Atomic Structure
Atomic Structure
SESSION -1
AIM
1) To introduce Fundamental particles
2) To introduce Thomson’s and Rutherford Atomic model
3) To introduce terms like atomic number, mass number and isotopes,
isobars, isotones
John Dalton coined the term atom. The atom is the fundamental
particle of matter and considered to be indivisible and
indestructible.
In fact, the atom as the whole is electrically neutral as number of
protons in it is equal to number of electrons.
The electron, proton and neutron are the main fundamental particles
of an atom.
Discovery of electron – study of Cathode rays:
J.J. Thomson observed that, when a high voltage is applied between
the electrodes fitted in discharge tube,at a very low pressure,some
invisible radiations are emitted from the cathode. At this stage
wall of the discharge tube near cathode starts glowing.
Gas at low Discharge tube
Pressure
Faint green glow
Cathode rays
To vacuum pump
ZnS coating
To vacuum pump
H. V
. Production of anode rays
Origin of anode or positive rays:
In the discharge tube the atoms of gas lose negatively charged
electrons. These atoms, thus, acquire a positive charge. The
positively charged particle produced from hydrogen gas was called
the proton.
H H+(proton)+ e-
Properties of Anode rays:
i) They travel in straight lines. However, their speed is much less
than that of the cathode rays.
ii) They are made up of material particles.
iii) They are positively charged,hence they called as canal rays or
anode rays.’
iv) The nature of anode rays depends on the gas taken in the
discharge tube.
v) For different gases taken in discharge tube the charge to mass
ratio (e/m) of the positive particles constituting the positive rays is
different.
Fundamental particles:
Beam of
particles + Nucleus
i. Most of the -particles passed through the gold foil without any
deflection from their original path.
Bcz atom has largely empty space as most of the -particles
passed through the foil undeflected.
ii. A few of the alpha particles are deflected fairly at large
angles while some are deflected through small angles.
Bcz there is heavy positive charge at the centre of the atom
which causes repulsions.
The entire mass of the atom is concentrated in the nucleus.
iii. A very few -particals are deflected back along their path.
According to Rutherford,
1. Atom is spherical and mostly hollow with a lot of empty space in it.
2. It has a small positively charged part at its centre known as
nucleus.
3. The nucleus is surrounded by electrons. The electrons revolve round
the nucleus with very high speeds in circular paths called orbits.
Symbol of Element
where X is the symbol for the element with superscript A and subscript
Z, both on the left hand side.
Isotopes: The atoms of the same element which have the same atomic
number but different mass numbers are called isotopes.
Exp- 6 C12 , 6 C13 , 6 C14 1 H1, 1H2 , 1H3
They have same number of nucleons. But they are differ chemically
because the chemical characteristics depend upon the number of
electrons which is determined by the atomic number.
Isotones:Isotones are the atoms of different elements which have the
same number of neutrons.
Eg: i. C , N , O (n = 8)
6
14
7
15
8 ii. Si , P , S
16
14
30
15
31
16
32
(n = 16)
SESSION – 2 AND 3
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EDUTECH
ATOMIC STRUCTURE
v) The radiations posses wave character and travel with the velocity
of light i.e. 3x108 m/sec because of the above characteristics, the
radiation are called electromagnetic radiations or waves.
Electromagnetic radiation is explained by following characteristics:
1. Wave length:
The distance between two successive crests, troughs or between any two
consecutive identical points in the same phase of a wave is called wave
length.It is denoted by the letter (lambda).
The wave length is measured in terms of meters (m), centimeters (cm),
angstrom units (A0) nanometers (nm), picometers (pm) and also in
millimicrons (m).
The S.I. unit of wavelength is meter, m
1A0 = 10–10 m or 10–8 cm
1nm = 10–9 m or 10–7 cm = 10A0
1pm = 10–12m or 10–10 cm =10−2 A0
2.Frequency:
The number of waves that pass through a given point in one second is
known as frequency of radiation. It is denoted by the ‘v’(nue).
Crest Crest
a
a
Trough Trough
Wave motion of the radiation
SI unit of frequency is per second(s–1) or Hertz (Hz). A cycle is said
to be completed when a wave consisting of a crest and a trough passes
through a point.
