SECOND SEMESTER

CHI HCT: 2.1 (Inorganic Chemistry)

Paper Name : COORDINATION CHEMISTRY

2.1.1 - UNIT-I
Preparation of coordination compounds : Introduction, Preparative methods- simple addition reactions, substitution reactions,
oxidation-reduction reactions, thermal dissociation reactions. Geometries of metal complexes of higher coordination numbers
(2-12).

Stability of coordination compounds: Introduction, trends in stepwise stability constants, factors influencing the stability of metal
complexes with reference to the nature of metal ion and ligands, the Irving-William series, chelate effect.

Determination of stability constants: Theoretical aspects of determination of stability constants of metal complexes by
spectrophotometric and polarographic methods.

Crystal field theory : Salient features of CFT, d-orbital splitting in octahedral, tetrahedral, square planar and tetragonal
complexes, Jahn-Teller distortions, measurement of 10 Dq and factors affecting it. Evidences for metal-ligand covalency.

Molecular Orbital Theory: MOT to octahedral, tetrahedral and square planar complexes without and with pi-bonding.

2.1.2 - UNIT-II
Electronic spectra: Introduction, selection rules and intensities, electronic spectra of octahedral and tetrahedral complexes,
Term symbols for dn ions, Orgel and Tanabe Sugano diagrams, charge-transfer spectra. Ligand-field transition. Charge
transfer and energy applications. Optical rotatory dispersion and Circular dichroism. Magnetic circular dichroism.

Magnetic properties: Introduction, magnetic susceptibility and its measurements, spin and orbital contributions to the magnetic
moment, the effects of temperature on µeff, spin-cross over, ferromagnetism, anti-ferromagnetism and ferrimagnetism.

Applications of infrared spectroscopy of coordination compounds: Metal complexes of ammine, nitro, nitrito, hydroxo, carbonato,
sulphato, cyano, cyanato and thiocyanato complexes.

2.1.3 - UNIT-III
Reactions and Mechanisms: Introduction. Substitution reactions- Inert and labile compounds, mechanisms of substitution.
Kinetic consequences of Reaction pathways Dissociation, interchange and association.Experimental evidence in octahedral
substitution- Dissociation, associative mechanisms, the conjugate base mechanism, the kinetic chelate effect.

Stereochemistry of reactions : Substitution in trans and its complexes, isomerization of chelate rings. Substitution reactions of
square-planar complexes-kinetics and stereochemistry of square-planar substitutions, evidence for associative reactions,
explanations of the trans effect.

Electron-transfer processes: Inner-sphere mechanism and outer-sphere mechanism, conditions for high and low oxidation
numbers.

Photochemistry of coordination compounds: Photochemistry of chromium(III) ammine compounds, Light-induced excited state
spin trapping in iron(II) compounds and MLCT photochemistry in pentammineruthenium(II) compounds.
CHO HCT: 2.2 (Organic chemistry)

Paper name : SYNTHETIC ORGANIC CHEMISTRY

2.2.1 - UNIT-I
Oxidation : Oxidation with chromium and manganese reagents (CrO3, K2Cr2O7, PCC, PDC, Sarret reagent, MnO2,
KMnO4, ozone, peroxides and peracids, periodic acid, OsO4, SeO2, NBS, Oppenauer oxidation, Sharpless epoxidation.

Reduction : Catalytic hydrogenation (homogeneous and heterogeneous) – catalysts (Pt, Pd, Ra-C, Ni, Ru, Rh), solvents
and reduction of functional groups, catalytic hydrogen transfer reactions. Wilkinson catalyst, LiAlH4, NaBH4, DIBAL-H,
Sodium cyanoborohydride, dissolving metal reactions (Birch reduction). Leukart reaction (reductive amination), diborane as
reducing agent, Meerwein-Ponndorf-Verley reduction, Wolff-Kishner reduction, Clemensen reduction, tributyl tinhydride,
stannous chloride, Bakers yeast, Organoboron compounds: Introduction and preparations. Hydroboration and its applications.

Reactions of organoboranes : isomerization reactions, oxidation, protonolysis, carbonylation, cyanidation. Reactions with
aldehydes or ketones (E and Z-alkenes).

