BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Semester II: AY 2021-22
Lecture- 01, 09 May 2022, Monday

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General Chemistry - Overview of handout
Instructor-in-Charge : ANIL KUMAR
Instructor(s) : S. C. Sivasubramanian,
Anil Kumar, Ajay Kumar Sah
Tutorial Instructors : Indresh Kumar, Surojit Pande,
Bharti Khungar, Pritam Kumar
Jana, Avik Kumar Pati, Satyajit
Patra, Bibhas Ranjan Sarkar
Course Description: Principles of thermodynamics, phase and
chemical equilibrium, electrochemistry, kinetics; atomic structure,
chemical bonding, solid state and structural chemistry, molecular
spectroscopy; organic compounds, functional groups, structure and
isomerism, stereochemistry, reactions and mechanisms, aromaticity,
coordination chemistry, chemistry of representative elements.

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General Chemistry - Overview of handout

Scope and Objective of the Course:

The course is composed of two parts. The first part
provides a comprehensive survey of various topics in
electronic structure of atoms and molecules, spectroscopy,
and bonding; and the second part focuses on understanding
of the structure and reactivities of Organic and Coordination
compounds. Organic structure identification by NMR
spectroscopy will be introduced in part two.
Overall objective of the course is that the student
should be exposed to some of the fundamental principles of
stability of chemical structures and should be able to
approach the chemical reactions in a systematic and logical
way based on electronic structure theory.
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 Books
Text Books
T1: P.W. Atkins and Julio de Paula, Elements of Physical Chemistry: 6th
Edition, Oxford University Press, Oxford, reprinted in 2015.
T2: T. W. Graham Solomons, Craig B. Fryhle and Scott A Snyder, Organic
Chemistry, 12th Edition, John Wiley & Sons, Inc. New York, 2017
Reference Books:
R1: J. D. Lee, Concise Inorganic Chemistry, 5th Edition, Blackwell
Science, Oxford, 1999.
R2: David Ball, Physical Chemistry, Brooks/Cole Thomson Learning,
2003.
R3: Huheey and Keiter, Inorganic Chemistry: Principles of Structure and
Reactivity, 4th Edition,
R4: R. T. Morrison and R. Boyd, ‘Organic Chemistry’, 6th Edition, PHI,
New Delhi, 1992.
BITS Pilani, Pilani Campus
Overview of handout
(14 Lectures) (13 Lectures)
• Quantum theory • NMR spectroscopy
• Atomic structure and • Conformation
Chemical bonding • Stereochemistry
• Spectroscopy: • Types of reactions:
 Rotational & Raman  Elimination; Addition;
 Vibrational  Substitution; Pericyclic
reactions
• Aromatic compounds
• Reaction Mechanisms
• Coordination compounds (10 Lectures)
 CFT; Distortion of Geometries;
 Stability of Complexes; Electronic Spectroscopy
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General Chemistry (Evaluation components)
Component Duration Weightage % Date and Time Remarks
[Marks - 200] (may change)
Mid- Sem. 90 min. 30 June 29 – July 02 Open book
Test. [60 M] Details later

Continuous Details 30 Continuous Closed/Open

Evaluation‡ later [60 M] Book
(Quiz/
Assignment)
Comprehensive 3 hours 40 Aug 13 (AN) Closed Book
Exam. [80 M]

‡A total four quiz/assignment (each of 20 marks) will be conducted

under continuous evaluation. Best three will be considered for final
evaluation.
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General Discussion

Why do chemical reactions happen ?

Two Principles:
1. All systems want to move towards a minimum
energy (stable) configuration.
2. All systems want to occupy more space
(expand/ more disorder).
Example:
A+ A  A2 Favored by Principle 1. Why?
All Bond formations are energy releasing processes.
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General Discussion
Other side of the coin:
A2  A +A Favored by Principle 2. Why?
All bond dissociations bring in more disorder; more
entropy; more space occupation.
Which principle works? Both
A+ A ⇄ A2
∆G = ∆H - T∆S = -ve for spontaneity
Some actual examples will be discussed in future lectures;
Let us focus on principle 1; i.e., Bond formation releases
energy; Can we show this from fundamental principles?
Yes. Objective of the initial lectures will be towards this.
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General Discussion
One more Question?
What is an orbital?
y = f(x) ; y is a function of x.
w = f(x, y, z); …..three independent variables.
ψ = f (r, θ, ɸ)

ψ if it satisfies certain conditions it will be an orbital;

An orbital is an one electron wavefunction.
Why these mathematical functions play an
important role in chemistry and physics? We will
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Quantum Theory: Background

Classical Physics:
Describes the motion of macroscopic objects,
from pendulum, projectiles to parts of machinery, as
well as astronomical objects such as spacecrafts,
planets, stars, and galaxies.
Newton’s Laws of motion (1687)
Newton’s Theory of gravity
Euler’s Law of motion
Galileo’s Contribution to astronomy
Classical Thermodynamics by Joule, Maxwell
Unaltered for three centuries till end of 19th Century
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 Classical Mechanics: Consequences
1. Predict a precise trajectory for particles with precisely
specified locations and momenta at each instant.
2. Any kind of motion can be excited to any arbitrary value
of the energy.
3. Waves and Particles are distinct concepts.

Certain Phenomena were unexplainable ???

