CHM 211 Module 1 Note

CHM 211 BASIC INORGANIC CHEMISTRY I-2UNITS
Wave Mechanical Treatment of Atomic Structure

Atomic Structure
Atomic structure which includes the number and arrangement of the electrons governs
its chemical and physical properties that is the possible distribution of the electrons about the
nucleus, the energies of the electrons and their magnetic properties etc.
Emission spectrum of Hydrogen Atom
When an electrical discharge is passed through hydrogen at low pressure, a pink-
coloured glow is observed. That is, the excited hydrogen atom emits light of definite
frequencies. If this is examined by a simple spectroscope, a few sharp coloured lines are
observed. The lines of spectrum are named after the men who discovered them.
Limit Limit 5332
109,678 27,420 12,186
10,000 5000
Lyman Balmer Paschen
UV Visible
Pfund
Brackett
Lyman
K=1
L=2
M=3 N=4
O=5 P=6
Paschen
Bohr Orbits of Hydrogen Atom

Balmer
2
The spectrum of atomic hydrogen
Lines nl nh Region
Lyman series nl=1 nh=2,3,4 etc In the Ultraviolet region
Balmer series nl=2 nh=3,4,5 etc In the Visible region
Paschen series nl=3 nh=4,5,6 etc In the Infrared region
Brackett series nl=4 nh=5,6,7 etc In the far Infrared region
Pfund series nl=5 nh=6,7,8 etc In the far Infrared region
When the lines corresponding to a particular wavelength are examined, it is seen that
they all fit the equation:
1 1 1
= R 2 − 2 
  nl nh 
Where λ= wavelength of the particular line
R is Rydberg’s constant =1.097 x 107 m-1=1.097 x 105 cm-1 or 109,677cm-1,
nh = quantum number describing the higher energy state
nl = quantum number describing the lower energy state
(i.e. nl and nh are integers where nh is greater than nl)
1 1 1
=  -Wave number  = R − 2
 2
 l nh 
n
1. Lyman series
1 1 
 = R 2
− 2  where − nh = 2,3,4,5
1 nh 
2. Balmer series
1 1
 = R 2
− 2  where − nh = 3,4,5
 2 nh 
3. Paschen series
1 1
 = R 2
− 2  where − nh = 4,5,6
 3 nh 
4. Brackett series
1 1
 = R 2
− 2  where − nh = 5,6,7
 4 nh 
5. Pfund
1 1
 = R 2
− 2  where − nh = 6,7,8
 5 nh 
3
Bohr’s Theory of atomic spectrum of hydrogen
In 1911, Rutherford provided the idea of an atom consisting of a positively charged
nucleus surrounded by electrons and Bohr used this model of an atom to explain the
anomally of the discrete internal energy.
In the year 1913, Bohr made the following assumptions;
1. The electrons move in an orbit around the central nucleus and only certain orbits are
allowed.
2. The electron does not radiate energy when in those orbits, and has associated with it a
definite amount of energy in each orbit.
3. Radiation is emitted when an electron undergoes a transition from one orbit to another
one of the lower energy.
Bohr imposed one condition so that he could derive the Rydberg formular; He stated that in
each orbit, the angular momentum of the electron, mvr must be quantized that is, half a value
given by;
nh
mvr = -----Equation 1; where m,v,r and h are mass, velocity of electron, radius of the orbit
2
and Planck’s constant respectively and n is called the quantum number of the orbit.
By using this assumption, it was determined that for each orbit, the energy and radius were
given by
hc
E = h = = hc -----Equation 2;

Where ΔE= difference in energy in the two levels
By knowing the mass and the charge of electrons, Bohr calculated the radii of the possible
orbits for the hydrogen atom from this equation 3;
 oh2n2
rn = -----Equation 3; (this expression lies on the centrifugal force acting on the
me e 2
electron)
Where  o =permittivity of a vacuum=8.854 x 10-12Fm-1
h= Planck’s constant=6.626 x 10-34Js

n= 1,2,3…
me=electron rest mass= 9.109 x 10-31kg
e=charge on an electron =1.062 x 10-19C
NOTE
A general equation from all the spectral frequency can be calculated
Rch
En = − -----Equation 4;
n2
4
If electron is in a level designated nH and falls into a lower level nL, then energy
emitted is
Rch Rch
E = E nL − E nH = − + 2
n L2 nH
1 1 
= Rch 2 − 2 
 nL nH 
1 1 
E = h = Rch 2 − 2 
 nL nH 
1 1 
 = c ,  1 = R  2 − 2 
 nL nH 
This equation is precisely same as the first one arrived empirically from the study of
the spectral lines of atomic hydrogen.
The Concept of Duality Behaviour of Electrons
Light radiation canbe considered either as a stream of photons or as a wave motion.
In 1924, de Broglie pointed out that a similar duality exists in the case of electrons. De
broglie showed by arrangement, based on the theory of relativity that if an electron of
momentum P could be described by a wave theory, in terms of a wavelength λ then
 = h P or h mv
Thus λ canbe expressed in terms of electron energy rather than momentum. A kinetic
energy(½mv2) of an electron mass m and velocity v is given by
½mv2=E-V where E is total energy V= potential energy thus
 E −V  h h
v 2 = 2  and  = =
 m  mv  E −V 
m 2 
 m 
Introductions to Uncertainty principle and Schrödinger’s equation
Uncertainty principle
• If an electron has wave-like properties, there is an important and difficult consequence: it
becomes impossible to know exactly both the momentum and position of the electron at
the same instant in time.
• Heisenberg's uncertainty principle, which states that there is a relationship between the
inherent uncertainties in the location and momentum of an electron moving in the x
direction:
5
ℎ
∆𝑥 ∆𝑝𝑥 ≥
4𝜋
where
Δ𝑥=uncertainty in the position of the electron
Δ𝑝𝑥 = uncertainty in the momentum of the electron
Schrödinger’s equation
Reference
1. General Chemistry, 7th Edition Kenneth W. Whitten Raymond E. Davis Larry Peck and George G.
Stanley
2. Inorganic chemistry by Catherine E. Housecroft and Alan G. Sharpe

CHM 211 Module 1 Note

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CHM 211 BASIC INORGANIC CHEMISTRY I-2UNITS

Wave Mechanical Treatment of Atomic Structure

Bohr Orbits of Hydrogen Atom

h= Planck’s constant=6.626 x 10-34Js

Introductions to Uncertainty principle and Schrödinger’s equation

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