INORGANIC CHEMISTRY

UNIT-I
Chemical Bonding and Structures: Atomic states and term symbols. Bonding and structure: Types
of bonds, orbital symmetry and overlaps, concept of Lewis, hybridization, VSEPR theory, VB theory
and MO theory with examples, properties, merits and drawbacks, Born Haber cycle, Born-Lande
equation,
Kapustinskii equation, partial covalent character, radius-ratio rules, structures of simple solids. Bond
energy and covalent radii, concept of resonance, molecular dipole moment; polarizing power and
polarizability, Fajan’s rules and Slater rules.

UNIT-II
Chemistry of main group elements: Periodic anomalies in main block elements, Inert Pair effect,
Relativistic effect.
Boron and Silicon based compounds: Boron hydrides (small boranes and their anions, B1−B4),
boron nitride, borazines, carboranes, metalloboranes, metallocarboranes; silicates, silicones,
diamond, graphite. Hydrides, oxides and oxy acids of Nitrogen, Phosphorous, Sulphur and halogens;
phosphazines, sulphurnitrogen compounds, inter halogen compounds, pseudo halogens.

UNIT-III
Acid-Bases: Bronsted-Lowry concept, proton transfer equilibria under aqueous conditions, non-
aqueous solvents and acid-base strength, periodic trends in aqua acid strength, oxoacids, anhydrous
oxides, Bronsted-Lowry acidity of aqueous cations, Lewis acid- base concept and frontier orbitals,
examples of Lewis acids and bases, quantification of Lewis basicity, inductive and steric effects on
Lewis acidity and basicity, frustrated Lewis pairs.
HSAB concept: Basis of HSAB concept, Frontier MO approach acid-base strength, hardness and
softness, symbiosis, applications of HSAB concept and Chatt theory
Non-aqueous solvents: Classification of solvents, Properties of solvents (dielectric constant, donor
and acceptor properties) protic solvents (anhydrous H2SO4, HF and glacial acetic acid) aprotic
solvents (liquid SO2, BrF3 and N2O4). Solutions of metals in liquid ammonia, hydrated electron.
Super acids. Acid- base concept in non-aqueous media.

UNIT-IV
Clusters and Cages: M-M bond and metal atom clusters, halide clusters, bonding in [ReCl8] 2-.
Metal carbonyl clusters- LNCC’s and HNCC’s. Electron counting in carbonyl/Nitrosyl clusters,
important reactions of metal carbonyls, preparation. Cluster valence electrons and Wade-Mingos-
Lauher rules. Structure elucidation based on CVE, Isolobal analogies. Applications of metal clusters.
Isopoly and heteropoly acids of W, Mo and V, preparations, properties, structure and applications,
Zintle ions.
Nobel Gases: Preparation, Structure, properties and bonding in halides and oxo-halides of xenon
compounds.

2
UNIT – I
Metal-Ligand equilibria in solution: Step-wise and overall formation constant and their
relationship, trends in step-wise constant, kinetic and thermodynamic stability of metal complexes,
factors affecting the stability of metal complexes with reference to the nature of the metal ion and
ligand, chelate effect, macrocyclic effect trans effect (sigma and pi bonding effect) and their
thermodynamic origin. Determination of binary formation constant by pH metry, spectrophotometry,
polarography and ion exchange methods. Introduction to redox chemistry of complexes. Redox
chemistry and analytical applications.

Structure and bonding - Structure and bonding in hydride, dihydrogen, dioxygen, isocyanide, CO,
NO, N2
and tertiary phosphine complexes of transition metals. [15 hrs]

UNIT- II
Metal- ligand bonding: Stereoisomerism- coordination numbers 3 to 8. Optical isomerism(ORD
and CD) Crystal field theory, salient features, spectrochemical series, splitting of d-orbitals in
tetragonal, square planar, trigonal bipyramidal and square-pyramidal geometry, applications of CFT-
colours of transition metal complexes, magnetic properties of octahedral complex, distortion of
octahedral complex, Jahn-Teller distortions CFSE and their uses, factors affecting CFSE, limitations
of CFT, experimental evidence for metal-ligand covalent bonding in complexes, nephelauxetic
effect, Ligand Field Theory, MO theory: Square planar complex tetrahedral and octahedral
complexes (including sigma and singma and π- interactions), angular overlap model. Redox
chemistry and analytical applications. [15 hrs]