? Black body radiation
? Photoelectric effect
? Electron diffraction
? Line spectra of atoms
……….Foundation of Quantum Mechanics
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Black body
• Study of Interaction of light with matter was in progress.
(How light was emitted or absorbed ??)
• Any object radiates energy, when heated. The amount of
energy emitted, and its frequency distribution depends on
the temperature (and on the material ?).
• Black Body: An opaque object that is a perfect absorber
and a perfect emitter.
- At room temperature, such an object
would appear to be perfectly black.
- If heated to a high temperature, it
will begin to glow with thermal radiation
Nearly-perfect
Actual black bodies don't exist in nature black body
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Black body radiation-the phenomena
• Such solid black bodies, when heated to glowing emitted a
continuous spectrum composed of all wavelengths of light,
called Black Body/cavity/complete/thermal radiations.
• The distribution of absorbed or emitted radiation depends
on the absolute temperature, not on the body material.

 At constant T, Intensity increases

as λ increases, attains a maximum

Intensity (I) or
Power density
value and then decreases. ?
 Not all the wavelengths of light are
emitted with equal intensity. Wavelength

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Wien’s Observation: 1893

Wilhelm Wien quantified the

relationship between blackbody
temperature and the wavelength
of the spectral peak.

With increase in T, the λmax shifts

towards shorter wavelength.
λmax T = b
b = 2.9 mmK = 0.29 cmK
[Wien’s Displacement Law]

The wavelength of maximum emission from a blackbody is

inversely proportional to its temperature.
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Stefan-Boltzmann Observations: 1884

The Stefan–Boltzmann law describes the power radiated

from a black body in terms of its temperature.
Area under the curve at T =
Total Power per unit surface area (M)
M is proportional to 4th power of absolute temperature

M = σT4 [Stefan-Boltzmann Law]

(W/m2) Used to estimate the
 = 5.6697 x 10-8 Wm-2K-4 temperature of Sun

The Sun at 5800 K and a hot campfire at perhaps

800 K give off radiation at a rate proportional to
the 4th power of the temperature

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 Blackbody Radiation: Explanation
I. Rayleigh-Jeans Explanation (1900-1905)
The Rayleigh-Jeans Radiation Law was a useful but not
completely successful attempt at establishing the functional
form of the spectra of thermal radiation through classical
arguments.
This attempt was based on certain assumptions (believed to be
true at that time).
Assumptions:
 Black body cavity is made up of charged particles which
behaves as tiny oscillators by thermal accelerations and emit
radiations.
 Energy emitted by atomic oscillations could have any
continuous value.

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Rayleigh-Jeans Law
Energy density (dE = d) is the energy per unit volume
associated with radiation of wavelength from λ to λ+dλ :

dE =  dλ = (8πkT/λ4) dλ
k =Boltzmann constant

 Energy density raises without

bound as λ decreases.
 Infinite energy density at
short wavelengths. (Infinite
energy in the system!

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Rayleigh-Jeans Law:
unsuccessful attempt to explain the black body radiation
spectrum.
Rayleigh-Jeans Equation predicts that
Oscillators of short wavelength (UV) are excited even at
room temperature.: This cannot be true

This paradox: Real

ULTRAVIOLET CATASTROPHE! Picture

 Quite Successful at long wavelengths.

 Rayleigh-Jeans Law predicts an Ultraviolet catastrophe that
does not occur in real.
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Blackbody Radiation: Explanation
II. Planck’s Explanation (1900-1905)
Attempts to describe the emission spectrum from a black
body at a given temperature through Quantization
hypothesis.

Crucial Assumption:
• An oscillator of frequency ν cannot
be excited to any arbitrary energy, but
to only to integral multiples of a
fundamental unit or quantum of
energy hν; h = 6.626 x 10-34 Js, the
Planck’s constant.
ΔE = nhν
i.e. Energy of an oscillator is quantized

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Planck Radiation Distribution Law

dE= d= (8π/λ4) dλ (hc/λ) [e(hc/λkT) -1]-1

Average
energy
c is speed of light, k is Boltzmann’s constant and h is Planck’s constant.

Planck’s proposed empirical

formula describe the curve of
blackbody radiation exactly for all
wavelengths.

Planck expression reproduces

the experimental distribution
with h = 6.626 x 10 –34 Js
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Planck Law: Success story
 Planck's hypothesis: An oscillator cannot be excited unless it
receives an energy of at least hν (as this is the minimum amount
of energy an oscillator of frequency ν may possess above zero).

 For high frequency oscillators (large ν, low λ), the amount of

energy hν is too large to be supplied by the thermal motion of
the atoms in the walls, and so they are not excited.
dE = (8πhc/λ5) dλ [e(hc/λkT) -1]-1

At small , ehc/kT   faster than 5

UV Catastrophe
(Exponential is large)
avoided
Energy density 0 as   0

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The Magic of Planck’s formula
Total energy radiated per unit area per
2𝜋𝑘 4 maxT = hc/5k (constant)
unit time: E =  T4 = T4
15𝑐 2 ℎ3 Wien’s Law
Stefan Boltzmann Law
Differentiate d/dλ = 0 for
E = ( (λ, T) dλ
calculating max (at low λ)

dE = dλ = (8π/λ4) (hc/λ) [e(hc/λkT) -1]-1 dλ

exp (hc/λkT) = 1 + hc/λkT +1/2(hc/λkT)2 + ……
For long wavelengths,
when hc/λ << kT Dropping

Rayleigh-Jeans formula
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