UPHESC CHEMISTRY ASSISTANT PROFESSOR SYLLABUS

UNIT 1

STRUCTURE AND BONDING

Atomic orbitals, electronic configuration of atoms (L-S coupling),periodic properties of elements

Ionic radii, ionisation potential, electron affinity,electronegativity, concept of hybridization

Molecular orbitals and electronic configuration of homonuclear and heteronuclear diatomic molecules. Shapes of polyatomic molecules and ions

VSEPR Theory

Symmetry elements and point groups for simple molecules, character tables and its application

Symmetry consideration in coordination compounds and symmetry aspects of molecular orbital and ligand field theories

UNIT-2

Chemistry of Non-transition Elements

General discussion on the properties of the non transitional elements

special features of individual elements

preparation, properties and structure of their halides, oxides etc

Polymorphism of carbon, phosphorus and sulphur

Synthesis, properties and structure of boranes, carboranes, borazines, silicates, carbides, silicones, phosphazenes, sulphur -nitrogen compounds, peroxo compounds of boron, carbon and sulphur, oxy acids of nitrogen, phosphorus, sulphur and halogens, interhalogens, pseudohalides and noble gas compounds

Bio inorganic chemistry

Metal ions in biology, molecular mechanism of ion-transport across membranes, oxygen uptake proteins, cytochromes and ferridoxins

UNIT-3

Chemistry of Transition Elements

Co-ordination chemistry of transition metal ions; structural aspects, isomerism, octahedral, tetrahedral and square planner crystal field splitting of d-orbitals, CFSE, magnetism and colour of transition metal ions, John-Teller effect, interpretation of electronic spectra including charge transfer spectra, Orgel diagrams, spectrochemical series, nephelauxetic series, quenching of orbital angular moment, spin orbit coupling

Stereochemistry of coordination compounds, stability constants of complexes and their determination, stabilization of unusual oxidation states

Mechanism of Inorganic Reactions

Substitution reactions, trans effect, electron transfer reactions

Fluxional molecules, palladium catalysed reactions

Organometallic Chemistry

Synthesis, structure and bonding, organometallic reagents in organic synthesis and in homogeneous catalytic reactions (hydrogenation, hydroformulation, isomerisation and polymerisation) π- metal complexes

Ligand Field and Molecular Orbital Theories

M.O. energy level diagrams of octahedral, tetrahedral and square planner complexes, Effect of π - bonding on the energy of t2g orbitals and on Dq. experimental evidences for metal-ligand orbital overlap

UNIT-4

Stereochemistry

Element of symmetry, chiral and aehiral molecules, R, S nomenclature, diastereomerism in acyclic compounds

Methods of asymmetric synthesis

Stereospecific and stereo-selective reactions

Interconversion of Fischer, Newman and Sawhorse projections

E, Z isomerism, conformational analysis of mono and disubstituted cyclohexanes

Effect of confirmation on reactivity in acyclic compounds and cyclohexanes

Reaction Mechanism

(a) General methods (non-kinetic) of study of mechanism of organic reactions :

Use of isotopes, crossover experiments, intermediate trapping, stereochemistry

Thermodynamic control and kinetic control of reactions

(b) Reaction Intermediates :

generation, geometry, stability and reactions of carbocations, carbanions, free radicals, carbenes & NHC, benzynes and non classical carbocations

(c) Substitution reaction :

SN1, SN2, SNi, SN1' and SN2' mechanisms, Neighbouring group participation in aliphatic nucleophilic substitutions

Electrophilic and nucleophilic aromatic subtitution reactions

(d) Elimination reactions :

E1, E2 and E1 cb mechanisms

orientation in E2 reaction (Saytezeff and Hofmann), Pyrrolytic syn-elimination

Stereochemistry of elimination reaction

(e) Addition Reactions :

Electrophilic addition to carbon-carbon multiple bond and its stereochemistry

Nucleophilic addition to carbon-oxygen double bond and activated Carboncarbon double bond

(f) Common Organic Reaction and Mechanism :

Aldol, Perkin, Dieckmann condensation, Reformatsky, Benzoin, Wittig, ReimerTiemann, Diels-Alder, Robinson annulation, Ene Barton reaction, Hofmann-LofforFreytage reactions, Shapiro reaction, Sharpless epoxidation reaction, Mannich reaction, Michael reaction, Stroke enamine reaction, Stetter reaction and Baylis-Hillman reaction

Rearrangements : Pinacol-Pinacolone, Wagner-Meerwein, Demjanove, Beckmann, Hofmann, Curtius, Schmidt, Lossen, Sommelet-Hauser, Favoroskii and Baeyer-Villiger rearrangement

UNIT-5

Reagents in Organic Synthesis

Use of following reagents in organic synthesis and functional group transformation

(a) Complex metal hybrids : LiAIH4, NaBH4, Sia2BH, mono and dialkyl boranes, disobutylaluminium hydride and tri-n-butyltin hydride

(b) Organometallic Compounds : Grignard reagents, Lithium dialkylcuperate, dialkylcadmium, alkyllitrhium and Trimethyl silyl iodide

(c) 1, 3-Dithiane, lithium diisopropylamide, DDQ, SeO2, Bayker's yeast, crown ether and phase transfer catalysts

Pericyclic Reactions

Classification and examples, Woodward-Hofmann's Rule, Elcetrocyclic reaction, Cycloaddition reaction ([2+2] and [4+2] only)

sigmatropic shifts {[1,3] -shift, [1,5]- shift and [3,3]-shift (Cope rearrangement and Claisen Rearrangement)}, FMO approach only

