General Chemistry (CHEM F111)

Lecture Section: 1

Lecture-1
01/10/2021
The Failures of Classical Physics
•Need to understand how atoms
and molecules behave and interact
How?
•Description of motion of
physical objects (Classical
Mechanics/ Newtonian
mechanics) used till early
20th century is suitable for
macroscopic objects
Newton
• Need to understand detailed structure of atom and
molecules
• Dalton : Concept of atoms (1803)

• Avogadro: Concept of molecules (1811)

• Thomson: Concept of electron (1897)

 Problems that led to Quantum
Concepts
Problems which can be explained using Quantum
Concepts

Black body radiation

Photoelectric effect
Line spectra of atoms
Heat capacity of solids
 Black body radiation
•Any object radiates energy. The
amount of energy emitted, and its
frequency distribution depends on the
temperature and on the material.
•Black body: It is truly a theoretical
object that absorbs all radiation
(100%!) that falls on it.
•Some materials, eg., graphite (96%
absorption/emission), surface coated
with Pt black (98%) approximate such
behaviour or a pinhole in a container
 Black body radiation
The spectral distribution of the power
emitted by a black body

Intensity

Wavelength
Electromagnetic spectrum
 Black body radiation
•Also an ideal emitter. Emits all wavelengths
•Thermal motion of atoms (oscillators) in
walls of black body excites corresponding
oscillations of electromagnetic field
•Experimentally studied by measuring the energy density
in cavity at desired T.
Radiates at all
Intensity wavelengths in
principle! Curve
touches X axis
at infinity
Wavelength
 Thermal Radiation

When viewed through an

IR Camera
Much of a person's energy is radiated
away in the form of infrared energy.
•Any dense object can radiate energy-
 Major experimental observations

Not all wavelengths are

emitted equally
At any temperature, the
intensity of emitted
light → 0 as the
wavelength → 0
It increases to some
maximum intensity Imax
at some wavelength max
•max : wavelength of the
radiation with greatest
contribution to energy density
 Black body radiation
Major observations
•Wien’s Law
•maxT = 2.99 mm K (Constant)


max T

T Common observation
with heated bodies; Red
 blue
 max vs Temperature
 max = 2.99 x 10-3 m
T(Kelvin)
T  max
310K 2.99 x 10-3 m
(body temp) =9.6x10-6m
3100
infrared light

5800K 2.99 x 10-3 m

(Sun’s surface) 58000 =0.5x10-6m
visible light
 Black body radiation
Stefan-Boltzmann Law:
Emittance M = aT4
(Power emitted per unit
surface area is
proportional to the 4th
power of temperature)
‘a’ =56.7 x 10-9 Wm-2K-4 Rapid increase in
area under curve
with increasing
temperature
 Black body radiation
Radiation
viewed as a
collection of
harmonic
oscillators.

Rayleigh-Jeans: Energy density d is the

energy per unit volume associated with
radiation of wavelength from  to +d, and is
proportional to the emittance
d = (8π kBT/ 4) d
 Black body radiation
Rayleigh-Jeans:
d = (8kT/4)d with k the Boltzmann
constant.
•The function rises without bound as  decreases
•Oscillators of short wavelength (UV) is excited (
is very high) even at room temperature
(ultraviolet catastrophe)
From Classical to Quantum Description
– how it happened?
"If a revolution occurred in physics
in December 1900, nobody seemed to
notice it. Planck was no exception..
Energy quantization - was scarcely
Max Karl noticed.. during the first few years of
Ernst the 20th century no one considered
Ludwig his (Planck’s) results to conflict with
Planck
the foundations of classical
physics.”- -H. Kragh, Phys. World, Dec. 2000
Energy Quantization
 Planck Formula (1900)
d = (hc/)(ehc/kT - 1)-1(8/4)d
Density of oscillators as before, but with c/,
average energy is h/(eh/kT – 1).
Crucial assumption that Planck had to make was
that an oscillator of frequency  cannot be
excited to any arbitrary energy, but only to
integral multiples of a fundamental unit or
quantum of energy h, with h = 6.626 x 10-34 J s,
the Planck constant, i.e., E = nh, n = 0,1,2,….
Quantization
Planck expression reproduces
the experimental distribution
with h = 6.626 x 10 –34 J s
 Success of Planck’s formula:
 = 8 hc / {5(ehc/kT - 1)}

Integrate Take
 over d derivative of
to get total  w-r-t 
power to get peak
radiated
aT4 maxT
Stefan Boltzman Law is Wien’s Law is
obtained obtained
x=4.956

maxT = hc/4.9k
= constant
 Success of Planck’s formula:

 = 8 hc / {5(ehc/kT - 1)}

Case 1: Small values of 

•At 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:
Case 2 : large values of 
Reduces to Rayleigh-Jeans
formula
 = 8 hc / {5(ehc/kT - 1)}

( hc/kT) << 1
( hc/kT) << 1
 Success of Planck’s formula:
 = 8 hc / {5(ehc/kT - 1)}

•Planck's hypothesis: An oscillator cannot be

excited unless it receives an energy of at least
hν (as this is 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
Planck Einstein
 Photoelectric Effect

Emission of electrons from metals when exposed to

(ultraviolet) radiation.
 Observations
1. No emission of electrons if the frequency of
radiation is below a threshold value
characteristic of the metal, however high the
intensity of the light.
2. Kinetic energy of emitted electrons varies
linearly with the frequency, and is independent
of light intensity.
3. For frequencies above the threshold value,
emission of electrons is instantaneous, no matter
how low the intensity of the light.
 Explanation (EINSTEIN 1905)
1. Light of frequency  may be considered as a
collection of particles, called photons, each of
energy h.
2. If the minimum energy required to remove an
electron from the metal surface is  (work
function), then if h < , no emission of
electrons occurs.
3. Threshold frequency 0 given by  = h0
4. For  > 0, the kinetic energy of the emitted
electron Ek = h   = h(  0).
Line Spectrum of Hydrogen atom
Transitions between quantized energy levels of
atom or molecule, with absorption or emission of
photon accounts for line spectra.
The frequencies (in wave numbers) at which the
lines occur in the spectrum of hydrogen are given
by the formula
= 1/ = RH(1/n12  1/n22)
where RH = 109677 cm-1 is the Rydberg constant, n1
and n2 > n1 are positive integers, the various series
corresponding to Lyman (n1 = 1), Balmer (n1 = 2),
Paschen (n1 = 3), Brackett (n1 = 4), Pfund (n1 = 5).
 Invalid Assumptions of Classical
Physics
1. Particle travels in a trajectory or path, with a
precise position and momentum at each instant.
2. Any type of motion can be excited to a state of
arbitrary energy.
3. ‘Waves’ and ‘Particles’ are distinct concepts.

These are excellent assumptions at the macroscopic

level, but break down when one considers the
behaviour of very small entities such as electrons,
atoms, molecules, etc.