PAPER-I
1.Atomic structure- Quantum theory , Heisenberg’s uncertainity principle, Schrodinger wave equation (time independent). Interpretation of wave function , particle in one – dimensional box, quantum numbers , hydrogen atom wave functions . Shapes of s, p and d orbitals .
2.Chemical bonding – Ionic bond, characteristics of ionic compounds, factors affecting stability of ionic compounds, lattice energy, Born – Haber cycle; covalent bond and its general characteristics , polarities of bonds in molecules and their dipole moments. Valence bond theory , concept of resonance and resonance energx. Mnlectlar orbhtal thenry (LCAN method(; bnnding in holonuclear molecular ; H2 +,H2 to Ne2, NO, CO, HF , CN , CN-, BeH2 and CO2 . Comparision of valence bond and molecular orbital theories, bond order , bond strength and bond length.
Solid State – Forms of solids , laws of constancy of interfacial angles, crystal systems and crystal classes (crystallographic groups). Designation of crystal faces, lattice structures and unit cell . Laws of rational indices. Bragg’s law . X-ray diffraction by crystals . Close packing , radious ratio rules , calculation of some limiting radius ratio values . Structures of NaCl, Zns, CsCl, CaF2, Cdl2 , and rutile . Imperfection in crystals , stoichiometric and nonstoichiometric defects , impurity defects , semi- conductors. Elementary study of liquid crystals.
4.The gaseous state – Equation of state for real gases, intermolecular interactions, liquefication of gases and critical phenomena , Maxwell’s distribution of speeds , intermolecular collisions , collisions on the wall and effusion .
5.Thermodynamics and statistical thermodynamics – Thermodynamic systems, states and processes , work , heat and internal energy; first law of thermodynamics, work done on the systems and heat absorbed in different types of processes; calorimetry, energy and enthalpy changes in various processes and their temperature dependence.
Second law of thermodynamics; entropy as a state function , entropy changes in various process, entropy – reversibility and irreversibility , Free energy functions; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem and third law of thermodynamics.
Micro and macro states; canonical ensemble and canonical partition function; electronic, rotational and vibrational partition functions and thermodynamic quantities; chemical equilibrium in ideal gas reactions.
6.Phase equilibria and solutions- Phase equilibria in pure substances; Clausius- Clapeyron equation; phase diagram for a pure substance; Phase equilibria in binary systems, partially miscible liquids- upper and lower critical solution temperatures; partial molar quantities , their significance and determination; excess thermodynamic functions and their determination.
7.Electrochemistry- Debye- Hucket theory of strong electrolytes and Debye- Huckel limiting Law for various equilibrium and transport properties .
Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. ofcell and its applications fuel cells and batteries.
Processes at electrodes; double layer at the interface; rate of change transfer , current density; overpotential ; electroanalytical techniques- voltameter , polarography, amperometry , cyclic- voltametry , ion selective electrodes and their use.
8.Chemical kinetics- Concentration dependence of rate of reaction; differential and integral rate equations for zeroth, first, second and fractional order reactions. Rate equations involving reverse, parallel, consecutive and chain reactions; effect of temperature and pressure on rate constant . Study of fast reactions by stop flow and relaxation methods. Collisions and transition state theories.
9.Photochemistry- Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.
10.Surface phenomena and catalysis- Adsorption from gases and solutions on solid adsorbents , adsorption isotherms Langmuir and B.E.T. isotherms; determination of surface area, characteristics and mechanism of reaction on heterogeneous catalysts.
11.Bio- inorganic chemistry – Metal ions in biological systems and their role in ion- transport across the membranes (molecular mechanism), ionophores, photosynthesis – PSI, PSII; nitrogen fixation, oxygen- uptake proteins , cytochromes and ferredoxins.
12.Co- ordination chemistry – (a) Electronic configurations; introduction to theories of bonding in transition metal complexes . Valence bond theory ,crystal field theory and its modifications ; applications of theories in the explanation of magnetism and electronic spactra of metal complexes.
(b) Isomerism in coordination compounds; IUPAC nomenclature of coordination compounds; stereochemistry of complexes with 4 and 6 coordination number ; chelate effect and polynuclear complexes; trans effect and its theories; kinetic of substitution reactions in square- planar complexes; thermodynamic and kinetic stability of complexes.
(C) Synthesis and structures of metal carbonyls; carboxylate anions, carbony 1 hydrides and metal nitrosy1 complexes.