2.2.2 - UNIT-II
Reagents and reactions in organic synthesis : Use of following reagents in organic synthesis and functional group
transformations : Lithium diisopropylamide (LDA), Gilmann reagent, dicyclohexyl carbodimide (DCC), dichlorodicyanoquinone
(DDQ), Silane reagents-trialkylsilyl halides, trimethylsilyl cyanide, trimethyl silane, phase transfer catalyst, crown ethers,
cyclodextrins, Ziegler-Natta catalyst, diazomethane, Woodward and Prevost hydroxylation, Stark enamine reaction,
phosphorous ylides - Wittig and related reactions, sulphur ylides – reactions with aldehydes and ketones, 1,3- dithiane
anions - Umpolung reaction, Peterson reaction. Palladium reagents: Suzuki coupling, Heck reaction, Negishi reaction.

Green Chemistry : Definition and principles, 29 planning green synthesis in the laboratory, green preparations- aqueous
reactions, solid state (solvent free) reactions, photochemical reactions, enzymatic transformations and reactions in ionic
liquids.

2.2.3 - UNIT-III
Molecular rearrangements : Introduction Carbon to carbon migration: Pinacol pinacolone, Wagner-Meerwein, Benzidine,
benzylic acid, Favorskii, Fries rearrangement, dienophile rearrangement. Carbon to nitrogen migration: Hofmann, Curtius,
Lossen, Schmidt and Beckmann rearrangements. Miscellaneous rearrangements: Wittig, Smiles, Bayer-Villeger rearrangement
and Barton reaction.

Retrosynthesis : Introduction to disconnection approach: Basic principles and terminologies used in disconnection approach.
One group C-X and two group C-X disconnections. Synthons and synthetic equivalents. Retrosynthesis and synthesis of
benzofurans, p-methoxy acetophenone, saccharine, α-bisabolene, nuciferal, tetralone, ibuprofen, functional group
transformations in organic synthesis; nitro to keto, nitro to aniline, acid to alcohol etc..
CHP HCT: 2.3 (Physical Chemistry)

Paper Name : PRINCIPLES OF PHYSICAL CHEMISTRY

2.3.1 - UNIT-I
Quantum Chemistry : Introduction to quantum mechanics: Schrödinger wave equation, time-independent and time dependent
Schrödinger wave equation and the relation between their solutions. Eigen functions and Eigen values. Physical interpretation
of wave function.

Concept of operators : Laplacian, Hamiltonian, Linear and Hermitian operators. Angular momentum operators and their
properties. Commutative and non commutative operators. Normalization, orthogonality and orthonormality of wave functions.
Postulates of quantum mechanics. Solutions of Schrödinger wave equation for free particles, particle in a ring, particle in
three dimensional box. Quantum mechanical degeneracy, tunnelling (no derivation). Wave equation for H-atom, 30
separation and solution of R, ф and θ equations. Application of Schrodinger equation to rigid rotator and harmonic
oscillator. Eigen functions and Eigen values of angular momentum. Ladder operator method for angular momentum.

2.3.2 - UNIT-II
Statistical thermodynamics : Objectives of statistical thermodynamics, concept of distribution, types of ensembles.
Thermodynamic probability and most probable distribution law.

Partition functions : definition, evaluation of translational, rotational and vibrational and electronic partition functions for
monoatomic, diatomic and polyatomic gaseous molecules. Sackur-Tetrode equation for entropy of translation function.
Calculation of thermodynamic functions and equilibrium constants in terms of partition functions.

Different distribution laws (Types of statistics) : Maxwell Boltzmann, Bose-Einstein and Fermi-Dirac Statistics (derivation of
the three distribution laws). Comparison of Bose-Einstein and Fermi-Dirac Statistics with Maxwell-Boltzmann statistics.
Problems and their solutions.

Phase rule studies: Thermodynamic derivation of phase rule. Application of phase rule to the two component systems -
compound formation with congruent melting point and incongruent melting points, Roozeboom’s classification. Application of
phase rule to three component systems- systems of three liquids and systems of two salts and water.

2.3.3 - UNIT-III
Polymers : Fundamentals of polymers - monomers, repeat units, degree of polymerization. Linear, branched and network
polymers. Classification of polymers, Polymerization - condensation, addition, free radical, ionic, co-ordination polymerization
and ring opening polymerization. Molecular weight and size, polydispersion.

