Heat Capacity

Heat capacity is the amount of heat dQ required to change a body’s temperature T by 1K

C = dQ/dT

Ideal Gas- Molecules do not interact with each other

An atom has 3 mutually independent directions of motion – Three degrees of freedom

Diatomic molecule – Five degrees of freedom (3 coordinates + 2 angular coordinates)

Separation varies – 6 degrees of freedom (maximal no. for a diatomic molecule) i.e 3 x 2

Energy is kT – Average potential energy of vibration is ½ kT.

Reference: Quantum Mechanics and Quantum Information: A Guide through the Quantum World (2013), 1st Edition,
Chapter 1 – “The Failure of Classical Physics”
An ideal gas equation is PV = NkT where P is Pressure, V volume, N is no. of molecules

For 1 mole of gas, N is Avogadro number i.e NA

PV = RT where R = NAk is the universal gas constant

Internal energy is given by where j’ = j + 1

where j is the number of degrees of freedom

Two types of heat capacities - Cv – Heat capacity at constant volume

Cp – Heat capacity at constant pressure
Classical Picture - Relation between Cv and Cp

where P is constant

Cv and Cp ratio is given by

• Classically, the number j’ and thereby Cp, Cv and  are all independent of T.

• This contradicts the experiments.

• Heat capacities of all substances at low temperatures turn out to be noticeably less
than predicted and go to zero in the limit T  0 !
• Heat capacities of all substances at low temperatures turn out to be noticeably less than
predicted
Classical Physics Prediction
• The same tendency is observed in the measurements of .

• Classical predictions – Constant. Experiments -  increases with T

• Decrease of Cv and increase of  at low T represent two sides of the same coin.
• Heat capacities of all substances at low temperatures go to zero in the limit T  0 !

Classical Physics
Heat capacities fall off with temperature in a
step-like fashion.

Each step associated with the freezing of one or

two degrees of freedom.

At the end, all the initial degrees of freedom are

frozen and accordingly heat capacities approach
zero.

But what is the degrees of freedom in the

beginning? Why that value? Why not a different
value?
Why Classical Physics failed to explain the heat capacity properly?

• It was the assumption that energy exchange between the systems is a

continuous process – WRONG ASSUMPTION

• Energy of a bound system of particles is a continuous variable

– WRONG ASSUMPTION

• The resulting discrepancy with observations shows that there was something
wrong with these classical notions of energy.
Limitations of Classical Physics

• Black Body Radiation (BBR) – Discussion later

• Heat Capacity

• Photoelectric Effect

• Atomic Spectra

• Double Slit Experiment

Black Body Radiation – How radiation reacts with matter?

Object that absorbs all the radiation falling on it When heated, radiates energy due to thermal agitation
Perfect Absorber Perfect Emitter

A perfect/ideal black body does not exist in nature – Only an assumption

Blackbody radiation and its characteristics
 Gases – Discrete Spectra

Blackbody radiation and its characteristics

• Continuous distribution of frequencies • For each frequency, there is a corresponding
energy density
• Light emission ranges the entire spectrum
continuously (IR to UV) • Radiation intensity depends only on its
temperature, not on material composition
Black Body Radiation Spectra Black Body Radiation Spectra
in terms of wavelength in terms of Frequency
• Classical Physics – Tries to explain this spectral distribution curve

• 1879 – Stefan – Boltzmann law defined total intensity emitted by a glowing object
1879 – Stefan – Boltzmann law defined total intensity (energy flux) emitted by a glowing
object
• 1889 – Wilhelm Wien – Relation between temperature and maximum emitting
wavelength (λmax)

i.e. λmax is inversely proportional to the temperature

The wavelength of the peak of the blackbody
radiation curve gives a measure of
temperature
Wien Radiation Law - Energy density distribution

Matches well with the experimental data at higher

frequencies ν (i.e at lower wavelength λ)

But fails at lower frequency (higher wavelength)

like IR
Works @ Lower λ
@ Higher ν

Fails @ Higher λ
@ Lower ν
Low frequency High frequency
(High wavelength) (Low wavelength)
Rayleigh-Jeans Radiation Law - Energy density distribution (Theoretical)

• Assumed radiation inside cavity at absolute temperature T

• Walls of the cavity are perfect reflectors

• Harmonic oscillation of charges, electrons result in radiation

– Harmonic case

• Radiation consists of EM standing waves

– Similar to harmonic oscillators

• Nodes are on the walls of the surfaces

• Electromagnetic energy density inside the cavity

=
Energy density of charged particles on cavity walls
Electromagnetic energy density in the frequency range υ to υ + dυ is given by by multiplying
the average energy of the oscillators by the number of modes (standing waves) of the
radiation in the frequency interval υ to υ + dυ

• Works perfectly with experimental data at low frequency (higher wavelength)

• At high frequency (lower wavelength), experimental data says energy density is finite
but theory says infinite values.
• At high frequency (lower wavelength), experimental data says energy density is finite
but theory says infinite values. According to classical Physics, a blackbody emits infinite
amount of energy in the lower wavelength region (UV, X-rays and so on.) called as
Ultra Violet Catastrophe.

Rayleigh-Jeans law fails at lower wavelength (high frequency)

ULTRAVIOLET CATASTROPHE

Works @ Higher λ
@ Lower ν

Fails @ Lower λ
(UV catastrophe)
@ Higher ν
 Rayleigh-Jeans law
Fails at higher frequency
(lower wavelength)

Lower wavelength Higher wavelength

Higher frequency Lower frequency
Higher energy Lower energy
Why Rayleigh-Jeans law fails? – Wrong assumptions

It was founded on an erroneous premise: the energy exchange between

radiation and matter is continuous; any amount of energy can be exchanged.

Derived using integration !

Planck Hypothesis
Rayleigh’s assumption – A standing wave can exchange any amount (continuum) of energy
with matter – Used integration to find energy distribution

Planck - Energy exchange between radiation and matter must be discrete – Used summation
Planck Hypothesis
- Assumed black body containing large number of oscillating particles/oscillator

- Each particle is oscillating with its characteristic frequency (υ)

- Radiation frequency is same as the oscillating frequency

- Energy of the radiation (of frequency υ) emitted by the oscillating charges (from the
walls of the cavity) must come only in integer multiples of hυ:

h – Universal constant,
hυ – Energy of quantum of radiation
υ – Frequency of oscillating particle (on the wall) and also the radiation

- Energy of an oscillator of frequency υ must be an integral multiple of hυ

- υ and hυ are different for different oscillators
- Classically – No restrictions on the frequency of vibration, and the energy
- E.g Pendulum, Spring

is Planck’s quantization rule or Planck’s postulate

- Energy of a photon is directly proportional

to the frequency of radiation

- Energy of an oscillator is quantized

- Energy of the radiation is quantized

- Using discrete summation instead of integration,

Planck derived energy distribution/energy density.
- Matches well with the experimental data for all wavelengths.

In terms of wavelength, Planck’s radiation law gives

Wien’s Radiation Law
– Fails at higher wavelength

Rayleigh-Jeans Radiation Law

– Fails at Shorter wavelength
- UV Catastrophe

Planck’s Radiation Law

– Works for all wavelength
Wien’s Radiation Law
– Fails at higher wavelength

Rayleigh-Jeans Radiation Law

– Fails at Shorter wavelength
- UV Catastrophe

Planck’s Radiation Law

– Works for all wavelength
For shorter wavelength

Planck’s Radiation Law

This is Wien’s law

For longer wavelength

Planck’s Radiation Law

This is Rayleigh-Jeans law

One can also get Stefan-Boltzmann law from Planck’s Law – Find it ?