(d) Complexes with aromatic systems, synthesis , structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadieny1 complexes ; coordinative unsaturation , oxidative addition reactions, insertion reactions, fluxional molecules and their characterization . Compounds with metal- metal bonds and metal atom clusters.
13. General chemistry of ‘f’ block elements- Lanthanides and actinides; separation , Oxidation states, magnetic and spectral properties; lanthanide contraction.
14. Non- Aqueous Solvents- Reactions in liquid NH3 , HF, SO2 and H2SO4.
Failure of solvent system concept , coordination model of non- aqueous solvents. Some highly acidic media, fluorosulphuric acid and super acids.
PAPER- II
1.Delocalised covalent bonding – Aromaticity, anti- aromaticity; Annulenes, azulenes, tropolones, kekulene, fulvenes, sydnones.
2.(a) Reaction mechanisms- General methods (both kinetic and non- kinetic of study of mebhanhsm nr organhc rdacthons illtstr`ted by dxamples- use of isotopes, cross- over experiment , intermediate trapping, stereochemistry ; energy diagrams of simple organic reactions- transition states and intermediates; energy of activation ; thermodynamic control and kinetic control of reactions.
(b) Reactive intermediates- Generation , geometry, stability and reactions of carbonium and carbonium ions, carbanions , free radicals, carbenes, benzynes and niternes.
(c) Substitution reactions- SNI, SN2, SNi, SN1, SN2, SNi and SRN1 mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compound including simple heterocyclic compounds- pyrrole, furan thiophene , indole.
(d) Elimination reactions- E1, E2 and E1 cb mechanism; orientation in E2 reactions- Saytzeff and Hoffmann; pyrolytic syn elimination- acetate pyrolysis, Chugaev and Cope eliminations.
(e) Addition reactions- Electrophilic addition to C.= C and C= C; nucleophilic addition to C= O, C=N, conjugated olefins and carbonyls.
(f) Rearrangements- Pinacol- pinacolune , Hoffmann, Beckmann, Baeyer- Villiger , Favorskii, Fries, Claisen, Cope, Stevens and Wagner- Meerwein rearrangements.
3. Pericyclic reactions- classification and examples , woodward- Hoffmann rules- electrocyclic reaction, cycloddition reaction s (2+2 and 4+2) and sigmatropic shifts (1,3,3,3and 1,5)FMO approach.
4. Chemistry and mechanism of reactions- Aldol condensation (including directed aldol condensation), Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe , benzoin and acyloin condensations; Fischer indole synthesis, Skraup, synthesis, Bischler- Napieralski , Sandmeyer, Reimer- Tiemann and Reformatsky reactions.
5. Polymeric Systems- (a) Physical chemistry of polymers- Polymer solutions and their thermodynamic properties; number and weight average molecular weights of polymers. Determination of molecular weights by sedimentation , light scattering, osmntic prersurd , viscnsitx , dnd froup an`lyshs mdthods.
(b) Preparation and properties of polymers- Organic polymers – polyethylene , polystyrene, polyvinyl 1 chloride, Teflon, nylon, terylene, synthetic and natural rubber. Inorganic polymers- phoshonitrilic halides, borazines, silicones and silicates.
(c) Biopolymers- Basic bonding in proteins , DNA and RNA.
6. Synthetic uses of reagents- OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na- Liquid NH3, LiA1H4 NaBH4n-Buli, MCPBA.
7. Photochemist- Photochemical reactions of simple organic compounds, excited and ground states , singlet and triplet states, Norrish- Type I and Type II reaction .
8. Principles of spectroscopy and applications in structure elucidation
(a) Rotational spectra- Diatomic molecules; isotopic substitution and rotational constants.
(b) Vibrational spectra – Diatomic molecules, linear triatomic mole- cules, specific frequencies of functional groups in polyatomic molecules.
(c) Electronic spectra- Singlet and triplet states. N-> ^* and ^ ->^* transitions; applications to conjugated double bond and conjugated carbonyls – Woodward- Fieser rules.
(d) Nuclear magnetic resonance- Isochronous and anisochronous protons; chemical shift and coupling constants; Applications of H’ NMR to simple organic molecules.
(e) Mass spectra- Parent peak , base peak, daughter peak, metastable peak, fragmentation of simple organic molecules, a cleavage , McLafferty rearrangement.
(f) Electron spin resonance- Inorganic complexes and free radicals.
