Entrance Exam syllabus for Ph.D Chemistry

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1. Stereochemistry: Configuration and chirality, optical isomerism, R,S-convention, enantiotopic and diastereotopic groups, methods of resolution, asymmetric synthesis. Geometrical isomerism E,Z-convention. Conformational analysis; effect of conformation on reactivity.

2. Reactive Intermediatates: Generation, structure and reactions of carbocations, carbanions, nitrenes and free radicals.

3. Nucleophilic substitution: Mechanisms, Classical and nonclassical carbocations. Reactivity effects of substrate structure, attacking nucleophile, leaving group and reaction medium. Aromatic Nucleophilic substitution: Mechanisms, reactivity, effect of substrate structure, leaving group and attacking nucleophile.

4. Electrophilic Substitution: Mechanisms, effect of substrates, leaving group and the solvent polarity on the reactivity. Aromatic- the Arenium ion mechanism, orientation and reactivity, energy profile diagrams, quantitative treatment of reactivity in substrates and electrophiles.

5. Addition to Carbon-Carbon Multiple Bonds: Mechanism, direction and stereochemistry, addition to alkenes and alkynes, Transition metal organometallics.

6. Addition to Carbon-hetero Multiple Bonds; Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles, Addition of Grignard reagents.
6. Elimination Reactions: Reaction mechanism, Direction, stereochemistry, formation of alkenes , alkynes and other multiple bonds.

7. Ring Expansion and Contraction: Demjanov ring expansion, Favorskii rearrangement.

REFERENCES:
1. Stereochemistry of Carbon Compounds by E. J. Eliel, Tata Mc Graw Hill, 2002.
2. Stereochemistry of Organic Compounds by D. Nasipuri, Wiley, 1994.
3. Organic Chemistry by J. M. Hornback, Books Coley, 1998.
4. Organic Chemistry by P. Y. Bruice, Prentice Hall , 1998.
5. Organic Reaction and their Mechanisms by P. S. Kalsi, New Age International Publishers , 2nd edition, 2007.
6. Modern Synthetic Reaction by H. O. House, W. A. Benjamin, Inc, 1972.


Thermodynamics and Chemical Kinetics
1. Law of Thermodynamics: Exact and Inexact Differentials, Cyclic Rule, Reciprocity Characteristics, Homogenous Function, Euler’s Theorm, third Law of thermodynamics, Nernst Heat theorm, Thermodynamic Properties at Absolute Zero, Entropy & Third Law of Thermodynamics.

2. System of Variable Compositions: Partial Molar Quantities, Chemical Potential and its Variation with Temperature and Pressure, Chemical Potential of Real Gases & Fugacity, Chemical Potential in ideal Gas Mixture, Concept of Escaping Tendency.

3. Physical Transformation of Pure Substances and Simple Mixtures: Phase Diagrams, Phase Stability and Phase Transitions, The Physical Liquid Surface, Thermodynamics function of Mixing.

4. Chemical Equilibrium: Spontaneous Chemical Reactions, Response of Equilibria to the Conditions, Thermodynamic Properties of Ions in Solution.

5. Chemical Kinetics: Collision theory of Reaction Rates, Arrhenius Equation and Activated Complex Theory, Comparison of Collision and Activated Complex Theory.

6. Advanced Chemical Kinetics: Applications of Activated Complex Theory, RRK and RRKM Theory, Theories of Unimolecular Reactions.

7. Dynamics of Complex Reactions: Ion-Ion Reactions, Ion-Dipole reactions, Enzyme Kinetics, polymerization Kinetics, Kinetic Salt, Salt Effect.

8. Dynamics of Fast Reactions: General Treatment of Chain Reactions, Theories of Branching Chain and Explosion, Flow Methods, Relaxation Techniques, Flash Photolysis.

REFERENCES:
1. Thermodynamics A core Course by R. C. Srivastva, S. K. Saha, A. K. Jain, PH I, New Delhi, 2007.
2. Physical Chemistry, P. Atkins, J. D. Paula, Oxford University Press, 7th Indian Edition, 2007.
3. An Introduction to Chemical Thermodynamics by R. P. Rastogi & R. R. Mishra, Vikas Publishing House, 6th Edition , 2007.
4. Chemical Kinetics by Keith J. Laidler, Pearson Education, 3rd Edition.
5. Chemical Kinetics by K. A. Corrnors, VCH, 1998.
6. Physical Chemistry by R. S. Berry, S. A. Rice & J. Ross, Oxford University Press 2nd Edition, 2000.
7. Fast Reactions J. N. Bradley, Oxford University press, 1975.


Main Group Chemistry
1. Chemistry of hydrogen: Ionized forms of Hydrogen, Protonic acids and bases, The Hydrogen Bond, its influence on Properties and influence on structure, Strength of hydrogen bonds and theoretical description.

