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Pilani Campus

Welcome
CHEM F111 : General Chemistry
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General Chemistry (Overview of handout)
(2018-19: II Semester)
(20 Lectures) (12 Lectures)
• Quantum theory • Conformation
• Atomic structure and• Stereochemistry
Chemical bonding • Types of reactions:
• Spectroscopy: • Elimination; Addition;
• Rotational & Raman Substitution; Pericyclic
• Vibrational • Aromatic compounds
• NMR • Reaction Mechanisms

• Coordination compounds (9 Lectures)

• CFT; Distortion of Geometries; Stability of Complexes;
Electronic Spectroscopy
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General Chemistry (Overview of handout)
(2018-19: II Semester)

Modules 14 (Lectures 41) Refer to Handout for Details.

Module 1-5 (12 Lectures) S. C. Sivasubramanian

Module 6-9 (13 lectures) Bibhas Ranjan Sarkar

Module 10-14 (16 lectures) Indresh Kumar

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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:J. E. Huheey, E. A. Keiter et al., Inorganic Chemistry: Principles of
Structure and Reactivity, 4th Edition, Pearson Education, 1993.
R4: R. T. Morrison and R. Boyd, ‘Organic Chemistry’, 6th Edition, PHI,
New Delhi, 1992.
BITS Pilani, Pilani Campus
General Chemistry (Evaluation components)

Component Durati Weightage Date and Remarks

on % Time
[Marks]
Mid- Sem. Exam. 90 min. 30 15-Mar-2019 Closed book
[90 M] 9-10:30AM

Continuous 15 min. 25 Continuous (i) 4 Quizzes: Variety of

Evaluation (each) [75 M] questions; MCQ, Fillings,
(Best 5 out of 6) short answers etc. (closed
book)
(ii) 2 Assignments: Pre
announced problem set;
evaluation in Tutorials
(closed book).
Comprehensive 3 hours 45 10-May-2019, (i) 20% Closed Book (Quiz)
Exam. [135 M] FN
(ii) 25% Open Book
(Descriptive)

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 General

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.
Example:
A+ A  A2 Favored by Principle 1. Why?
All Bond formations are energy releasing
processes.

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 General

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
Real Examples will be discussed in some lectures
of Inorganic, and Organic portions.

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 General

Thermodynamics deals with Bulk matter.

How does the energy minimization occurs during

bond formation between atoms?

To understand these microscopic level

phenomena we have to use something other
than classical physics known as quantum
physics.

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 General

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.
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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 spacecraft, planets, stars, and galaxies.
Newton Laws of motion (1687)
Newton Theory of gravity

Newton, Euler, Lagrange, Hamilton, Galileo et al.,

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.

• 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 value and
?
Intensity (I) or
Power density
then decreases. Thus not all the
wavelengths of light are emitted equally.

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.
Used to estimate the temperature of hot bodies from a distance (Sun,
stars)
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Stefan-Boltzman 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)
 = 5.6697 x 10-8 Wm-2K-4

The Sun at 5800K (Surface) 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 (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 rises 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 Real
Picture

This paradox:
ULTRAVIOLET CATASTROPHE!

 Quite Successful at long wavelengths.

Θ 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 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 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’s 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 ), 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
unit time: E = 2π5k4/15c2h3)T4 maxT = hc/5k (constant)
= σT4 Stefan Boltzman Law Wien’s Law

Differentiate d/dλ and = 0

E = ( (λ, T) dλ for 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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Classical Mechanics: Failures

Example 2:
Photoelectric Effect

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Photoelectric Effect

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Failure of Classical Physics to Explain
Photoelectric Effect
Classical Believes The Facts
 No. of Electrons emitted • No electrons are ejected if the
should depend on intensity and frequency of radiation is below a
not on frequency. threshold value characteristic of
the metal.

 K.E. should depend on the • K. E. of emitted electrons

amplitude of the oscillation of the varies linearly with the frequency,
incident radiation. and is independent of light
intensity.
 The energy of the incident light • For frequencies above the
is spread over as a wave front and threshold value, emission of
some time will be required by an electrons is instantaneous, no
electron to absorb enough energy to matter how low the intensity of
escape. the light. (Absence of time lag)
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Photoelectric Effect: Einstein Explanation

 Einstein (1905) applied Planck’s quantized-energy assumption

 Light of frequency  may be considered as a collection of

particles, called photons, each of energy h.
Particle Character of Light

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Photoelectric Effect: Einstein Explanation

 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

 = h0

 For  > 0, Ek = h   = h(  0).

1/2mv2 = h   = h(  0).

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