3.Velocity:
Electromagnetic spectrum:
V I B G Y O R
PhotoElectric Effect:
When radiations with certain minimum frequency (ν0 ) strike the surface
of a metal, the electrons are ejected from the surface of the metal.
It is called photoelectric effect,electrons emitted are called
photoelectron.
Incident light
Detector
Metal Surface
Evacuated glass tube
Electrons
− +
− +
Photoelectric effect
For each metal a certain minimum frequency is needed to eject the
electrons called as threshold frequency ( o ) which differs from metal to
metal.
K.E. of photoelectron
o
According to Einstein, E = h
Kinetic energy of photo electron Ek = E - = h − h o
SESSION - 4
Beam
•
VIBGYOR
Slit Prism
Photographic
plate
These colors are so continuous that each of them merges into the next.
Hence, the spectrum is called continuous spectrum.
It may be noted that on passing through the prism, red colour with the
longest wavelength is dedicated least while violet colour with shortest
wavelength is deviated the most.
b. Discontinuous Spectrum:When gases or vapours of a chemical
substance are heated in an electricArc or in a Bunsen flame,
light is emitted. If the ray of this light is passed through a prism,
a line spectrum is produced.
• A discontinuous spectrum consisting of distinct and well defined
lines with dark areas in between is called line spectrum. It is also
called atomic spectrum.
• The emission spectrum consisting of a series of very closely spaced
lines is called bandspectrum.
Band spectrum is the characteristic of molecules. Hence it is also
known as molecular spectrum. The band spectrum is due to vibrations
and rotations of atoms present in a molecule.
defined lines.
2. The line spectrum is 2. The band spectrum is
the characteristic of characteristic of molecules
atoms and is also called and is also called
atomic spectrum. molecularspectrum.
3. The line spectrum is 3. The band spectrum is due
due to transition of to vibrations androtations of
electrons in an atom. atoms in a molecule
rotations of atoms in a
4. The line spectrum is 4. The band spectrum is given
given by inert gases, by hot metals and
metal vapours and molecular nonmetals.
atomised nonmetals.
SESSION – 5 AND 6
AIM-To introduce Bohr’s and Sommerfeld’s Atomic models
To overcome the objections of Rutherford model and to explain the
hydrogen spectrum,Bohr proposed a quantum mechanical model.
POSTULATES OF BOHR’S THEORY
• The electrons revolve round the nucleus with definite velocity in
certain fixed closed circular paths called orbits (or) shells (or)
stationary state. These shells are numbered as 1, 2, 3, 4 or
termed as K, L, M, N from the nucleus.
For the atom to be stable an equal centrifugal force must act away
from the nucleus. This centrifugal force is equal to –mv2/r, where ‘m’
is the mass of electron and ‘r’ is the radius of the orbit.
In a stationary orbit
–Ze2 −mv2 Ze2
r2
= r
or r
= mv2
𝑛ℎ
As per Bohr’s quantum condition, mvr = 2𝜋
nh 𝑛2 ℎ 2
∴v= 2πmror v2= 4𝜋2 𝑚2𝑟2
−Ze2
P.E of electron = 𝑟
Total energy of electron, En = K.E + P.E
2 2 2
En=Ze2r − Zer = − 12 Zer
Substituting the value of r, we get energy of electron in nth orbit,
−Ze2 4π2 mZe2 −2π2 mZ2 e4
En = 2n2 h2
or En= n2h2
Substituting the values of m, e, h and𝜋 in the equation, we get
−13.6 ×𝑍 2
En = 𝑛2
eV per atom
−313.6×𝑍 2
or En = 𝑛2
k cal mol–1
2 –1
or En = −1312×Z
n2
kJ mol
−2.18×10−11 𝑍 2
or En = erg per atom
𝑛2
−2.18×10−18 𝑍 2
orEn = j/atom
𝑛2
2π2 mK2 Z2 e4
In S.I units: En = − n2 h2
1
WhereK = 4𝜋𝜖 and 𝜀𝑜 beingpermittivity of air and is equal to
0
–1
8.854 × 10–12 Farad metre
• Derivation of Rydberg equation:
When a gas is subjected to electric discharge or heated by a flame,
the electrons in the ground state of the atom absorb energy and they
are promoted to higher quantum states. As theyare not stable in
these states, they emit energy and return to ground state or any
other lower energy states.If E2 is the energy of the higher energy
state, E1 is the energy of the lower energy state and 𝜈 is the
frequency of emitted radiation E2 – E1 = h𝜈
If the numbers of the higher and lower energy states are n2 and n1
2 4 1
respectively, En2 = −2πhmZe
2 . 2
n 2
−2π2 mZe4 1
En1 = .
