λ
λ = wave length , E=Energy of Radiation, h=Planck’s constant, 6.625 × 10−34 J.S ( )
C=Velocity of light ( 3 × 108 m / s ) , ν = frequency, ν = wave number,
 Units of wave length ( λ ) is A 0 , 1A 0 = 10 −10 m = 10 −8 cm , 1nm = 10 −9 m
 Units of frequency ( ν ) is sec −1 or Hz, 1M Hz = 106 Hz
 Units of wave member ν is m−1 ()

1 - SM - Atomic Structure (1-37) Cbs

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Chapter

 SPECTRUM AND TYPES OF SPECTRA

Emission Spectrum: It is the spectrum of a radiation emitted by a substance in its excited

Sodium Dark space

Band emission spectrum

Absorption spectrum: It is the spectrum produced by absorption of radiation.

Production of absorption spectrum

Sodium Bright background space

Differences between Absorption spectrum and Emission spectrum

• It is produced by absorption of • It is produced by emission of radiation.

Differences between Line spectrum and Band spectrum

• It has sharp, distinct, well defined • It has many closed lines.

Atomic Spectra of Hydrogen

(c) These series lie in three regions of electromagnetic spectrum

Table Spectral line in H-spectrum

 BOHR’S ATOMIC MODEL

 An atom consists of a dense nucleus

 Ordinarily an electron continues to move in a particular stationary state without losing

 If energy is supplied to an electron, it may jump (excite) instantaneously from lower

Energy absorbed or released in an electron jump, (∆E) is given by

 RADIUS OF HYDROGEN ATOM:

According to Bohr’s postulate of angular momentum quantization, we have

n2h2 12 × (6.626 ×10 –34 )2

(i) If Z is a constant, then

(ii) If n is a constant, then

• Total energy (ET):

Calculation of Energy of an orbit:

Z2 1eV = 1.602 ×10–12 erg

(i) If Z is a constant, then

Therefore the energy of electron goes on increasing as the number of shells

(ii) If n is a constant, then

Quantization of electronic energy levels

n=5 –13.6/52 = –0.54 0.54 13.05

n=2 1st Excited State –13.6/22 = –3.4 3.4 10.2

Ground State –13.6 eV 13.6 eV 0 eV

Electronic energy levels of hydrogen atom

Total Energy increases as we more away from the nucleus .

Ionization Energy or Ionization Potential

Velocity of electron of Bohr’s orbit

Dividing equation (1) with (2),

(ii) If n is a constant, then

Therefore, velocity goes on increasing with increase in the atomic number.

Dual Character (Particle and Wave Character of Matter and Radiation):

Derivation of de-Broglie Equation

In case, a charged particle carrying charge Q coulomb is accelerated by applying a

DISTINCTION BETWEEN ELECTROMAGNETIC WAVES AND MATTER WAVES

Bohr’s theory versus de Broglie equation:

 HEISENBERG’S UNCERTAINTY PRINCIPLE

Explanation of Heisenberg’s uncertainty principle

1. Principal quantum number (n):

Note: 1. Outer most shell is called as valence shell

2. Azimuthal quantum number or angular momentum quantum number or orbital

n=1 n=2 n=3 n=4

 For a given value of “ l ” the total value of ‘m’ is equal to ( 2l + 1)

• For s sub-shell, l = 0. Thus, m = 2 × 0 + 1 = 1

• For p sub-shell, l = 1. Thus, m = 2 × 1 + 1 = 3

 The total number of orbitals present in an energy level is determined by the

l Name of sub shell ‘m’ values (orbitals) Name of orbitals

• The number of degenerate orbitals of p subshell = 3 (px, py and pZ).

 Numbering of electrons in orbitals is shown below.

QUESTIONS ON QUANTUM NUMBERS

2. Beryllium’s fourth electron will have the four quantum numbers: