BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

8/5/2012

BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

Text Books:
T1: P.W. Atkins and Julio de Paula, Elements of Physical
Chemistry: 5th Edition, Oxford University Press, Oxford
2009
T2: T. W. Graham Solomons and Craig B. Fryhle, Organic
Chemistry, 8th Edition, John Wiley & Sons, Inc. New York,
2004.

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General Chemistry CHEM F111):

An Introduction

Reference Books:
R1: J. D. Lee, Concise Inorganic Chemistry, 5th Edition,
Blackwell Science, Oxford, 1999.

R2: R. T. Morrison and R. Boyd, Organic Chemistry, 6th

Edition, PHI, New Delhi, 1992.

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General Chemistry CHEM F111):

An Introduction

Quantum theory
Atomic structure and spectra
Chemical bonding
Spectroscopy of various types

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General Chemistry CHEM F111):

An Introduction

Chemical reaction thermodynamics

Chemical Kinetics

Electrochemistry

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BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

Conformations
Stereochemistry
Different types of reactions

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BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

Aromatic compounds
Coordination compounds
Structure and stability
Chelates and Isomerism

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General Chemistry CHEM F111):

An Introduction
Component

Duration

Wt %

Date/Time

Remarks

Mid Semester
Test

90
min

30%

7.10.2012
4.00 - 5.30
pm

Closed
book

25%

Continuous

45 16%
% Quiz
29%

5.12.2012
Forenoon

Closed
book

Do

Open
book

Tutorial
Comprehensive
Examination

8/5/2012

180
min

BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

*Tutorial Hour
A review of the highlights of the materials covered
in the lectures
Further discussion and interactions
Clarification of doubts
Problem solving
Periodical and continuous evaluation
8/5/2012

BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

Tutorial Hour Tests: Two types

A set of objective type questions (different types),

which the student will have to answer and submit
during the tutorial class.
A set of problems will be assigned periodically, of
which one to be solved in the tutorial hour of the
following week.
Students must attend the tutorial section in which
they are registered.
8/5/2012

BITSPilani, Pilani Campus

General Chemistry CHEM F111):

An Introduction

Quantum Theory

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Why Quantum Theory??

Description of motion of physical objects (Classical
Mechanics/ Newtonian mechanics) used till early
20th century is suitable for macroscopic objects

Any kind of motion can be excited to any arbitrary

value of the energy
A particle travels in a trajectory, a path with a
precisely defined position and momentum at each
instant
Waves and particles are distinct concepts
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Why Quantum Theory??

The idea of duality
is rooted in a debate
over the nature of
light and matter
dating back to the
1600s.
Christiaan Huygens
1629 -1695
light consists of
waves
8/5/2012

Sir Isaac Newton

1643 -1727
light consists of
particles
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Quantum Theory
These are excellent approximations at the macroscopic
level, but break down when one considers the behavior of
microscopic entities such as electrons, atoms, molecules
etc.
Black body radiation

Photoelectric effect
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Quantum Theory
Heat capacity of solids
Line spectra of atoms

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Quantum Theory
People RARELY get quantum mechanics of their
first exposure.
Many aspects of quantum mechanics are counter
intuitive and thus, visual learners will likely have
more trouble than those that tend to think in the
abstract.
We will introduce it now in hopes it will be easier
the more you are exposed to it.
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Blackbody
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 approximate such
behavior or a pinhole in a container

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Blackbody Radiation
Blackbody
radiation:
The radiation emitted
from the hole is called
blackbody radiation.
Problem: To account for
the spectral distribution
of the power emitted by
a black body.
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Quantum Theory
Wiens displacement law:
The peak of the curve shifts towards longer
wavelength as the temperature falls and it satisfie
maxT = 2.9 mm K
(Constant)

Can be used in
measuring
the
temperature on the
surface of the sun.
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max

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Quantum Theory
Stefan and Boltzmanns law:
The radiation energy is
proportional to the 4th power of
the associated temperature.
Emittance M = aT4

(Power emitted per unit Surface

Area and proportional to
Energy density)
a =5.67 x 10-10 Wm-2K-4
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Quantum Theory
The above laws describes the blackbody radiation
very well.