UNIT– III
Electronic spectra of coordination compounds:Spectroscopic ground states, selection rules, term
symbols for dn ions, Spin-Orbit coupling, Racah parameters, Orgel, Correlation and Tanaube-Sugano
diagrams, spectra of 3d metal-aqua complexes of trivalent V, Cr, divalent Mn, Co and Ni, CoCl 42- ,
calculation of Dq, B and β parameters, Jahn-Teller distortions and spectra, CT spectra. Spectral
properties of Lanthanide and Actinide metal complexes. Photochemical reactions of transition metals
complexes: Basic photochemical processes, Kasha’s rule, quantum yield, Jabolnskii diagrams, photo
substitution reactions, photo-redox reactions, ligand photoreactions, and metal complexes as
photosensitizers. [15 hrs]
UNIT– IV
Magnetic properties of coordination compounds: Origin and Types of magnetic behaviour,
magnetic susceptibility and its determination- Gouy, Faraday, VSM method Quinke’s method, Evans
NMR method, Magnetic titrations. Curie’s law and Curie-Weiss law, Diamagnetic correction, orbital
contribution, spinorbital coupling, ferro and antiferromagnetic coupling, spin crossover. Magnetic
properties of axially symmetric crystal field, high spin/low spin equilibrium, Magnetic properties of
Lanthanide and Actinide metal complexes.

Higher coordination numbers, symbiosis, Introduction to ligand substitution reactions: Inert and
labile compounds, mechanism of substitutions – reaction pathways, Linear free energy relationships,
selected
examples, Introduction to redox chemistry of complexes.

UNIT-I
Ligand substitution reactions of complexes: Labile, inert, stable and unstable complexes,
classification of mechanisms - associative (A), dissociative (D) and interchange (I a and
Id).Mechanism of ligand substitution in octahedral complexes- kinetics, factors affecting substitution
in octahedral complexes: Leaving group, chelate and metal effects. Acid-Base catalysis: Acid
catalyzed aquation and anation reactions, base hydrolysis, conjugate base hydrolysis,
stereochemistry of octahedral substitution. FuossEigen equation and factors determining A or D
mechanisms, lability and inertness of complexes. Mechanism of ligand substitution in square planar
complexes- factors affecting substitution, trans-effect and its theories, cis-effect, designing synthetic
routs to cis-platin and other complexes of Pt group elements.
Metal exchange and ligand exchange reaction, and reaction of the coordinated ligand.[15 hrs]

UNIT – II
Redox process and reactions of coordinated ligands: Electron transfer reactions, complementary
and non-complementary, outer sphere electro transfer- Marcus equation, their excited state electron
transfer, Inner sphere electron transfer-one and two electron transfer and use of electron transfer
reactions for the synthesis of complexes. Kinetics, effect of metal and ligands, Bridging group
effects. Mixed metal Complexes (Electron transfer), mixed valence complexes. Mechanism of atom
transfer processes, halogen, Oxo-and hydride transfer reactions, electron transfer reactions.
Applications of redox process in bioinorganic chemistry: Reactions involving N 2, H2O2 and
molecular oxygen. Reactions of coordinated Ligands: Acid dissociation, hydrolysis of amino acid
esters, peptides, proteins, substitution, amine exchange, trans amination, thermodynamic and kinetic
template effects, metal assisted macrocyclization. Chemistry of variable oxidation states of
Transition metals: Low and High oxidation states, negative oxidation states, stability, effect
of concentrations on stability, electronic configuration, EMF, properties. Application of XPS
in oxidation state analysis. MOSSBAUER SPECTROSCOPY: Mossbauer effect and Mossbauer
nuclei, isomer shift, quadrupole splitting and magnetic hyperfine interactions, Chemical isomer
shift, elucidation of electronic structures of Fe(II) and Fe(III) systems.

