Physical Organic Chemistry

Paper Code: 
CHY - 425(D)
Credits: 
3
Contact Hours: 
45.00
Max. Marks: 
100.00
Objective: 
To learn the physical aspects of organic reactions, which are studied earlier.
 
9.00
Unit I: 
Principle of Reactivity and Isotope Effect
Mechanistic singnificance of entropy, enthalpy and Gibb’s free energy, Arrhenius equation, transition state theory, uses of activation parameters, Hammond’s postulate, Marcus theory of electron transfer, reactivity and selectivity principles, theory of isotope effects, primary and secondary kinetic isotop effects, heavy atom isotop effects, tunneling effect, solvent effects.
 
9.00
Unit II: 
Structural Effects on Reactivity
Linear free energy relationships (LFER), the Hammett  equation, substituent, constants, theories of substituent effects, interpretation of σ values, reaction constant ρ, deviations from Hammett equation, dual-parameter corrections, inductive substituent constant, the Taft model σI - and σR – scales. 
 
9.00
Unit III: 
Steric and Conformational Properties
Various type of steric strain and their influence on reactivity, steric acceleration, molecular, measurements of steric, effects upon rates, steric LFER, conformational barrier to bond. Rotation-spectroscopic detection, of individual conformers , acyclic and monocyclic, systems, rotation around partial double bond, Winstein-Holness and Curtin-Hammett principle.
 
9.00
Unit IV: 
Acids, Bases, Electrophiles, Nucleophiles and Catalysis
Acid-base dissociation, electronic and structural effects and basicity, acidity functions and their applications, hard and soft acids and bases, nucleophilicity, scalesl nucleofugacity, the 
α- effect , ambivalent nucleophiles, acid-base catalysis- specific and general catalysis, Bronsted catalysis, nucleophilic catalysis, catalysis by non-covalent-micellar catalysis.
 
9.00
Unit V: 
Molecular Dynamics
Principle of molecular association and organization as exemplified in biological macromolecules like anzymes, nucleic acids, membranes and model systems like micelles and vesicles, molecular receptors and design principle, cryptands, cyclophanes, calixeranes, cyclodextrines, supramolecular reactivity and catalysis, molecular channels and transport processes, molecular devices and nanotechnology.
 
Essential Readings: 
  1. Molecular Mechanics, U. Burkert and N.L. Allinger, ACS Monograph 177, 1982
  2. Mechanism and Theory Inorganic Chemistry, T.H. Lowry and K.C. Richardson, Harper and Row.
  3. Physical Organic Chemistry, N.S. Isaacs, ELBS/Longman
  4. Supramolecular Chemistry; Concepts and Perspectives, J.M. Lehn, VCH
 
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