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Structure of atom
Content
• Electrons come out as soon as a beam of light falls on the surface of the metal if the
frequency of incident light is greater than threshold frequency.
hν = hνo + K.E
Concept of Photon:
A particle travelling with the speed of light must be mass less (rest mass, mo = 0) or its effective
mass during motion will be infinite.
mo
m=
1 − v 2 /c 2
Note : Photoelectric effect explains the particles nature of light. But light has both wave and
particles properties i.e. it has dual nature.
Bohr’s Atomic Model:
• Bohr’s model was given in order to remove the drawbacks of Ruther ford’s model. The
main postulate of the Bohr’s theory are:-
i. The electron in the hydrogen atom can move around the nucleus in a circular path of
fixed radius and energy. These paths are called orbits.
ii. As long as electron stays in the same orbit, it does not radiate energy.
The emission or absorption of energy takes place only when the electron jumps from
one energy level to another. This takes place in the form of photons.
∆E = E2 - E1 = hv
iii. The angular momentum of electron in closed cell is quantized.
nh
= mvr
2π
• According to Bohr’s theory of hydrogen atom
I. The stationary states for electron are given as n = 1, 2, 3. these integral numbers are
known as principal quantum numbers.
th
II. Expressions for radius, energy and velocity of electron moving in n orbit of hydrogen
atom (or hydrogen like species).
h2 n2
1. r = n2 2 = 0.529 × Å
4π m(Ze / 4πε0 )
2
Z
1 2π2m(Ze 2 / 4πε 0 )
2
Z2
2. E = − 2 = – 21.8 × 10 –12
× erg per atom
n h2 n2
Z2 Z2
= – 13.6 × 2 eV per atom = – 313.6 × 2 Kcal per mol
n n
2π(Ze2 / 4πε0 ) Z
3. ν = = 2.18 × 108 × cm/sec.
nh n
• The expression of spectral transitions is
1 1
∆E = Z2 Rhhc 2 − 2
n1 n2
where RH, known as Rydberg constant,
2π2m(e 2 / 4 πε0 )
2
RH = 3
= 1.09678 × 10 7 m−1
hc
Hydrogen Spectra
• The emission spectrum of hydrogen was first studied by Bohr in 1914. The situation in
this case being simplified by the fact that the hydrogen atom has only one electron. the
spectrum of hydrogen consists of five sets of discrete lines occurring in the ultra-violet,
visible and infra-red regions of the electromagnetic spectrum. These sets are known as
Lyman series, Balmer series, Paschen series, Brackett series and Pfund series, after the
men who detected them.
• It was also found that the lines in the series were related to one another and could be
represented in a single formula
1 1 1
= RH 2 − 2
λ n m
λ is the corresponding wavelength, RH is a constant (Rydberg constant), n and m are
whole numbers related to the series as follows:
Lyman series n=1 M = 2, 3, 4 …
Balmer series n=2 m = 3, 4, 5 …
Paschen series n=3 m = 4, 5, 6 …
Brackett series n=4 m = 5, 6, 7 …
Pfund series n=5 m = 6, 7, 8 …
• Bohr model failed to
i. Explain the spectra of atom containing more than one electron.
ii. Explain the fine structure in the spectrum of H – atom using high resolution
spectroscopic techniques.
iii. Explain the ability of atoms to form molecules by chemical bonds
• The important discoveries which results in the failure of Bohr model were:
i. Dual behavior of matter i.e., De Broglie’s Equation: According to which electron
has a dual character, both as a material particle and as a wave. Wavelength λ, of
a particle of mass m, moving with velocity V is expressed as
h
λ= (h = Planck’s constant)
mV
ii. Heisenberg uncertainty principle i.e., According to this principle “it is not possible
to determine precisely both the position and the momentum ( or velocity) of a
h
microscopic moving particle”. Mathematical expression is ∆x ×∆p ≥
4π
• In an atom, large numbers of orbital are possible which can be distinguished by size,
shape and their orientation. Each orbitalis defined by three quantum numbers, n, l and m
i. Principle quantum number (n) determines the size of atom, the number of
orbitals in a given shell (n) = n2 and its value varies 1 to n.
ii. Azimuthal quantum number (l) defines the three dimensional shape of the
orbital. For the given value of n, l can have n values ranging from 0 to n-1.
iii. Magnetic quantum number determines the orientation of orbital in space, the
number of values of m is given by 2 l + 1. Its value varies from – l to 0 to + l
iv. Spin quantum number determines the spin of an electron. It has two values. S =
1/2 (clockwise direction), s = -1/2 (anticlockwise direction)
• Electrons are filled in to various orbitals in order to increasing energy. This is known as
the Aufbau’s principle. The energy of orbital depends upon (n + l) value. The increasing
order of energy of orbital is 1s < 2s <2p < 3s < 3p < 4s < 3d < 4p <5s< 4d < 5p <6s < 4f
< 5d <6p <7s <5f <6d <7p
• Orbitals of same energy are called degenerate orbitals (like px, py, pz)and according to
Hund’s rule of maximum multiplicity no pairing of electrons starts in degenerate
orbitals until or unless each one is singly filled.
• The orbital can accommodate maximum of two electrons with opposite spins and no
electrons in an atom can have same set of four quantum numbers. This is known as
Pauli’s Exclusion principle.
• Orbital Angular Momentum of Electron:
h
L= l(l + 1)
2π
l = azimuthal Q.N. = 0,1,2,3 ---------, for s,p,d,f ------------ sub – shells of orbitals, respectively
• Z - component of orbital angular momentum of an electron in an orbital is given by
h
L = m
2π
Where m = –l to +l including zero (only integral value)
If θ be the angle between Z – axis and angular momentum vector then
h h
L2 = L cosθ Or m = l(l + 1) Cosθ
2π 2π
Or m = l(l + 1) cosθ
Since m ≠ l(l + 1) , so, θ ≠ 0
h
☛ Spin angular momentum of electron, Ls = s(s + 1)
2π
☛ Number of possible spectral lines that may be emitted by a sample of one electron system
n(n − 1)
(atom or ion) containing all or some speeds excited to nth energy level =
2
Vn
☛ Number of revolutions per second made by an electron in nth orbit = =n
2πrn