[15 hrs]

UNIT-III
Photochemistry of co-ordination complexes: Fundamental concepts, Jablonski diagram,
classification of photochemical reaction. Electronic transitions in metal complexes - metal centered
and charge transfer transitions - various photophysical and photochemical processes of coordination
compounds - unimolecular charge-transfer photochemistry of cobalt (III) complexes - mechanism of
CTTM photoreduction. Ligand field photochemistry of Cr(III) complexes - Adamson’s rule -
photoactive excited states - V-C model - photophysics and photochemistry of Ru-polypyridine
complexes - emission and redox properties - photochemistry of organometallic compounds - metal-
carbonyl compounds - compounds with metal-metal bonding - Reinecke’s salt - chemical
actinometer. Application in water photolysis, Nitrogen and CO2reduction. Metal porphins
compounds, phthalocyanines complex, photoinduced emission and aggregation emission.
[15 hrs]

UNIT-IV
Metal complexes as drugs and therapeutic agents: Introduction, antimicrobial agents, antiviral
agents, antiarthritis agents and anticancer agents. Antidote complexes.

Medicinal Bioinorganic Chemistry: Bioinorganic Chemistry of quintessentially toxic metals. Lead,

Cadmium, Mercury, Aluminium, Chromium, Iron, Copper, Plutonium. Toxic effects-Mechanism of
toxic effects Detoxification by metal chelation - Chelating agents for Hg, Pb, Cd, As toxicity. Drugs
that act by binding at the metal sites of Metalloenzymes. Chemotherapy: Chemotherapy with
compounds of certain non-essential elements. Platinum complexes in cancer therapy – Cisplatin and
its mode of action and side effects: – Cytotoxic compounds of other metals – Gold containing drugs
as anti-rheumatic agents and their mode of action - Lithium in Psychopharmacological drugs.
Radiopharmaceuticals – Technetium. Metal complexes in diagnosis-gold complexes in magnetic
resonance imaging (MRI). Introduction to
nanomedicine and applications. [15 hrs]
ORGANOMETALLICS

UNIT-I
Organometallic Chemistry 1: Compounds with transition metal to carbon bonds: classification of
ligands, nomenclature, Bonding: Ionic vs Covalent model, MOT back bonding and eighteen electron
rule; Counting electrons in complexes, Hapticity, Limitations of 18-electron rule, Oxidation states
stability, transition metal carbonyls: range of compounds and structure, bonding, Inner and outer
sphere coordination, Polynuclear carbonyl complexes, vibrational spectra of metal carbonyls,
preparation, reactions; transition metal organometallics: square planar complexes, Carbonylates,
Carbonyl hydrides, Ligands similar to CO, Non aromatic metal alkyls, Metal carbenes, metal
alkylidenes and metal alkylidynes; Bridging alkyls, Structure and bonding: metal-olefin bond and
arene metal bond MO approach. Nitrogen activation.

UNIT-II
Organometallic Chemistry 2: Compounds with ligands having extended pi systems: cyclic pi
systems, bis(cyclopentadienyl) compounds, MO of metallocenes, cyclopentadienyl carbonyl
compounds, bis(arene) compounds, arene carbonyl compounds; isolobal analogy, Extensions of
analogy, Applications of the analogy metal-metal multiple bonds, Metal-carbonyl-metal bonds,
transition metal clusters; clusters and catalysis; hydride and dihydrogen complexes; bridging
hydrides, Non carbon ancillary ligands, Phosphines, organometallic fluxionality.

UNIT-III
Organometallic Chemistry 3: Organometallic reactions and catalysis: Ligand dissociation and
substituition – stereochemical aspect, Ligand cone angles, Redox effects, oxidative addition,
reductive elimination, Nucleophiles activity, Nucleophilic and electrophilic attack of coordinated
ligands, carbonalyte anions, insertion, hydride elimination, abstraction; Catalysis : Homogenous and
heterogenous catalysis, alkene hydrogenation, Tolman catalytic loop, Synthesis gas,
hydroformylation, Wacker process, ZieglerNatta polymerisation, cyclo oligomerisation, olefin
isomerisation, olefin metathesis, Monsanto acetic acid synthesis, Fischer-Tropsch process,
hydrosilylation. Organometallic Nitrogen fixation.

