M.Sc.

CHEMISTRY
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Paper-IV PHYSICAL CHEMISTRY

Lessons : 1 - 33

SCHOOL OF DISTANCE EDUCATION

ANDHRA UNIVERSITY,
VISAKHAPATNAM - 530 003
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SCHOOL OF DISTANCE EDUCATION

ANDHRA UNIVERSITY
VISAKHAPATNAM

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 M.Sc. (Previous) Chemistry
Paper - IV Physical Chemistry

Authors
1) Prof. K.M.M.Krishna Prasad 3) Prof. V. Suryanarayana Rao
Dept. of PNCO Sri Krishna Deva Raya University
Andhra University Anantapur
(1-9 and 11-15) (18,19)

2) Dr. K.Ramakrishna 4) Prof. R. Sambasiva Rao

Dept. of PNCO Dept. of PNCO Andhra
Andhra University University
(10) (16,17 and 20to 33)

EDITOR
Dr. R. Sambasiva Rao
Professor of Chemistry
Dept. of PNCO
Andhra University

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 Contents
L. No. Title Page No.

Syllabus
Model Question Paper
UNIT - I
01. Solids 01

02. X-Ray Diffraction Studies 05

03. The Bond Model 15

04. Theories of Specific Heats of Solids 23

05. Transport Properties of Gases 30

UNIT - II

06. Physical Methods for the Elucidation of

Molecular Structure 38

07. Nuclear Magnetic Resonance Spectroscopy 46

08. The Chemical Shift 53

09. Application of NMR Studies in Structural Elucidation 61

10. Electron Spin Resonance Spectroscopy 67

UNIT - III

11. Thermodynamics 75

12. Free Energy Functions 92

13. Free Energy Change Accompanying A Chemical Reaction 100

14. Nernst Heat Theorem 114

15. Third Law of Thermodynamics 123

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 Contents
L. No. Title Page No.

UNIT - IV

16. Kinetics Introduction 128

17. Collision Theory 131

18. Kinetic Isotope Effect 139

19. Salt Effect on Rate of a Reaction 146

20. Solvent Effect 151

21. Hammett Equation 162

22. Chain Reactions 168

23. Parellel Reaction 173

24. Acid-Base Catalysis 183

25. Fast Reactions 193

UNIT - V

26. Electro Chemistry 207

27. Determination of E0 (Standard Potential) 213

28. Effect of Complexation on Redox System 220

29. Photo Chemistry 223

30. Fluorescence 225

31. Stern-Volmer Equation 230

32. Grothus Draper Law 235

33. Photochemical Equilibrium 244

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 SYLLABUS
Paper IV - Physical Chemistry
Unit I :
States of Matter : Transport properties of gases - Thermal conductivity, viscosity
and diffusion, Theories of liquid structure - calculation of collision numbers.
Solids : X-ray diffraction studies - Fourier synthesis - crystal structure determination -
lattice types and lattice dimensions - crystal defects - linear point and edge defects - Band theory
solids - Theories of specific heats of solids - semiconductors and their properties.

Unit II :
Physical Methods for the elucidation of molecular structure - magnetic properties of
molecules - theories of magnetic susceptibility - Application of magnetic susceptibility
measurements to coordination compounds - spin-spin interactions - Chemical shift and its origin -
experimental methods - application of NMR studies in structural - elucidation - application to
structure of ethanol, acetophenone, acetamide, dimethyl formamide and styrene
- electron spin resonance - principle and experimental technique - line shapes and line widths - g-
value - hyperfine interactions - applications of ESR Studies to the structure of free radical, metal
complexes and biological systems.

Unit III :
Thermodynamics : Free energy entropy and enthalpy - Chemical equilibrium -
thermodynamic criteria of the chemical equilibrium - effect of temperature on equilibrium con-
stant - Vant Hoff isochore - Maxwell relations - Gibbs-Duhem equation Duheme - Margules
equation - classius - clapeyron equation - Nernst heat theorem and third law of thermodynamics -
determination of absolute entropy electro kinetic potential - Membrane potential.

Unit IV :
Kinetics : Theories of reaction rates - collision and transition state theories - study of fast
reactions using flow and relaxation methods - Kinetic isotope effects - reactions in solution -
primary and secondary kinetic salt effects - Effect of dielectric constant - elementary ideas of
linear free energy relations. Hammett and Taft equations - Chain reactions - consecutive parallel
and opposing reactions involving uni molecular steps only - Catalysis - homogeneous and
heterogeneous - acid - base and redox catalysis.

Unit V :
Photochemistry : Laws of photochemistry - photo physical processes fluorescence -
delayed fluorescence and phosphorescence - Stern - volmer equation - Inter system crossing -
internal conversion - photolysis - photosensitization and photochemical equilibrium.

Unit VI :
Electrochemistry : Theories of strong electrolytes - Debye - Onsager equation -
electrochemical cells - concentration cells with and without transference - effect of complexation
on redox potential Determination of activity coefficients from E.M.F. data.

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