h2 n21
−2π2 mZe4 1 1
En2 − En1 = [ − ]
h2 n21 n22
En2 − En1
But En2 − En1 = hcν̅ and ν̅ =
ch
1 −2π2 mZe4 1 1
ν̅ = = [ − ]
λ ch2 n21 n22
2πZe2
v= cms−1
n
Substituting the values of 𝜋, e and h in the above expression
2.18×108 ×𝑍 –1
vn= cm s
𝑛
Thus the velocity of electron in the first orbit of hydrogen atom is
2.18 ×108 cm s–1. As the number of the orbit increases, the velocity of
the electron decreases.
Explanation of Hydrogen Spectrum by Bohr’s Theory:
Bohr’s theory successfully explains the origin of lines in hydrogen
emission spectrum. Hydrogen atom has only one electron. It is present
in K shell of the atom (n = 1). When hydrogen gas is subjected to
electric discharge, energy is supplied. The molecules absorb energy
and split into atoms. The electrons in different atoms absorb different
amounts of energies. By the absorption of energy the electrons are
excited to different higher energy levels.
Minor axis
n=4,k=4
n=4,k=3
n=4,k=2
• n=4, k=1, k 0
SESSION- 7
AIM
1) To introduce de Broglie’s theory
2) To introduce Heisenberg’s Uncertainty principle.
DUALNATURE OF MATTER(DE BROGLIE’S WAVE THEORY)
Light exhibits different properties such as diffraction, interference,
photoelectric effect, compton effect, reflection and refraction. The
phenomenon of diffraction and interference can be explained by the
wave nature of the light. But the phenomenon of photoelectric effect
and Compton Effect can be explained by the particle nature of the
light.Thus light has dual nature.DeBroglie proposed that matter like
radiation, should also exhibit dual behaviour.
hc
Einstein’s generalization of Planck’s theory is given as, E = hν =
λ
Einstein’s mass energy relationship is E = mc2
Equating above two equations, we get
hc h h
= mc2 or = mc or λ = mc
λ λ
Where ‘c’ is the velocity of light. If the velocity of micro particle is
h
‘v’ then, λ=
mV
ℎ
(Δx) (Δv) ≥
4𝜋𝑚
SESSION –8 AND 9
AIM
1) To introduce wave mechanical model of atom.
2) To introduce Quantum numbers.
3) To understand shapes of orbitals and Probability distribution.
THEORY
Classical mechanics, based on Newton’s laws of motion, was successful in
explaining the motion of macroscopic bodies like falling stones or motion
of planets around the sun etc. But it failed when applied to
microscopic particles like electrons, atoms, molecules etc.Hence new
branch introduced called as ‘Quantum mechanics’.
Schrodinger Wave Equation:
Quantum mechanics, as developed by Erwin Schrodinger is based on the
wave motionassociated with the particles. The Schrodinger differential
wave equation is given by
∂2 ψ ∂2 ψ ∂2 ψ 8π2 m
+ + + (E − V)ψ
∂x2 ∂z2 ∂y2 h2
1 0 (1s)
2 0 (2s), 1 (2p)
• When l =1, m can have 3 values m = –1, 0, +1. The sub-level ‘p’
has three space orientations or three orbitals. The three orbitals
are designated as px, py and pz.
• When l = 2, m can have 5 values m = –2,–1, 0, +1, +2. The sub-
level ‘d’ has five space orientations or five orbitals. The five
orbitals are designated as dxy, dyz, dzx, dx2−y2 and dz2 .