The problem exists in the relation between the

radiation power M(T) and the wavelength .
Two typical theoretical formulas for blackbody
radiation was proposed: One is given by Rayleigh
and Jeans and the other by Wein.
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Quantum Theory
Rayleigh-Jeans Law
In 1890, Rayleigh and Jeans obtained a formula
using the classical electromagnetic (Maxwell)
theory and the classical equipartition theorem of
energy in thermotics.
It states that the density of energy in a region of
the eletromagnetic field due to radiation of
wavelength is proportion to 1/4

Energy Density ( ,T ) 8KT C1 T

4

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Quantum Theory
Rayleigh-Jeans formula
was correct for very long
wavelength in the far
infrared but hopelessly
wrong in the visible light
and ultraviolet region.

Energy density rises without bound as decreases

It was regarded as ultraviolet Catastrophe.
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Quantum Theory
Weins formula:

Later on in 1896, Wein derived another important

formula using thermodynamics.

M (T ) C2 e
5

C3
T

Unfortunately, this formula is only valid in the short

wavelengths region.
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Quantum Theory
Plancks Magic formula
Crucial assumption that
Planck make 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 i.e.,
E = nh, n = 0,1,2,.
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h = 6.626 x 10-34 J s,
the Planck constant,
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Quantum Theory
Plancks distribution dE = d
Where Energy density () = (8hc/5)(ehc/kT - 1)-1
c is the speed of light, k is Boltzmanns constant and
h is Plancks constant.
Planck
proposed
empirical formula describe
the curve of blackbody
radiation exactly for all
wavelengths.
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Quantum Theory
Success of Plancks formula:
= 8 hc / {5(ehc/kT - 1)}
Integrate over
d to get total
power radiated

Take derivative of
w-r-t to get peak

aT4 ; Stefan Boltzman

Law is obtained

maxT ; Wiens
displacement Law is
obtained

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Quantum Theory
Success of Plancks formula:
= 8 hc / {5(ehc/kT - 1)}
At small , ehc/kT faster than 5
(Exponential is large)
0 as 0
Energy density 0 as 0
UV Catastrophe avoided
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Quantum Theory
Success of Plancks formula:

hc
For very large wavelength, when
1
kT
e

hc
kT

hc 1 hc
1


kT 2 kT

Drop the second order and higher order terms, and

Rayleigh-Jeans formula could be obtained.
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BITSPilani, Pilani Campus

Quantum Theory
Success of Plancks formula:
For smaller wavelength of blackbody radiation,

1
e

hc
kT

hc

kT

Weins formula can be obtained.

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Quantum Theory
Plancks empirical formula matched all the
different classical physics results obtained by the
Maxwell electromagnetic theory, thermodynamics
and statistics! However, no one knew why at that
time. This phenomenon seemed unbelievable,
incredible and even impossible, but is true!

Planck himself did not believe his such a wonderful

hypothesis and he spent about ten years to solve
the same problem using classical physics.
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Quantum Theory

Photoelectric Effect

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Quantum Theory
Observations
No emission of electrons if the frequency of
radiation is below a threshold value characteristic
of the metal.
Kinetic energy of emitted electrons varies
linearly with the frequency, and is independent of
light intensity.
For frequencies above the threshold value,
emission of electrons is instantaneous, no matter
how low the intensity of the light.
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Quantum Theory
Explanation (EINSTEIN 1905)
Light of frequency may be considered as a
collection of particles, called photons, each of
energy h.

If the minimum energy required to remove an

electron from the metal surface is (work
function), then if h < , no emission of electrons
occurs
Threshold frequency 0 given by = h0
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Quantum Theory
Explanation (EINSTEIN 1905)

For > 0, the

kinetic energy of
the
emitted
electron Ek = h
= h( 0).

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