General Chemistry (CHEM F111)

Lecture 1, 19-10-2022

K. Sumithra
General Chemistry (CHEM F111)

The Scope and Objective

•Physical Chemistry :
The electronic structure of atoms and molecules
Chemical bonding
Thermodynamics
Chemical kinetics
Molecular Spectroscopy
•Organic Chemistry
•Conformations
•Stereochemistry
•Reaction mechanisms
•Inorganic Chemistry
•Co-ordination complexes
•Crystal Field Theory (CFT)
•Chelates and Isomerism
 Main Text books:

T1: P.W. Atkins & Julio de Paula, ‘The Elements of

Physical Chemistry’, International edition (Oxford
University Press, Oxford 2017).

T2: T. W. Graham Solomons and Craig B. Fryhle,

‘Organic Chemistry’, 10th Edition, John Wiley & Sons,
Inc. New York, 2011.

T3: J. D. Lee, ‘Concise Inorganic Chemistry’, 5th

Edition, Wiley 2008.
 Reference :

R1. L. G. Wade Jr. and M.S. Singh, ‘Organic

Chemistry’, 6th Edition, Pearson Education
Inc., 2006.

R2. D. W. Ball, ‘Physical Chemistry’, First

Edition, Indian Edition (Thomson, 2007).
 Handout ..
L N Topic Learning Objectives Text
1-4 Quantum Origins of Quantum T1: 7A,
Theory Mechanics, Black body 7B, 7C,
radiation, Wave 7E
function,…..

S.S. Self study

Tutorial Hour
•A review of the lectures
•Discussion and interactions
•Clarification of doubts
•Problem solving
Evaluation Scheme:

Component Duration Weightage Date and Nature of

(%) Time component
Mid-semester 90 min 30 - Closed
Exam Book
Class Tests - 30 To be Open Book
(Assignments)# announced
Comprehensive 180 min 40 - Closed
Examination Book
Tutorials: The tutorial hour is used for a quick review of the material covered in
the lectures, clarification of doubts, and problem-solving.

# Makeup is not permissible for the evaluation components (except in extreme

situations), which would be decided by the Instructor in charge & the team.

6. Chamber Consultation Hours: To be announced through a separate notice.

7. Notices: Notices concerning the course will be displayed on the Chemistry

Department Notice Board / CMS or communicated through email.

8. Academic Honesty and Integrity Policy: Academic honesty and integrity are
to be maintained by all the students throughout the semester and academic
dishonesty is highly unacceptable.

9. Make-up-policy: Make-up would be considered for very genuine reasons

only.
Welcome to the world of Quantum
Mechanics
Origin of Quantum Mechanics

Physics in the late 19th Century

1. Classical mechanics
Newton’s law applies universally

Any motion arbitrary

energy
2. The world is deterministic.

3. Light is an electromagnetic wave

Waves and particles : Distinct concepts
 Assumptions of Classical Physics
1. Any type of motion can be excited to a state of
arbitrary energy: Oscillation of a pendulum
 Assumptions of Classical Physics
2. Particle travels in a trajectory or path, with a
precise position and momentum at each instant.

Predicts a precise trajectory

 Assumptions of Classical Physics
3. ‘Waves’ and ‘Particles’ are distinct concepts.

Excellent assumptions at the macroscopic

level, but break down at the microscopic level

Classical Physics : Cannot explain the

behaviour of very small entities such as
electrons, atoms and molecules.
• Need to understand detailed structure of
atoms and molecules
Classical mechanics : fails

1. When small energy transfers are involved

2. For objects of too small mass
Timeline:

Mechanics to understand the detailed

structure of atoms and molecules

~ 1900 - 1920
Few Experiments that challenged
Classical Physics
Black body radiation
Photoelectric effect
Line spectra of atoms
Heat capacity of solids
Interference
Diffraction
Conclusion
Newton’s laws do not apply to
the microscopic world!
Classical mechanics fails
Outcome New Rules

QUANTUM MECHANICS!
-a new philosophy
Stephan Hawking : Quantum mechanics is the
basis of modern developments in chemistry,
Molecular biology, and electronics, and the
foundation for the technology that has
transformed the world in the last fifty years

R. P. Feynman :
Quantum Mechanics deals with “Nature as
she is – absurd”
Quantum Mechanics
•Describes rules that apply to electrons
in atoms and molecules

•Non-deterministic, Probabilistic

 Explains the unsolved problems of

the late 19th Century
 Explains bonding, structure and
reactivity in Chemistry
Electromagnetic spectrum
 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-

Black body radiation
Properties of a perfect blackbody
 Perfect absorber or emitter of radiation

The distribution of absorbed or emitted radiation

depends only on the absolute temperature, not on the
blackbody material

•Graphite 96% Absorption/Emission

•Surface coated with lamp black/
Platinum black (98%)
 Black body radiation
• Perfect black body : Impossible to
construct
• Pin hole in a container Ferry
• A closed double walled hollow sphere
 Black body radiation

Problem: To account for the spectral distribution

of the power emitted by a black body

Radiates at all
wavelengths
Intensity in principle!
Curve
touches X axis
at infinity
Wavelength
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- Features
1. Wien’s Displacement Law
•maxT = 2.99 mm K (Constant)

•max and T are inversely related!

•max : Greatest contribution to energy density

max
 Shorter
wavelengths
contribute more to
the energy density
as temperature is
raised and
the color shifts t
Application of Wien’s Displacement Law

(T λmax = 2.9 mm K) In Astrophysics

Estimation of the Temperatures of Stars

Maximum Emission of the Sun occurs at
λmax = 490 nm. What is it’s surface
temperature?
The Surface Temperature of Sun
T = 2.9mmK/ λmax
= (2.9 x 10-3 m K) / (490 x 10-9 m)
= 5918 K
we can calculate the temperature of
an object without touching it
 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 : 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

 Stefan-Boltzman Law ; Emittance M = aT4

T =1000K, Emittance, M= 5.7 x 10 4

Wm-2
What is the emittance at 3000K ?
T=3000K, M= 34 x 5.7 x 10 4 Wm-2
M3000K = 81 x M1000K
Emittance : Area under the
curve
Rapid increase with increasing
temperature
Attempted explanation of black body radiation
with classical mechanics
Main assumption

Electromagnetic radiation can be of any

wavelength

 Classical – Rayleigh-Jeans law based on

equipartition principle
Observed

Rayleigh-Jeans Theory
Black body radiation : Rayleigh-Jeans formula

Energy density =
Energy/volume

Energy density d is the energy per unit volume

associated with radiation of wavelength from  to
+d, and is proportional to the emittance :
k d
Rayleigh-Jeans formula : d =

rho
 k d
Consequences d =

 Works at long wavelengths (low frequencies) but
fails badly at short wavelengths( high frequencies)
As λ decreases, ρ increases without going through
maximum
Oscillations of short wavelength are
strongly excited at room temperature

Even cold objects

would emit!
Violation of law of
conservation of energy!
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!
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.
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,….
 Planck’s Formula (1900)
k hk
  
 hk T _
e B 1

  hc
 ehckBT _ 1


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