Photochemistry

Photochemistry processes, Jablonski diagram, exciplexes, photosensitisations

Photochemistry of alkenes (cis-trans isomerisation), Photochemical addition reactions of 1,3:1,4 and 1,5-dienes, dimerisations

Photochemistry of Carbonyl compounds : Norrish Type-I and Norrish Type-II of cyclic and acyclic ketones, Paterno-Buchi reaction, Photoreduction

Rearrangement given by β, γ- unsaturated ketones, cyclohexenons and 2,5-cyclohexadienones

Photochemistry of aromatic compounds, skeletal isomerisation

Aromaticity

Huckel's rule and concept of aromaticity

Nonbenzenoid aromatic compounds (Monocyclic aromatic ions, annulene and bicyclic nonbenzenoid aromatic compounds)

Heterocyclic Chemistry

Synthesis, aromaticity and reactivity of furan, thiophene, pyrole, pyridine, quinoline and isoquinoline

UNIT-6

Electro -chemistry

Redox potential, electrochemical series, redox indicators

Kohlrausch's law of independent migration of ions

Transport number and its determination, Hydrolysis of salts, pH and buffer solutions, type of single electrodes and elctrode potentials, concentration cell with and without transference, liquid junction potential, fuel cell

Nuclear Chemistry

Radioactive decay and equilibrium

Nuclear reactions

fission and fusion, mass defect, fission products and yields

Radioactive techniques

Tracer technique, neutron activation analysis, counting techniques such as G.M. ionisation and proportional counter

Solids

Cubic Crystal Systems, Dislocations in solids, Schottky and Frenkel Defects, electrical properties, insulators and semiconductors, superconductors, band theory of solids, solid states reactions

UNIT-7

Spectroscopy

Basic principles and applications of IR, Ramam, ESR, NMR, Massbauer and Photoelectron spectroscopy in structural elucidation of simple inorganic and coordination compounds including F & P containing inorganic compounds

Elementary principles and application of electronic (UV), vibrational (IR), PMR, C-13 NMR and Mass spectral technique for structural elucidation of organic compounds and Compounds Containing F

Topics in Analytical Chemistry

Adsorption partition, exclusion electrochromatography, solvent extraction and ion exchange methods, electroanalytical techniques, voltammetry, cyclic voltammetry, polarography, amperometry, coulometry and conductometry, ion selective electrodes, annodic stripping voltammetry, TGA, DTA etc

UNIT-8

Thermodynamics

Variation of internal energy with temperature and volume, Enthalpy as a function of temperature and pressure, relation between Cp and Cv, Kirchoff's equation, JouleThompson coefficient, Inversion temperature, Important thermodynamic quantities (w, q, ΔE, Δ”H) in an isothermal expansion of an ideal gas and adiabatic expansion of an ideal gas, Spontaneous processes

Carnot cycle, Statement of second law, concept of entropy,Thermodynamic equation of state (Energy as a function of T and V, enthalpy as a function of T and P), Variation of entropy with Temperature and Volume, Helmholtz and Gibbs free energy, Gibbs-Helmholtz equation, Thermodynamic criteria of equilibrium

Clapeyron and Claucious equation, Hoff equation, Thermodynamic derivation of Phase Rule and distribution law, Partial molar Quantities, Chemical potential and other thermodynamic functions

Effect of Temperature and Pressure on chemical potential; chemical potential of real gas and fugacity of real gas

Nernst heat theorem and its application to non-condensed system, statements of third law, The relationship between entropy constant and Nernst Chemical constant, Determination of entropy from the third law

Chemical Kinetics and Catalysis

Differential and integral rate equations for zero, first, second and third order reactions, Half-life period, Kinetics of first order opposing, consecutive and parallel reactions, Effects of temperature on reaction rate, energy of activation and collision theory of bimolecular gaseous reactions

Steady-State approximation, Lindemann's theory of reaction rates

Thermodynamic formulation of rate constant, comparision of collision and absolute reaction rate theory

calculation of transmission co-efficient, Primary and Secondary salt effects, kinetics of homogenious, acid -base and enzyme catalysis, heterogenious catalysis

UNIT-9

Chain reactions and Photochemistry

Chain reaction, free radical chains (Rice-Herzfeld mechanism for the decomposition of ethane), Einstein's law of Photochemical equivalence, Quantum efficiency, Kinetics of some photochemical reactions (Decompositions of acetaldehyde, dimerization of anthracene)

Statistical Thermodynamics

Quantum states and complex ions, The combinatory rule, System with definite total energy. Degeneracy of energy levels

Probability and most probable distribution, translational, rorational, vibrational and electronic partition function

Internal energy and heat capacity in terms of partition function

Thermodynamic function for gaseous system, Molar heat capacity of gases, Heat capacity of monoatomic crystal

The Einstein model, Debye's theory of solid heat capacities of Crystal at very low temperatures, Calorimetric entropy, spectroscopic entropies, expression for equilibrium constant in terms of partition functions, BaseEinstein statistics, Fermi-Dirac statistics, Comparision of M-B, B-E and F-D statistics

UNIT-10

Fast Reaction

Luminescence and energy transfer processes

Study of Kinetic by stopped flow technique, relaxation method, flash photolysis and magnetic resonance method

Non-equilibrium Thermodynamics

Postulates and methodologies, linear laws, Gibbs equation, Onsager reciprocal theory

Macromolecules

Number-average and weight average molecular weights; determination of molecular weights. Kinetics of polymerization

Stereochemistry and mechanism of polymerisation