UNIT-IV
Organometallics Chemistry 4: Chemistry of Organolithium, Organomagnesium, Activity of
Nucleophiles, Organoboranes, organosilicon and selected transition metal compounds, copper
complexes, Vasaka complex, Bonding of Pd and Rh with olefins applications in C-C , C-N bond
formations, Heck reaction, Carbonylation, hydroformylation, olefin isomerism, arylation, aryl
amination using Pd reagents, olefin metathesis, Stille coupling, Sonogashira reaction, Buchwald
reaction and Pauson -Khand reaction. Surface supported organometallic catalysts. Asymmetric
catalysis, Organometallics in medicinal applications.

SOLID STATE CHEMISTRY AND ADVANCED MATERIALS

UNIT-I
The solid state: Types of solids, Bonding in solids, isomorphism and polymorphism, laws of
crystallography, lattice types, lattice energies, Packing efficiencies, X-ray diffraction, Bragg’s
equation, Miller indices, Bragg Method, Experimental methods-powder and rotating crystal methods,
indexing of powder and rotating crystal photographs.Debye Scherrer method of X-ray structure
analysis of crystals, indexing of reflections, identification of unit cells from systematic absence in
diffraction pattern, structure of simple lattice and X-Ray intensities, structure factor and its relation
to intensity and electron density, phase problem, procedure for an X-ray structure determination.
Defects in crystals, Stoichiometric
imbalance in crystals. [15 hrs]

UNIT-II
Solid State Reactions: General principle, nucleation and growth process of crystals, types of
reactions: Additive, structure sensitive, decomposition and phase transition reactions, tarnish
reactions, kinetics of solid state reactions, factors affecting the reactivity of solid state reactions.
Methods of Single Crystal Growth Solution growth; Melt Growth-Bridgeman, Czochralski,
Kyropoulus, Chemical Vapour Transport; plasma enhanced deposition, catalytic chemical vapour
deposition, arc discharge method,Fused Salt
Electrolysis; Hydrothermal method; Flux Growth. [15 hrs]

UNIT-III
Electronic Properties and Band Theory: Metals, insulators and semi-conductors, free electron
theory and its applications, electronic structure of solids, band theory, band structure of metals,
insulator, and semiconductors, doping in semiconductors, photoactive semiconductors, Junction
Properties: Metal-metal junctions, metal-semiconductor junctions, p-n junctions, industrial
applications of semiconductors: mixed oxides, spinels and other magnetic materials. Super
conductors:Meissner effect, type I and II super conductors, isotope effect, basic concepts of BCS
theory, manifestations of the energy gap,ionic conductivity in solids, diffusion, drift conductivity,
optical properties of solids, photo-conduction and photoelectric effects, laser action, solid state laser
and their applications. Thermal conductivity in metals,
semiconductors and insulators. [15 hrs]

UNIT-IV
Advanced materials: Advanced semiconductor materials, electronic materials, solar energy
conversion materials, Photonics and spintronics materials, solid state structural aspects - electrode
materials in electrochemical energy conversion devices, solid state electronic and Ionic conductors,
Thermo electric and piezoelectric, perovskites, Superconducting materials, Photoluminescent
materials, Inorganic-organic hybrid materials:Synthesis of metal oxides and its composite
nanoparticles by sol-gel, solvothermal and hydrothermal method.Porous materials: Hard and soft
template methods : Carbonaceous materials, metal
oxides. [15 hrs]

STRUCTURAL METHODS IN
INORGANIC CHEMISTRY-III

UNIT-I
Basic concept of spectroscopy: Overview of basic concepts: Light-matter interaction, transition
dipole moment, selection rules for electronic transitions.

Laser: Einstein coefficients, introduction to lasers, application of lasers in spectroscopy.