1.Atomic structure- Quantum theory , Heisenberg’s uncertainity principle, Schrodinger wave equation (time independent). Interpretation of wave function , particle in one – dimensional box, quantum numbers , hydrogen atom wave functions . Shapes of s, p and d orbitals .
2.Chemical bonding – Ionic bond, characteristics of ionic compounds, factors affecting stability of ionic compounds, lattice energy, Born – Haber cycle; covalent bond and its general characteristics , polarities of bonds in molecules and their dipole moments. Valence bond theory , concept of resonance and resonance energx. Mnlectlar orbhtal thenry (LCAN method(; bnnding in holonuclear molecular ; H2 +,H2 to Ne2, NO, CO, HF , CN , CN-, BeH2 and CO2 . Comparision of valence bond and molecular orbital theories, bond order , bond strength and bond length.
Solid State – Forms of solids , laws of constancy of interfacial angles, crystal systems and crystal classes (crystallographic groups). Designation of crystal faces, lattice structures and unit cell . Laws of rational indices. Bragg’s law . X-ray diffraction by crystals . Close packing , radious ratio rules , calculation of some limiting radius ratio values . Structures of NaCl, Zns, CsCl, CaF2, Cdl2 , and rutile . Imperfection in crystals , stoichiometric and nonstoichiometric defects , impurity defects , semi- conductors. Elementary study of liquid crystals.
4.The gaseous state – Equation of state for real gases, intermolecular interactions, liquefication of gases and critical phenomena , Maxwell’s distribution of speeds , intermolecular collisions , collisions on the wall and effusion .
5.Thermodynamics and statistical thermodynamics – Thermodynamic systems, states and processes , work , heat and internal energy; first law of thermodynamics, work done on the systems and heat absorbed in different types of processes; calorimetry, energy and enthalpy changes in various processes and their temperature dependence.
Second law of thermodynamics; entropy as a state function , entropy changes in various process, entropy – reversibility and irreversibility , Free energy functions; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem and third law of thermodynamics.
Micro and macro states; canonical ensemble and canonical partition function; electronic, rotational and vibrational partition functions and thermodynamic quantities; chemical equilibrium in ideal gas reactions.
6.Phase equilibria and solutions- Phase equilibria in pure substances; Clausius- Clapeyron equation; phase diagram for a pure substance; Phase equilibria in binary systems, partially miscible liquids- upper and lower critical solution temperatures; partial molar quantities , their significance and determination; excess thermodynamic functions and their determination.
7.Electrochemistry- Debye- Hucket theory of strong electrolytes and Debye- Huckel limiting Law for various equilibrium and transport properties .
Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. ofcell and its applications fuel cells and batteries.
Processes at electrodes; double layer at the interface; rate of change transfer , current density; overpotential ; electroanalytical techniques- voltameter , polarography, amperometry , cyclic- voltametry , ion selective electrodes and their use.
8.Chemical kinetics- Concentration dependence of rate of reaction; differential and integral rate equations for zeroth, first, second and fractional order reactions. Rate equations involving reverse, parallel, consecutive and chain reactions; effect of temperature and pressure on rate constant . Study of fast reactions by stop flow and relaxation methods. Collisions and transition state theories.
9.Photochemistry- Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.
10.Surface phenomena and catalysis- Adsorption from gases and solutions on solid adsorbents , adsorption isotherms Langmuir and B.E.T. isotherms; determination of surface area, characteristics and mechanism of reaction on heterogeneous catalysts.
11.Bio- inorganic chemistry – Metal ions in biological systems and their role in ion- transport across the membranes (molecular mechanism), ionophores, photosynthesis – PSI, PSII; nitrogen fixation, oxygen- uptake proteins , cytochromes and ferredoxins.
12.Co- ordination chemistry – (a) Electronic configurations; introduction to theories of bonding in transition metal complexes . Valence bond theory ,crystal field theory and its modifications ; applications of theories in the explanation of magnetism and electronic spactra of metal complexes.
(b) Isomerism in coordination compounds; IUPAC nomenclature of coordination compounds; stereochemistry of complexes with 4 and 6 coordination number ; chelate effect and polynuclear complexes; trans effect and its theories; kinetic of substitution reactions in square- planar complexes; thermodynamic and kinetic stability of complexes.
(C) Synthesis and structures of metal carbonyls; carboxylate anions, carbony 1 hydrides and metal nitrosy1 complexes.