Average molecular weight concepts : Number, weight and viscosity average molecular weight. Determination of molecular
weights - viscosity method, osmotic pressure method, sedimentation and light scattering methods.

Kinetics of Polymerization : Condensation, addition, free radical, ionic, co-ordination polymerization.

Phase transitions in polymers and thermal characterization : Glass transition, crystallinity and melting- correlation with the
polymer structure.

Polymers in solution : Criteria of polymer solubility, thermodynamics of polymer solutions.

Colloids : Types and classification, Micelles: Surface active agents, micellization, hydrophobic interaction, critical micellar
concentration (CMC), factors affecting the CMC of surfactants, micellar catalysis.
CHG HCT: 2.4 (Spectroscopy)

Paper Name : MOLECULAR SYMMETRY AND SPECTROSCOPY

2.4.1 - UNIT-I
Molecular symmetry and group theory : Symmetry elements and symmetry operations.

The Point Groups Used with Molecules : Concept of a group, definition of a point group. Classification of molecules into
point groups. Subgroups. Hermann-Maugin symbols for point groups. Multiplication tables (C2V, C2h and C3V). Matrix
notation for the symmetry elements. Classess and similarity transformation.

Representation of groups : The Great Orthogonality theorem and its consequences. Character tables (Cs, Ci, C2, C2v, C2h
and C3v). Symmetry and dipole moment. Applications of group theory: Group theory and hybrid orbitals.

Symmetry in Chemical bonding : Group theory to Crystal field theory and Molecular orbital theory (octahedral and tetrahedral
complexes).

Symmetry in Vibrational Spectroscopy : Determining the symmetry groups of normal modes for non-linear molecules (H2O,
NH3, CH4, trans-N2F2) and linear molecules (CO, HCl, HCN and CO2) (Integration method).

2.4.2 - UNIT-II
Microwave spectroscopy : Rotation spectra of diatomic Molecules - rigid and non rigid rotator model. Rotational quantum
number and the selection rule. Effect of isotopic substitution on rotation spectra. Classification of polyatomic molecules based
on moment of inertia. Rotation spectra of polyatomic molecules (OCS CH3F and BCl3). Moment of inertia expression for
linear tri-atomic molecules. Applications - Principles of determination of Bond length and moment of inertia from rotational
spectra. Stark effect in rotation spectra and determination of dipole moments.

Vibration spectroscopy : Vibration of diatomic molecules, vibrational energy curves for simple harmonic oscillator. Effects of
anharmonic oscillation, expressions for fundamental and overtone frequencies. Vibration - rotation spectra of carbon
monoxide. Vibration of polyatomic molecules – The number of degrees of freedom of vibration. Parallel and perpendicular
vibrations (CO2 and H2O). Combination, difference and hot bands. Fermi resonance. Force constant and its significance.
Theory of infrared absorption and theoretical group frequency. Intensity of absorption band and types of absorptions.
Applications: Structures of small molecules: XY2 – linear or bent, XY3 – planar or pyramidal.

Raman spectroscopy : Introduction, Raman and Rayleigh scattering, Stokes and anti Stokes lines, polarization of Raman
lines, depolarization factor, polarizability ellipsoid. Theories of Raman spectra - classical and quantum theory. Rotation-
Raman and vibration-Raman spectra. Raman activity of vibrations, rule of mutual exclusion principle. Vibration modes of
some simple molecules and their activity.

2.4.3 - UNIT-III
UV Visible spectroscopy : Quantitative aspects of absorption – Beer’s law, Technology associated with absorption
measurements. Limitations– real, chemical, instrumental and personal. Theory of molecular absorption. Vibration- rotation fine
structure of electronic spectra. Types of absorption bands- n to π*, π to π*, n to σ* and σ to σ*, C-T and ligand
field. Instrumentation.

Applications : Qualitative and quantitative analysis of binary mixtures, measurements of dissociation constants of acids and
bases, determination of molecular weight. Woodwards empirical rules for predicting the wavelength of maximum absorption for
olefins, conjugated dienes, cyclic trienes and polyenes, α,ß-unsaturated aldehydes and ketones, benzene and substituted
benzene rings.