• When l = 3, m can have 7 values m = –3,–2,–1,0,+1,+2,+3. The
sub-level ‘f’ has seven space orientations or seven orbitals.
The magnetic quantum number gives orientation of orbitals in
space. All the orbitals present in a sublevel have same energy
and shape. They are called ‘degenerate orbitals’, which differ in
their spatial orientation.
• Each value of ‘m’ constitutes an orbital in the sublevel.
• Maximum no. of electrons in subshell : 2(2𝑙+1) or (4 𝑙+2).
Atomic Orbital:
The three dimensional space around the nucleus where the probability
of finding the electron is maximum is called an atomic orbital.
Differences between orbit and orbital:
Orbit Orbital
1. n orbit is a well-defined circular 1. An orbital is the region of space
path 1.aroundthe
An orbitalaround
is the the nucleus
region wherearound the
of space
around the nucleus in which the theprobability of finding the
electronrevolves. electron is maximum (95%)
Node- The three dimensional space around the nucleus where the
probability of finding the electron is minimum or zero.
y
z
Nucleus
node
x
(2s)
(1s)
Types of Nodes:
Nodes are of two types: a) Radial Node b) Angular Node
A radial node is the spherical region around then nucleus, where the
probability if finding the electron is zero (Ψ2 = 0).
Similarly,nodal plane(angular plane) have zero probability of finding
electron.
Calculation of no. of nodes:
No. of Radial nodes = n−𝑙 − 1
No. of angular nodes = 𝑙
Total no. of nodes = n-1
Ex: In a 3p -orbital
No. of Radial nodes = 3-1-1 = 1
No. of angular nodes = 1
Total no. of nodes = 2.
Shapes of Orbitals:
• s –Orbitals: s- Orbital can accommodate electrons with l = 0 and
these orbitals are present in every orbit starting from 1st orbit.
SESSION – 10
AIM-To introduce Electronic Configuration
ENERGY OF ORBITALS
The energy of an electron in a hydrogen atom is determined only by
the principal quantum number. Within a shell, all hydrogen orbitals
havethe same energy, independent of the other quantum numbers.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
Although the shapes of 2s and 2p orbitals are different, an electron
has the same energy when it is in 2s orbital or 2p orbital. The
energy of an electron in a multielectron atom depends, not only on its
principal quantum number, but also on its azimuthal quantum number.
The s, p, d and f orbitals within a given shell have slightly different
energies in a multi electron atom.
Electronic configuration of multi electron atoms:
The distribution and arrangement of electrons in the main shells,
subshells and orbitals of an atom is called electronic configuration of
the element.
• Aufbau Principle:
“In the ground state of the atoms, the orbitals are filled in order of
their increasing energies”.
In other words electrons first occupy the lowest energy orbital available
to them and enter into higher energy orbitals only after the lower
energy orbitals are filled.
The relative energy of an orbital is given by
(n +l )rule. As(n+l) value increases, the energy of orbital increases.
• The orbital with the lowest (n + l) value is filled first.
• When two or more orbitals have the same (n +l) value, the one
with the lowest ‘n’ value (or) highest ‘l ’ value is preferred in
filling.
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EDUTECH
ATOMIC STRUCTURE
The two electrons have the same value for n, same value for l and
same value for m but differ in s.
• Hund’s rule of maximum multiplicity:
According to this rule, when electrons are filled in degenerate orbitals
of a subshell, pairing of an electron takes place only when each
orbital of the subshell is filled with one electron each.It can be also
stated that, in ground state of an atom, the configuration which has
more number of unpaired electrons is most stable.
Thus in s, p, d and f subshells, pairing starts from 2nd, 4th, 6th and
8th electrons respectively.
Ex: Electronic configuration of N (7) is 1s2 2s2 2p3.
The electrons in 2p subshell are occupied sing ally. i.e., 1s2 2s2 2𝑝𝑥1 2𝑝𝑦1 2𝑝𝑧1
Stability of atoms
Extra stability is associated with atoms in which degenerate orbitals
are either half-filled or completely filled due to
(1) Symmetrical distribution of electrons