2. Chemistry of S-block metals: Hydrides, Halides, Oxides, Peroxides, Superoxides, Suboxides, Hydroxides, Oxoacid salts Complexes Crowns and Crypts of Alkali Metals and coordination complexes of Alkaline Earth Metals.

3. Chemistry of Boron and Aluminum: Boranes, Bonding in boranes, topology of boranes, synthesis and reactivity. Carboranes and mettallocarboranes,Borazine and boron nitride. Chemistry of Aluminum Halides. Aluminum Alkyls. Low oxidation state Al compounds.

4. Chemistry of Silicon: Organosilicon Compounds. Sillicates and Aluminosilicates. Low-valent Silicon compounds, silylenes and R3Si+.

5. Inorganic rings, Cages, Clusters and Polymers: Phosophazenes, Cyclophosphazenes , Polyphosphozenes and the polymers derived from them. Polysilanes.

6. Chemistry of halogens and nobel gases: Inter Halogens, Poly Halide Anions, CFC’s , Ozone layer and Clathrates.

7. Chemistry of group 12 elements: Halides & Oxygen compounds, chalcogenides & Related compounds, low-valent compounds & Formation of coordination complexes.

References:
1. Main Group Chemistry, W. Henderson, Royal Society of Chemistry, 2000.
2. Advanced Inorganic Chemistry, F. A. Cotton and G. Wilkinson et. al, Sixth edition John Wiley & Sons, 2003.
3. Inorganic Chemistry, J. E. Huheey et. al, Fourth edition, Pearson, 2005.
4. Concepts & Model of Inorganic Chemistry, B. Douglas et. al, 3rd John Wiley & Sons, 2001.
5. Chemistry of Elements, N. N. Greenwood, Pergamon Press, 2000.
6. Inorganic Chemistry 4th edition D. F. Shriver and P. W. Atkins, Oxford University, Oxford, 2006.


Basic Biological Chemistry
1. Cell :Types of cells and structure and functions
2. Introduction to Biomolecules: Carbohydrates, Proteins, Amino acids, Lipids and phospholipids, Biological membranes, transport across membranes.

3. Nucleic Acids: Base pairing, double helices, DNA replication, transcription and translation.

4. Enzymes: enzyme kinetics and mechanism, nature and application of enzymes.

5. Biotechnology and its Applications: Genetic engineering, Potential laboratory biohazards of genetic engineering, Polymerase chain reaction, Pharmaceutical and biopharmaceuticals, Vaccines and monoclonal bodies ,Waster water and sewage treatment, landfill technologies.

6. Transmission of Nervous impulse & mechanism: Neurons and its Structure, Nerve Transmission, Nerve poisons.

REFERENCES:
1. Biotechnology, by J. E. smith, 4th edition, Cambridge, 2004.
2. Principle of Biochemistry by Lehinger, Nelson and Cox, CBS publisher 1993.
3. Principles of Biochemistry ,by T.N. Pattabiraman , Gajanana book publishers and

Distributors, 1993.

Quantum Chemistry
1. Foundations of Quantum Mechanics: Operators, Postulates, Matrices and Schrodinger Equation.

2. Linear Motion and harmonic Oscillators: Translational, harmonic, particle in a box a penetration through barriers.

3. Rotational motion and hydrogen atom: Particle in a ring & on a sphere, motion in a columbic field.

4. Angular momentum: Angular momentum operators, definition of states, Composite systems.

5. Techniques of Approximation: Perturbation theory, variation theory, HF theoretic, time dependent perturbation.

6. Atomic Structure: Hydrogen, Helium & multi electron system.

7. Molecular Structure: Born- openheimer approximation MO theory of mono, dia & polyatomic molecules, band theory of solids.

8. Electronic Structure: SCF method electron correlation Density functional theory, gradient method, semi-empirical methods & software packages for calculations.

9. Molecular Rotation & Vibration: Rotation & Vibration in diatomic, polyatomic molecules.

10. Electronic Transition in molecules: Rotational, Vibronic and electronic states & fates of excited species.

REFERENCES:
1. Quantum Chemistry, I. N. Levine, Prentice Hall, 2000.
2. Molecular Quantum Mechanics, P. W. Atkins and R. S. Friendman, OUP, 1997.
3. Physical Chemistry-by P. W. Atkins, Oxford University Press, 1990.
4. Introduction to Quantum Mechanics with Applications to Chemistry, L. Pauling and E. B. Wilson, Dover NY, 1985.


Pharmaceutical Chemistry
1. Drug Discovery and Drug Development: Introduction, Present and Past, Drugs and the medicinal chemist, Classification of drugs, Drug targets specification, Choice of Bioassay, In Vivo and in Vitro tests, Pit falls.

2. Drug Action at Receptors: Receptor role, Neuro-transmitters and Hormones, Change of shape by the receptors, Design of Agonists and Antagonists, Drug action on DNA and RNA.