Molecular luminescence spectroscopy: Basic principles of fluorescence and phosphorescence,
excitation and deactivation processes (energy level diagram), factors affecting fluorescence and
phosphorescence, quenching of fluorescence, fluorescence (or phosphorescence) intensity,
fluorescence and chemical structure, instrumentation for fluorimetry and phosphorimetry,
application of fluorimetry and phosphorimetry, fluorescent indicators,comparison between
fluorimetry and phosphorimetry, chemiluminescence, spectral studies of some inorganic complexes.

[12
hrs]
UNIT- II
Advanced optical Spectroscopy: Surface plasmon spectroscopy, multiphoton spectroscopy,
singlemolecule spectroscopy, and applications.

Electron spectroscopy: Principle, working, components, instrumentation and applications in

chemical analysis.

Electron energy loss spectroscopy: Principle, working, components, instrumentation, and

applications for
chemical analysis.
[12 hrs]

UNIT - III
Imaging and Depth Profiling techniques: basic principle, instrumentation and application of
scanning electron microscopy (SEM); secondary Auger microscopy (SAM); scanning probe
microscopy (SPM); scanning tunneling microscopy (STM); transmission electron microscopy
(TEM); low energy electron diffraction (LEED).

Destructive techniques: Basic principle, instrumentation and application

of Atiomic absorption spectrocopy AAS, inductively coupled plasma-atomic emission spectroscopy
(ICP-
AES). [12 hrs]

UNIT-IV
Non-destructive techniques: Basic principle, instrumentation and application of Wavelength and
energy dispersive X-ray fluorescence spectroscopy (WDS and EDS); X-ray absorption spectroscopy
(XANES and EXAFS); secondary ion mass spectrometry (SIMS); temperature programmed
desorption (TPD); thermal desorption spectroscopy (TDS).

Structure characterization of any advanced materials by Fluorescence Spectra, XPS, EELS,

SEM,
AFM, STM, TEM, HR-TEM, IC-AES, EDS, XANES, SIMS, TPD and TDS.

ORGANIC CHEMISTRY

UNIT-I
Nature of Bonding and Aromaticity in Organic Molecules-Delocalization, Conjugation,
Resonance, Mesomericeffects Inductive effect, Hyperconjugation, Tautomerism, Hybridization.
Concepts of Aromaticity, non-aromaticity and antiaromaticity, Aromaticity in non-benzenoids
compound, Alternant and non-alternant hydrocarbons, Transition state structure, Hammond
postulate, Curtin-Hammett principle, kinetic and thermodynamic control, Hard and soft acids and
bases. [15 hrs]

UNIT-II
Reaction Mechanisms and intermediates- Generation structure, stability and reactivity of
carbocations, carbanions, carbon free radicals, carbenes and nitrenes. Effect of structure on
reactivity: Classification of reactions and mechanisms. Nucleophilic substitution reaction at a
saturated carbon: SN1, SN2, SNi .Aromatic Substitution Reactions: Electrophilic Substitution
Reactions: The arenium ion mechanism. Orientation and reactivity. Energy profile diagrams.
Nucleophilic substitution reactions: The SNAr,

ArSN1, and benzyne mechanisms. Elimination Reactions: The E1, E2 and E1cB mechanisms and
Orientation of the double bond. Saytzeff and Hoffmann rules. [15 hrs]
UNIT-III
Stereochemistry-I: Geometrical isomerism, cis-trans and E-Z nomenclature. Optical isomerism:
Elements of symmetry, chirality, topocity, and prochirality. Optical activity, Absolute and relative
configurations, D/L, d/l notations. CIP rules, assigning R, S configuration. Methods of resolution of
racemic mixtures.

Optical activity due to helicity, M P conventions, Chiral derivatizing agents, Chiral solvating agents.
Fischer, Newman, Sawhorse and flying wedge projections and their interconversions.
Conformational analysis of acyclic (butane) and cyclic alkanes (cyclopentane, cyclohexane mono
and di substituted).

