Chemistry I (CHEM C141)

K. Sumithra

Chemistry-I (CHEM C141)

The Scope and Objective

The electronic structure of atoms and

molecules
Chemical bonding
Molecular Spectroscopy
Phase and chemical equilibrium
Chemical kinetics.

CHEM C141 Chemistry I

Quantum theory
Atomic structure and spectra
Chemical bonding

Spectroscopy of various types

CHEM C141 Chemistry I

Thermodynamics and thermochemistry

Statistical thermodynamics

Phase equilibria
Mixtures

CHEM C141 Chemistry I

Chemical reaction thermodynamics

Chemical Kinetics

Main Text:
The Elements of Physical Chemistry,
P.W. Atkins & Julio de Paula, Fifth
edition (Oxford University Press, Oxford
2009).

Reference :
(i) Physical Chemistry, G. M. Barrow, Fifth
Edition, Special Indian Edition (Tata
McGraw Hill Publishing Company
Limited, New Delhi 2007).
(ii) Physical Chemistry, D. W. Ball, First
Edition, Indian Edition (Thomson, 2007).

Component

Duration

Wt %

Date/Time
dd/mm/yy

Remarks

Test I

50
min

20%

4.9.2010

Closed
book

Test II

50
min

20%

9.10.2010

Open
book

Test III

50 min

20%

20.11.2010

Closed
book

Comprehensive
examination

3 hrs

40 16%
% Quiz

3.12.2010

-do-

24%

-do-

Tutorial Hour
A review of the lectures
Discussion and interactions
Clarification of doubts
Problem solving

Origin of Quantum Mechanics

Physics in the late 19th Century

1.Classical mechanics
Newtons law applies universally
Any motion
arbitrary
energy
2.The world is deterministic.
3.Light is an electromagnetic wave
Waves and particles : Distinct concepts

Invalid Assumptions of Classical Physics

1. Any type of motion can be excited to a state of
arbitrary energy: Oscillation of a pendulum

Invalid Assumptions of Classical Physics

2. Particle travels in a trajectory or path, with a
precise position and momentum at each instant.

Invalid Assumptions of Classical Physics

3. Waves and Particles are distinct concepts.
These are excellent assumptions at the macroscopic
level, but break down when one considers the
microscopic level:
Behaviour of very small entities such as electrons,
atoms, molecules, etc.

 Need to understand detailed structure of

atoms and molecules
Timeline:
Dalton : Concept of atoms (1803)
Avogadro: Concept of molecules (1811)
Thomson: Concept of electron (1897)

Experiments that defied Classical

Physics
Black body radiation
Photoelectric effect
Line spectra of atoms
Heat capacity of solids
Interference
Diffraction

Conclusion
Newtons 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 deals with
Nature as she is amazing!

"And anyone who thinks they can

talk about quantum theory without
feeling dizzy hasn't yet understood
the first thing about it."
Niels Bohr.

Quantum Mechanics
Describes rules that apply to electrons in
atoms and molecules
Non-deterministic, Probabilistic
-Explains unsolved problems of the late
19th Century
-Explains bonding, Structure and
reactivity in Chemistry

Electromagnetic spectrum

Thermal Radiation
Blackbody Radiation

Much of a person's energy is radiated

away in the form of infrared energy.

Blackbody radiation

T
Common observation
with heated bodies; Red
blue

Black body radiation

Any dense object can radiate energyProperties of a perfect blackbody
A blackbody is a perfect absorber or emitter of radiation

The distribution of absorbed or emitted radiation

depends only on the absolute temperature, not on
blackbody material

Graphite

96% Absorption/Emission

Surface coated with lamp black/

Platinum black

Black body radiation

Perfect black body
Pin hole in a container

Fery

Black body radiation

Problem: To account for the spectral
distribution of the power emitted by a
black body
Radiates at all
wavelengths in
principle! Curve
touches X axis
at infinity

Intensity

Wavelength

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 = 2.99 mm K (Constant)

max

T
Common observation
with heated bodies; Red
blue

 Shorter
wavelengths
contribute more
to the energy
density as
temperature is
raised and
the color shifts t

Application of Wiens Displacement Law

(T max = 2.9 mm K)
Estimation of the Temperatures of Stars
Maximum Emission of the Sun occurs at
max = 490 nm. What is the surface
temperature?
The Surface Temperature of Sun
T = 2.9mmK/ max
= (2.9 x 10-3 m K) / (490 x 10-9 m)
= 5918 K

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

Stephan-Boltzman Law ; Emittance

T =1000K, Emittance, M= 5.7Wm-2

What
is the emittance
? -2
T=3000K,
M= 34atx3000K
5.7Wm

M3000K = 81 x M1000K
Emittance : Area under
the curve
Rapid increase with
increasing temperature

Attempted explanation of black body radiation with

classical mechanics
Main assumptions

Electromagentic radiation was regarded as

waves in jelly like ether
Ether could oscillate at any frequency so
waves could exist in it of any wavelength
Rayleigh-Jeans law

Expt
Rayleigh-Jeans Theory

Black body radiation : Rayleigh-Jeans formula

Energy density d is the energy per unit

volume associated with radiation of wavelength
from to +d, and is proportional to the
emittance :
Rayleigh-Jeans formula : d =

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

Black body radiation : UV Catastrophe

Rayleigh-Jeans Formula:
d =

The function rises without bound as decreases

Even cold objects would emit UV and visible!