CHEMISTRY I (CHEM C141)

Dr. K. Sumithra

Lecture 2: 6/8/2010

Summary of the last Lecture:

Failure of Classical Mechanics
Problems that led to Quantum Theory
Black Body Radiation Features
Wiens Displacement Law
Stephan-Boltzmann Law
Classical Theory :
Rayleigh-Jeans Theory
UV Catastrophe

Major experimental observations

Not all wavelengths of light 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

Black body radiation- Features

1. Wiens Displacement Law
maxT = 2.9 mm K (Constant)

max

T
Common observation
with heated bodies; Red
blue

Stephan-Boltzman Law ; Emittance

M = Power/Area = aT4

M3000K = 81 x M1000K

Emittance : Area under

the curve
Rapid increase with
increasing temperature

Black body radiation : Rayleigh-Jeans formula

Energy density d - energy per unit volume

associated with radiation of wavelength from
to +d
Rayleigh-Jeans formula : d =

Rayleigh-Jeans Law

kB = 1.38065 x 10-23 J K-1

No quantization of energy, the oscillators

could emit any energy

Consequences

d =

Works at long wavelengths (low frequencies) but fails

badly at short wavelengths( high frequencies)
As decreases, increases without going through
maximum
Oscillations of short wavelength are
strongly excited at room temperature

Rayleigh-Jeans Formula: UV Catastrophe

The function rises without bound as decreases

Even cold objects would emit UV and visible!

Expt
Rayleigh-Jeans Theory

Classically :
1.Radiation from a blackbody is the result of
electrons oscillating with frequency .
( It is like electrons in antenna, emitting
radio waves!)
2. The electrons can oscillate (& radiate)
equally well at any frequency.

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

Planck Formula (1900)

Crucial assumption
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
h = 6.626 x 10-34 J s, the Planck constant
E = nh, n = 0,1,2,.

Plancks Formula (1900)

hk

hk T _

hc
ehckBT _ 1

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

Success of Plancks formula:

hc

ehckBT _ 1

Integrate
over to get
total power
radiated
M=aT4
Stefan Boltzman Law is
obtained

Take
derivative of

w-r-t
to get peak
maxT = constant
Wiens
displacement Law
is obtained

x=4.956

max

hc
=
4.956kT

maxT = hc/4.9k
= constant

Success of Plancks formula:

hc

ehckBT _ 1

Case1 : small
ehc/kT faster than 5
(Exponential is large)
0 as 0
Energy density 0 as 0
UV Catastrophe avoided

Success of Plancks formula:

Case2 : large values of
Reduces to Rayleigh-Jeans
formula
hc

ehckBT _ 1

Quantum Mechanics
Restriction on the value of energy
The energy of oscillators is proportional
to the frequency of the oscillators.
Quantum Ideas
1.The energy of the oscillator
2. E = nh, n = 0,1,2,.
h

: Quantum of energy

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

Quantization of energy
Energies in atoms
are quantized, not
continuous.
Quantized means
only certain
energies allowed.

continuum

discrete

Quantization of energy!

Quantization

Planck expression reproduces the experimental

distribution with h = 6.63 x 1034 J s

Success of Plancks formula

hc
ehckT _ 1

Planck's hypothesis:

An oscillator cannot be excited unless it receives an

energy of at least h (as this the minimum amount of
energy an oscillator of frequency may possess above
zero).
For high frequency oscillators (large ), the amount
of energy h 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 Plancks formula

Quantum Ideas
1.The energy of the oscillator
2. E = nh, n = 0,1,2,.
h

: 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).

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.
h = hc/ = (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
2.63 eV > 2.09 eV
Photoelectrons will be ejected

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.

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 :
= 1/ = RH(1/n12 1/n22)
where RH = 109677 cm-1 , is the Rydberg constant
n1 and n2 > n1 are positive integers
n1

n2

Region

Lyman

2,3,4,.

Ultraviolet

Balmer

3,4,5,.

Visible

Paschen

4,5,6,.

Near IR

Bracket

5,6,7,.

IR

Atomic Models
Rutherfords Planetary Model

Bohr atom model

Coulombic force and the centripetal force balance

Electron of mass m, in circular orbit of radius r, about
stationary nucleus of mass mN, charge Ze
mv2/r = Ze2/4 r2

Bohr Model
1. Specific orbits, discrete quantized energies.
2. The electrons do not continuously lose energy
gain or lose by jumping from one orbit to another
3. quantization of angular momentum
L = mvr = nh/2 = n, n = 1,2,3,.
Success
Could explain Rydbergs formula
Theoretical background for Line Spectra

Bohr model Inadequacies

Primitive Model
Semi-classical
The spectra of larger atoms.
The relative intensities of spectral lines
The existence of fine and hyperfine structure
in spectral lines.
The Zeeman effect - changes in spectral lines
due to external magnetic fields

Waves and Particles

Main experiment showing light as particles
is the
Photoelectric effect

Two properties of waves are:

Interference
Diffraction
The ability for something to behave as a
wave and a particle at the same time is
known as wave-particle duality.

Wave-Particle Duality
Wave-Particle duality shows:

Light can act like a wave and like a

particle.
Particles can act as waves

Double-slit Experiment

Interference: Superposition of two or

more waves to generate new patterns
Constructive; destructive