(d) Complexes with aromatic systems, synthesis , structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadieny1 complexes ; coordinative unsaturation , oxidative addition reactions, insertion reactions, fluxional molecules and their characterization . Compounds with metal- metal bonds and metal atom clusters.
13. General chemistry of ‘f’ block elements- Lanthanides and actinides; separation , Oxidation states, magnetic and spectral properties; lanthanide contraction.
14. Non- Aqueous Solvents- Reactions in liquid NH3 , HF, SO2 and H2SO4.
Failure of solvent system concept , coordination model of non- aqueous solvents. Some highly acidic media, fluorosulphuric acid and super acids.
PAPER- II
1.Delocalised covalent bonding – Aromaticity, anti- aromaticity; Annulenes, azulenes, tropolones, kekulene, fulvenes, sydnones.
2.(a) Reaction mechanisms- General methods (both kinetic and non- kinetic of study of mebhanhsm nr organhc rdacthons illtstr`ted by dxamples- use of isotopes, cross- over experiment , intermediate trapping, stereochemistry ; energy diagrams of simple organic reactions- transition states and intermediates; energy of activation ; thermodynamic control and kinetic control of reactions.
(b) Reactive intermediates- Generation , geometry, stability and reactions of carbonium and carbonium ions, carbanions , free radicals, carbenes, benzynes and niternes.
(c) Substitution reactions- SNI, SN2, SNi, SN1, SN2, SNi and SRN1 mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compound including simple heterocyclic compounds- pyrrole, furan thiophene , indole.
(d) Elimination reactions- E1, E2 and E1 cb mechanism; orientation in E2 reactions- Saytzeff and Hoffmann; pyrolytic syn elimination- acetate pyrolysis, Chugaev and Cope eliminations.
(e) Addition reactions- Electrophilic addition to C.= C and C= C; nucleophilic addition to C= O, C=N, conjugated olefins and carbonyls.
(f) Rearrangements- Pinacol- pinacolune , Hoffmann, Beckmann, Baeyer- Villiger , Favorskii, Fries, Claisen, Cope, Stevens and Wagner- Meerwein rearrangements.
3. Pericyclic reactions- classification and examples , woodward- Hoffmann rules- electrocyclic reaction, cycloddition reaction s (2+2 and 4+2) and sigmatropic shifts (1,3,3,3and 1,5)FMO approach.
4. Chemistry and mechanism of reactions- Aldol condensation (including directed aldol condensation), Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe , benzoin and acyloin condensations; Fischer indole synthesis, Skraup, synthesis, Bischler- Napieralski , Sandmeyer, Reimer- Tiemann and Reformatsky reactions.
5. Polymeric Systems- (a) Physical chemistry of polymers- Polymer solutions and their thermodynamic properties; number and weight average molecular weights of polymers. Determination of molecular weights by sedimentation , light scattering, osmntic prersurd , viscnsitx , dnd froup an`lyshs mdthods.
(b) Preparation and properties of polymers- Organic polymers – polyethylene , polystyrene, polyvinyl 1 chloride, Teflon, nylon, terylene, synthetic and natural rubber. Inorganic polymers- phoshonitrilic halides, borazines, silicones and silicates.
(c) Biopolymers- Basic bonding in proteins , DNA and RNA.
6. Synthetic uses of reagents- OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na- Liquid NH3, LiA1H4 NaBH4n-Buli, MCPBA.
7. Photochemist- Photochemical reactions of simple organic compounds, excited and ground states , singlet and triplet states, Norrish- Type I and Type II reaction .
8. Principles of spectroscopy and applications in structure elucidation
(a) Rotational spectra- Diatomic molecules; isotopic substitution and rotational constants.
(b) Vibrational spectra – Diatomic molecules, linear triatomic mole- cules, specific frequencies of functional groups in polyatomic molecules.
(c) Electronic spectra- Singlet and triplet states. N-> ^* and ^ ->^* transitions; applications to conjugated double bond and conjugated carbonyls – Woodward- Fieser rules.
(d) Nuclear magnetic resonance- Isochronous and anisochronous protons; chemical shift and coupling constants; Applications of H’ NMR to simple organic molecules.
(e) Mass spectra- Parent peak , base peak, daughter peak, metastable peak, fragmentation of simple organic molecules, a cleavage , McLafferty rearrangement.
(f) Electron spin resonance- Inorganic complexes and free radicals.
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