Resonance Raman Spectroscopy : Resonance Raman Effect and its applications. Non linear Raman effects: Hyper, stimulated
and inverse Raman effects. Coherent Anti Stokes Raman Scattering and its applications.
Chemistry Practical
Physical Chemistry
Part – A
1. Study of kinetics of hydrolysis of methyl acetate in presence of two different concentrations of HCl/H2SO4 and report
the relative catalytic strength.

2. Study of kinetics of reaction between K2S2O8 and KI, first order, determination of rate constants at two different
temperatures and Ea.

3. To study the kinetics of saponification of ethyl acetate by conductivity method at two different concentrations of NaOH
and report the relative catalytic strength.

4. Determination of partial molar volume of salt-water system (NaCl-H2O/KCl H2O/KNO3-H2O) systems.

5. To study the kinetics of reaction between acetone and iodine - determination of order of reaction with respect to iodine
and acetone.

6. Study the kinetics of decomposition of diacetone alcohol by NaOH, determine the catalytic coefficient of the reaction and
comparison of strength of alkali.

7. Determination of energy of activation for the bromide-bromate reaction. 8. Kinetics of reaction between sodium formate
and iodine and determination of energy of activation.

9. Determination of heat of solution of organic acid (benzoic acid/salicylic acid) by variable temperature method (graphical
method).

10. Determination of degree of association of benzoic acid in benzene by distribution method.

11. To determine the eutectic point of a two component system (Naphthalene-m dinitrobenzene system).

12. Analysis of a binary mixture (Gylcerol & Water) by measurement of refractive index.

13. Determination of the molecular weight of a polymer material by viscosity measurements (cellulose acetate/methyl
acrylate).

PART – B
1. Conductometric titration of a mixture of HCl and CH3COOH against NaOH.

2. Conductometric titration of sodium sulphate against barium chloride.

3. pH titration of (a) HCl against NaOH (b) Copper sulphate against NaOH and (c) CH3COOH/HCOOH against NaOH
- determination of Ka.

4. Determination of equivalent conductance of weak electrolyte (CH3COOH) at infinite dilution following Kohlrausch law.

5. Determination of dissociation constant and mean ionic activity coefficient of weak acids
(CH3COOH/HCOOH/ClCH2COOH) by conductivity method.

6. Potentiometric titration of KI vs KMnO4 solution.

7. Determination of dissociation constant of a weak acid (CH3COOH/HCOOH/ClCH2COOH) by potentiometric method.

8. Potentiometric titration of a mixture of halides (KCl+KI/KCl+KBr/KBr+KI) against AgNO3.

9. To obtain the absorption spectra of coloured complexes, verification of Beer’s law and estimation of metal ions in
solution using a spectrophotometer.
10. Potentiometric titration of K2Cr2O7 against FAS determination of redox potential and concentration of Fe2+ ions.

11. Conductometric titration of oxalic acid against NaOH and NH4OH.

12. Coulometric titration I2 vs Na2S2O3.

13. Determination of acidic and basic dissociation constant and isoelectric point of an amino acid by pH metric method.

14. Kinetics of photodegradation of indigocarmine (IC) using ZnO/TiO2 as photocatalyst and study the effect of
[ZnO/TiO2] and [IC] on the rate of photodegradation.
Organic Chemistry Practical

PART-A
Multistep synthesis :

1. Preparation p-bromoaniline from acetanilide.

2. Preparation of n-butyl bromide from n-butyl alcohol.

3. Oxidation of cyclohexanol to adipic acid.

4. Esterification: Preparation of benzoccaine from p-nitrotoluene.

5. Diazotization (Sandmeyer’s reaction): Preparation of p-chlorobenzoic acid from p-toluidine.

6. Preparation benzilic acid from benzoin.

7. Preparation of o-hydroxy benzophenone from phenyl benzoate via Fries rearrangement.

8. Preparation of benzanilide from benzophenone oxime via Beckmann rearrangement.

9. Preparation of benzoic acid from benzaldehyde (Cannizzaro Reaction).

10. Preparation of 2,4-dinitrophenylhydrazine from 2,4-dinitrochlorobenzene.

11. Preparation of m-nitrobenzoic acid from methylbenzoate.

12. Preparation of chalcone.

PART-B
Qualitative analysis : Separation of binary mixtures, identification of functional groups and preparation of suitable solid
derivatives.