BITS Pilani

Pilani Campus

CHEM F312 : Physical Chemistry IV

Semester I: AY 2022-23
Lecture-01, 5 Sep 2022, Monday

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 Physical Chemistry IV
(Overview of handout)
1. Course Description:
Weak forces; surface chemistry: interphase region,
thermodynamics, surface films on liquids, adsorption of gases on
solids, colloids, micelles, and reverse micellar structures;
transport processes: kinetics, thermal conductivity, viscosity,
diffusion, sedimentation; electrical conductivity in metals and in
solutions; reaction kinetics, measurement of rates; integrated
rate laws; rate laws and equilibrium constants for elementary
reactions; reaction mechanisms; temperature dependence of
rate constants; rate constants and equilibrium constants; rate law
in non ideal systems; uni, bi and tri molecular reactions, chain
reactions, free-radical polymerizations; fast reactions; reactions
in solutions; heterogeneous and enzyme catalysis; introduction
to statistical mechanics; theories of reaction rates; molecular
reaction dynamics.
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 Physical Chemistry IV
(Overview of handout)
2. Scope and Objective of the course:
This is the last one of the four Physical Chemistry courses named
for M.Sc. Chemistry (Integrated 4 year degree) Programme. The
course mainly covers chemical changes in terms of chemical
kinetics, surface and interfacial phenomena, and the associated
theories. The objective is to understand the chemical changes
and also to be able to connect these changes to structure and
equilibrium properties learnt in the previous courses.

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 Physical Chemistry IV
(Overview of handout)
3. Text Book :
T1. Levine Ira N., Physical Chemistry, 6th ed., Tata McGraw-Hill,
New Delhi, 2011.
Reference Book :
R1: Peter Atkins and Julio de Paula, Atkins’ Physical Chemistry,
10th Ed., Oxford University Press, Oxford, 2014.

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 Physical Chemistry IV
(Overview of handout)

Lecture Hours:
Mon-Wed-Fri 10 am (3rd hr.)

Tutorial:
Dr. Pritam Kumar Jana
Thursday 5pm (10th hr.)

Chamber Consultation Hr.:

Saturday 5th Hour 12 noon (SCS) -3268 V
You can contact me by mail for any issues.

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 Physical Chemistry IV
(Overview of handout)
Partition function, thermodynamic
Statistical
1-4 information from canonical partition T1: 21.2 – 21.4
Mechanics
function.
Molecular partition function, The
T1: 21.5 –21.6,
5-8 “ Boltzmann distribution, equilibrium
21.8- 21.9
constants, entropy and third law.
Rates of
Definition of rate, derivation of
chemical
concentration time relationship for T1: 16.1 - 16.4
reactions;
simple reactions, determination of rate (16.7)
9-12 Integrated
law, half-life of reactions, reactions
rate laws;
approaching equilibrium, Exptl.
Finding of
Procedures to obtain rate laws.
rate law.

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 Physical Chemistry IV
(Overview of handout)
Elementary reactions, composite
reactions, steady-state T1: 16.5 -
Elementary
13- approximation, rate determining 16.6,
reactions,
15 step, rate constants and 16.9-
Mechanisms
equilibrium constants; rate laws for 16.10
non-ideal systems.
Temperature
16 effects on Concept of activation energy T1: 16.8
rates
Unimolecular
17- and Lindemann-Hinshelwood T1: 16.11
19 Trimolecular mechanism - 16.12
reactions

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 Physical Chemistry IV
(Overview of handout)

Polymerization kinetics, free-

20- Chain T1:
radical polymerization
21 reactions 16.13
reactions
Fast
reactions T1:
22- Concepts of relaxation,
and 16.14 -
24 diffusion controlled reactions
reactions in 16.15
solutions
Homogene T1:
25- Enzyme catalysis, Michaelis-
ous 16.16 -
26 Menton equation
catalysis 16.17
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 Physical Chemistry IV
(Overview of handout)
Adsorption of Extent of adsorption, Physisorption
27-
gases on and chemisorptions, Adsorption T1: 16.18
28
solids isotherms
29- Heterogeneo
Rates of surface processes T1: 16.19
30 us catalysis
Theories of
31 Collision Theory T1: 22.1,
reaction rates
32- Reaction trajectory; Molecular T1: 22.2-
“
33 reaction Dynamics 22.3

34- T1: 22.4,

“ Transition State Theory
35 22.6-22.7

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 Physical Chemistry IV
(Overview of handout)
Reactions Extending the gas phase theories to the
36 T1: 22.8
in solution solution phase
Electric dipole moment, Polarization, R1: 16A –
Weak Interaction between dipoles, Interaction 16B
37
forces between induced dipoles, Hydrogen bonding, T1: 13.14,
Total attractive and repulsive interactions 21.10
Molecular interactions in gases, Liquid- T1: 7.6 - 7.8
Surface
38 vapour interface, surface films, R1: 16C
Chemistry
Thermodynamics of surface layers
Colloids,
Classification, Preparation, Structure & R1: 17C-
micelles,
stability of colloids, Micelle formation, 17D
39 and reverse
Reverse micellar structures, bilayers, T1: 7.9
micellar
Determination of size & shape
structures
Kinetics, viscosity, diffusion, sedimentation,
Transport T1: 15.1 -
40 electrical conductivity of solids and
processes 15.7
electrolyte solutions
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 Physical Chemistry IV
(Overview of handout)

Components Duration Marks (% Date & Time Exact

weightage) Details Remarks
Mid – Sem. Test 1 hr 30 min 70 (35) Nov 3, Thu – AN1 OB
To be
Tutorials: quiz, 30 min 60 (30) Continuous (3 annou- @
assignments (each) out of 4) -nced
etc. by
AUGSD
Comprehensive 3 hrs. 70(35) Dec 26, Mon - FN OB
Examination

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Statistical Mechanics
Statistical Mechanics

A bridge for
Quantum Mechanics  Thermodynamic properties

Molecular Properties: Geometry, intra/inter molecular

forces etc.

Thermodynamic Properties: entropy, viscosity etc.

Equilibrium Stat. Mech. = Statistical Thermodynamics.

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Statistical Mechanics

A lot from Kinetic Theory of Gases ( Maxwell &

Boltzmann, Gibbs, Einstein)

Initial Development was based on Classical Mechanics;

Corrected for Quantum Mechanical results.

Wave equation  QM equation if we apply deBroglie

condition : p = h/λ

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Statistical Statistical Mechanics

We will mostly develop the theory assuming ideal gas

conditions in this course.

At the end we will try to connect with some non-ideal

systems

System: Macroscopic Thermodynamic System

Molecules/particles: Fundamental microscopic entities

that compose the system. (Photons/electrons etc. are
also included)

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Statistical Statistical Mechanics

Macrostate: Thermodynamic state of the system.

Enough parameters to characterize the system,
Composition, Temp, Pressure/Volume etc.

Example: 18.0g of water, 54o C, 17.2 cm3 etc.

Microstate: For a macrostate many microstates are

possible. Also known as quantum state.
Consider 18.0 g of water: The wavefunction has to
include 6.02x 1023 x (10 electrons + 3 nuclei) spin,
spatial coordinates. Impossible to solve or use.

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