Conformations in fused rings. [15 hrs]

UNIT-IV
Carbohydrates and Vitamins: Introduction, Kiliani-Fischer synthesis, Determination of
configuration of the monosaccharides, conformational analysis of monosaccharides. Reactions of
Carbohydrates, Synthesis of aldonic, uronic, Aldric acids and alditols. Structure elucidation of
sucrose and maltose. Structures of lactose, gentiobiose and meliobiose. Vitamins –Structure and
Biological importance of vitamins A C and E. Synthesis of- Vitamin B1 (thiamine), B2(riboflavin),
B5(pantothenic acid), B9(folic acid), H (biotin),
K1 and K2. [15 hrs]
UNIT-I
Addition to carbon-heteroatom multiple bonds: Mechanism of metal hydride reduction (LiAlH4,
NaBH4,
NaBH(OAc)3, NaBH3(CN)) of saturated and unsaturated carbonyl compounds, acids, esters and
nitriles.
Addition of Grignard reagents and organolithium reagents to carbonyl compounds and unsaturated
carbonyl Compounds. Hydrolysis of nitriles and addition of amines isocyanates Wittig, Mannich and
Stobbe reactions.

Addition to carbon-carbon multiple bonds: mechanistic and stereochemical aspects of addition

reactions involving electrophiles, nucleophiles and free radicals. Regio, stereo- and
chemoselectivities. Orientation and reactivity. Addition to cyclopropane ring. Michael reaction.

Self-Study: Vilsmeier-Haack reaction, Gatterman reaction, Gattermann-Koch reaction and Hoesh

reaction. Von Richter reaction, Sommelet-Hauser and Smiles rearrangements, Addition of alkenes
and/or alkynes to
alkenes and/or alkynes. Ene synthesis. [15 hrs]

UNIT-II
Molecular Rearrangements: Molecular rearrangements: Definition and classification. Molecular
rearrangements involving i) electron deficient carbon: Wagner- Meerwein, Pinacol-Pinacolone, and
Wolf rearrangement. ii) electron deficient Nitrogen: Hofmann, Lossen, Curtius, Schmidt
rearrangements iii) electron deficient Oxygen: Baeyer-Villiger oxidation. iv) Base catalysed
rearrangements: Aldol condensation, Benzoin, Knoevengel, Sommlett-Hauser and Smiles
rearrangement.

Multi-component Reactions: Studies on the mechanistic aspects and use of the following reactions
in organic synthesis: Passerini-Ugi; Hantsch; Biginelli; Doebner-Miller; Ritter; Jacobson; Betti;
Robinson-
Schopf; Barbier; Baylis-Hilmann; Ivanov and Suzuki coupling reaction. [15 hrs]

UNIT-III
C-C and C-N bond forming reactions: Darzen’s reaction, Use of acetylides in C-C bond formation
reactions. Acid-catalyzed self-condensation of olefins, Prins reaction, Shapiro reaction, Dieckmann
cyclization, Robinson annulations, Hofmann-Loeffler-Freytag reaction. Hofmann-Martius reaction.
Acyloin condensation. Houben-Hoesch reaction. Stork-enamine synthesis. Meyer synthesis. Use of
nucleophilic nitrogen and electrophilic carbon (NH3, amines and nitrite as nucleophiles in
substitution, NH3 and amines in addition to ketones and aldehydes) and electrophilic nitrogen and
nucleophilic carbon (nitration, nitrosation) for the bond formation reactions.

Self-Study: Chichibabin reaction, Skraup synthesis, Mitsunobu reaction, N-Nitroaromatic amine

rearrangement, Fisher-Hepp reaction, Japp-Klingemann reaction. [15 hrs]

UNIT-IV
Reagents in organic synthesis: Use of the following in organic synthesis and functional group
tansformations. Aluminium iso-propoxide, NBS, LDA, DCC, DDQ, 1,3-Dithiane (reactivity and
umpolung), Sulphur ylides, PPA, Yamaguchi reagent. Woodward and Prevost hydroxylation

Oxidations-I: Cr (VI) oxidants, Mn (VII) oxidants, OsO4- and co-oxidants SeO2, Pb (OAc)4, IBX and
related reagents.