3. Drug Design, Drug-Target Interactions: Introduction, Variation of Substituent, Expansion of the Structure, Chain expansion/Contractions, Ring expansion/Contractions, Ring Variation, Ring Fusions, Isosteres.

4. Pharmacokinetics: Drug distribution and survival, Pharmacokinetic issues in drug design like Chemical and Metabolic stability, Hydrophilic / hydrophobic balance, Ionization, size and number of hydrogen bonding interactions, Drug dose levels, solubility and membrane permeability, variation of different groups to alter polarity.

5. Prodrugs: Introduction, Effect of prodrugs on: improved membrane permeability, prolonged drug activity, masking drug toxicity and side effects, increased chemical stability, targeting of drugs, prodrugs activation by external influence.

6. Drug administration: Introduction, oral administration, sublingual administration, rectal administration, epithelial administration, inhalation, injection and implants.

REFERENCES:
1. Textbook of Pharmacology, W. C. Bowman, and M. J. Rand, Blackwell Scientific 1980.
2. Medicinal Chemistry-the role of organic chemistry in drug, C. R. Ganellin, and S. M. Roberts, , research, Academic Press 1993.
3. Medicinal Chemistry-principles and practice, F. D. King, , The Royal Society of Chemistry 1994.
4. Burger’s Medicinal Chemistry and drug discovery, M. E. Wolff, 5th edition Volume 1-5. Wiley 1995.

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Stereochemistry
Baldwin’s Rule and Dunitz’s angle of attack
Cieplak Model
Felkin-Ahn Model
Optical purity
Sterospecific and stereoselective synthesis
Conformation analysis of cycloalkanes
Cram’s Model
Enatiotopic and diastereotopic atoms, groups & faces

Organic Reaction Mechanisms
Arndt-Eistert Synthesis
Beckmann Rearrangement
Pinacol-Pinacolone Rearrangement
Sandmeyer reaction
Smiles Rearrangement
Wagner-Meerwein Rearrangement
Benzil-Benzilic acid
Carbanions
Carbenes
Favorskii Rearrangement
Free radicals
Gattermann-Koch reaction
Hunsdieker reaction
Mechanism of nucleophilic substitution
Nitrenes

Oxidation and Reduction
Baeyer Villiger Oxidation
Catalytic Hydrogenation
Prevost Reaction
Swern oxidation
Wolf Kishner Reduction
Clemmenson’s Reduction
Metal Reductions
Meerwin Pondorf Varely Reduction
Oppenauer oxidation

Heterocyclic Chemistry
Diels-Alder Reaction
Pal-Knorr synthesis
Principles of heterocyclic synthesis

Chromatography
Classification of stationary and mobile phase
Principle and examples of detection methods
Thin Layer Chromatography (TLC)
Column Chromatography
Normal and Reverse Phase Chromatography
Paper Chromatography
Preparative TLC

Reaction Mechanism of Transition Metal Complexes
Acid hydrolysis
Application of valence bond and crystal field theory
Redox reactions
Substitution reaction in square complexes
Trans effect
Base hydrolysis
Electron transfer reactions
Energy profile of a reaction
Kinetics of octahedral substitution
Reactivity of metal complexes

Metal carbonyls and related complexes
Structure and bonding
Structure and bonding of transition metal complexes
Synthesis, reaction and vibrational spectra

Metal-Ligand Bonding
Concept of a Ligand field
Scope of Ligand field theory
Qualitative demonstration of ligand field effect

Introductory Quantum Chemistry
Black body radiation
Emergence of quantum mechanics
Planck’s concept of quantization
Planck’s equation
Uncertainty principle
Wave particle duality

Electrochemistry
Debye-Huckel Theory
Derivation of Debye-Huckel-Onsager equation
Primary & secondary cell
Fuel cell
Potentiometric titrations
Determination of pH and solubility product
Thermodynamics
Batteries

Chemical kinetics
Activation parameters and their significance
Catalyst
Collision theory
Complex reactions
Transition state theory
Unimolecular reactions and Lindamann’s theory
Correlations for nucleophillic reactions
Eyring equation
Taft four-parameter equation
The Swain – Scott equation and the Edward equation
Theories of reaction rates
Thermodynamic formulation of transition state theory

Thermodynamics
First and II laws of thermodynamics
Concept of entropy-entropy
Entropy changes in various processes
Entropy as a function of V and T, P and T
Clapeyron equation
Clausius-Clapeyron equation
Closed system
Chemical potential of ideal gases
Ideal-gas reaction equilibrium
Hoff equation
Entropy change in isolated systems
Entropy changes on mixing of ideal gases
Clausius inequality
Entropy change as criterion for spontaneity and equilibrium
Third law of thermodynamics
Evaluation of absolute entropies
Standard entropies and entropy changes of chemical reactions
Helmholtz and Gibbs
Phase equilibrium