General Chemistry (CHEM F111)

Lecture 2, 21-10-2022
RECAP
Black body radiation- Features
1. Wien’s Displacement Law
•maxT = 2.99 mm K (Constant)

•max and T are inversely related!

max

T
RECAP
Black body radiation : features

2. Stefan-Boltzmann Law:
Emittance M = aT4
(Power emitted per unit
Surface Area)
‘a’ =5.67 x 10-8 Wm-2K-4

Rapid increase with increasing temperature

Black body radiation : UV Catastrophe
Rayleigh-Jeans Formula:
k d
d =


The function rises without bound as  decreases

•Even cold objects would emit UV and visible!
  Black Body Radiation - features
• Planck’s Distributions:
• Concept of Quantization

 hc
 ehckBT _ 1

 Planck’s Formula (1900)
k hk
 
 ehk T _
B 1

 hc
 ehckBT _ 1


h = 6.626 x 10-34 J s, Planck constant

Success of Planck’s formula:
 hc
 ehckBT _ 1


Integrate  Take

over  to get derivative of
total power  w-r-t 
radiated to get peak
maxT = constant
M=aT4 Wien’s
Stefan Boltzman Law is displacement Law
obtained
is obtained
 x=4.956
hc maxT = hc/4.9k
max = = constant
4.956kT
 Success of Planck’s formula:

 hc
 ehckBT _ 1


Case1 : small 
•ehc/kT   faster than 5
(Exponential is large)
•  0 as   0
•Energy density 0 as   0
•UV Catastrophe avoided
Success of Planck’s formula:
Case2 : large values of 
Reduces to Rayleigh-Jeans
formula
 hc
 ehckBT _ 1


( hc/kT) << 1
 Quantum Mechanics
Restriction on the value of energy
Quantization
The energy of oscillators is proportional
to the frequency of the oscillators.
1. The energy of the oscillator α ν
2. E = nh, n = 0,1,2,….

hν : Quantum of energy

h = 6.626 x 10-34 J s, Planck constant

Energy is quantized in the tiniest of scales
 Planck’s Theory
Energy cannot be radiated or absorbed
in any arbitrary amounts,

but only in discrete “quantum” amounts.

Concept of Quantization

Planck’s concept of quantization of energy

helped to explain the full spectrum of
Black Body Radiation
 Quantization of Energy

Experimental Evidence: Black Body Radiation,

Line spectra of atoms, etc
 Classical vs Quantum world
At atomic & subatomic
In everyday life, scales,
quantum effects quantum effects
can be safely are dominant & must
ignored be considered

Laws of nature
This is because developed without
Planck’s constant is consideration of
so small quantum effects do not
work for atoms
 Quantization

Limitation of energy
values to certain
values Planck expression reproduces the experimental
distribution with h = 6.63 x 10–34 J s
 Success of Planck’s formula
 hc
 ehckT _ 1
Planck's hypothesis:
An oscillator cannot be excited unless it receives an
energy of at least hν (as this the minimum amount of
energy an oscillator of frequency ν may possess above
zero).
For high frequency oscillators (large ν), the amount
of energy hν is too large to be supplied by the thermal
motion of the atoms in the walls, and so they are not
excited.
Catastrophe avoided
Basic Idea behind Planck’s formula

Quantum Ideas

1. The energy of the oscillator ν

2. E = nh, n = 0,1,2,….

hν : Quantum of energy
Are electromagnetic radiations that
simple as we think?

A new view of light?

 Photoelectric Effect

Emission of electrons from metals when exposed to

(ultraviolet) radiation.
Observations
1. No emission of electrons below a threshold value
characteristic of the metal – Work function

2. Kinetic energy varies linearly with the

frequency

3. Above the threshold value, emission of electrons

is instantaneous.

Emission - Independent of light intensity.

 Explanation (EINSTEIN 1905)

1. Light : collection of particles, called photons,

each of energy h.
2. If h < , no emission of electrons occurs.
3. Threshold frequency 0 ,  = h0
4. For  > 0, the kinetic energy of the emitted
electron Ek = h   = h(  0).

Ek = h   h = 6.626 x 10-34 J s, Planck’s constant

Linear equation, PLOT kinetic energy of emitted
electrons against the frequency of radiation used,
Ek vs  h can be calculated from the slope
How to measure Kinetic energy experimentally?

By measuring the stopping potential

Ek = h   = h(  0) = -eVs

Example
The work function of rubidium is 2.09 eV (1 eV =
1.602 x 10-19 J). Can blue (470 nm) light eject
electrons from the metal?
Need to find out energy of radiation,
convert 470 nm to eV.
hν = hc/λ = (6.626 x 10-34 J s) x (3.00 x 108
m/s) / (470 x 10-9 m)
= 4.23 X 10-19 J = 2.63 eV
Energy of blue light >
workfunction 2.09 eV
Photoelectrons will be ejected
 This experiment gives a powerful evidence
to the existence of photons
(i) Are photoelectrons restricted to metal sources?
(ii)Can we use radiations other than UV?
Application
Photoelectron spectroscopy (PES)

Ultraviolet PS with UV
X-ray PS with X-rays
• Binding energies of valence and core electrons
• Indirectly prove the existence of molecular
orbitals
Line Spectra

Electric discharge
Molecules Dissociate to atoms

Excited Atoms emit radiations of discrete

wavelengths.

A spectrum of discrete lines!

Most compelling evidence for QUANTIZATION

 Line Spectra
Hot gas emits photons with the characteristic wavelengths
corresponding to the transitions between different energy
levels of the atoms or molecules in the gas. This leads to
bright lines in the spectrum.
 Theoretical
background for Line
Spectra : Bohr Theory

Bohr frequency
relation

Transitions between quantized energy levels of atom

or molecule, with absorption or emission of photon
accounts for line spectra.
Line Spectrum of Hydrogen atom
The frequencies (in wave numbers) at which the lines
occur in the spectrum of hydrogen : Rydberg’s
= 1/ = RH(1/n12  1/n22) Empirical
formula
where RH = 109677 cm-1 , is the Rydberg constant
n1 and n2 > n1 are positive integers
n1 n2 Region

Lyman 1 2,3,4,…. Ultraviolet

Balmer 2 3,4,5,…. Visible
Paschen 3 4,5,6,…. Near IR
Bracket 4 5,6,7,…. IR
Pfund 5 6,7,8,…. Far IR
 Wave-Particle Duality
Wave-Particle duality shows:

Light can act like a wave and like a

particle.

Particles can act as waves

Matter waves : Waves associated with

particles
 Waves and Particles
Main experiment showing light as
particles are the
Photoelectric effect
Black body radiation

Two properties of waves are:

Interference
Diffraction
If electron is acting as a wave,
We should see diffraction and interference
of matter waves
 Wave-Particle Duality
Wave-Particle duality shows:
Light can act like a particle.
Particles can act as waves

Interference: Superposition of two or

more waves to generate new patterns

Double-slit Experiment Constructive; destructive

Young’s double-slit experiment
can be done with electrons

Electron behaving as a wave!

The wavefronts resulting
from two slits.
 Electron Diffraction
Firing electron at an object and observing the
scattering (analogous: X-ray and neutron
diffraction): Davisson and Germer 1925

electron beam was scattered by the surface atoms at the exact angles
predicted for the diffraction of waves, with a typical wavelength