Oxidations-II: ozone, peroxides (H2O2, t-BuOOH, dibenzoylperoxide) and per acids (Preparation,
properties and applications of CF3COOOH, m-CPBA, monoperphthalic acid) as oxidizing agents.
Reductions: Complex metal hydrides, dissolving metal reductions (including Birch, Benkeser,
Clemmensen reductions), diimide reduction, catalytic hydrogenation (homogeneous and
heterogeneous), Hydrogenation of double and triple bonds, hydrogenation of aromatic
rings.McMurry reaction. Pummer, Willgerdo.

[15 hrs]
Self-Study: Corey-Chaykovsky reagent, Raney-Nickel, diazomethane, TMS-chloride, HIO4, Ag2O,
DMSO,
Dess-Martin oxidation. Wolf-Kishner reduction Corey-Bakshi-Shibata and Tishchenko reactions,
Junjappa-
Ila hetero aromatic annulation reaction.

PHYSICAL CHEMISTRY

UNIT – I
Chemical Thermodynamics
Thermodynamics: Brief overview of thermodynamic laws, Concepts of Work, heat, energy,
Enthalpy, entropy and free energy. Expansion of work, Molar heat capacities, Joul Thomson
experiment, Carnot cycle, Entropy change during spontaneous process. Gibbs and Maxwell relations,
Helmholtz and Gibbs free energies. Thermodynamic criteria of equilibrium and spontaneity.
Variation of free energy with temperature and pressure. Third law of thermodynamics - calculation of
absolute entropies.

Partial molar properties: Partial molar volumes and their determination by intercept method and
from density measurements. Chemical potential and its significance. Variation of chemical potential
with temperature and pressure. Formulation of the Gibbs Duhem equation.
[15 hrs]

UNIT – II
Statistical Thermodynamics
Fugacity: Determination of fugacity of gases. Variation of fugacity with temperature and pressure.
Activity and activity coefficients. Variation of activity with temperature and pressure. Determination
of activity coefficient by vapor pressure, depression in freezing point, solubility measurements by
electrical methods.

Thermodynamics of dilute solutions: Raoult’s law, Henry’s law. Ideal and non-ideal solutions.
Statistical Thermodynamics: Different ensembles and Partition functions-translational, rotational,
vibrational and Electronic partition functions BE, FD, MB statistics and distribution, ensembles,
partition functions and molecular partition functions, mean energy, Residual entropy, heat capacity of
mono and diatomic gases, Einstein theory of heat capacity of solids. [15 hrs]

UNIT – III: CHEMICAL KINETICS

Kinetics: Theory of reaction rates, kinetics of complex reactions, Parallel, consecutive and
reversible reactions. Determination of order of reaction. Energy of activation and its experimental
determination.

Simple collision theory - mechanism of bimolecular reaction. Lindemann’s theory, Hinshelwood’s

theory, for unimolecular reaction (No derivation). Activated complex theory of reaction rate,
classical thermodynamic treatment, partition function, statistical thermodynamic treatment. Kinetics
of reactions in solution - Salt effect, effect of dielectric constant (single sphere and double sphere
model), effect of pressure, volume and entropy change on reaction rates.

Fast reactions: Study of kinetics by flow techniques, equation for contact time, stopped flow and
continuous flow methods. Relaxation method, equation for relaxation time, temperature jump and
pressure jump methods, flash photolysis, pulse radiolysis and shock tube method. Potential energy
surface, theoretical calculation of energy of activation. [15 hrs]
UNIT – IV: Electro Chemistry
Introduction, Mobility and conductivity of electrolytes, Arrhenius theory of strong and weak
electrolytes and its limitations, Concept of activity and activity coefficients in electrolytes, Debye-
Huckel theory of strong electrolytes, Debye Huckel-Onsager equation, Debye-Huckel limiting
equation for activity coefficient. A brief survey of Helmholtz-Perrin, Gouy-Chapman and Stern
electrical double layer (No Derivation). Liquid junction potential and its determination. Transport
Number: Determination of transport number by Hittorf method and e.m.f method. Effect of
temperature and concentration on transport number. Reversible and irreversible electrodes, reversible
and irreversible cells. Electrode and cell potentials, Polarization, over voltage. Experimental
determination of over voltage. decomposition potential Equations for concentration over potential,
diffusion current – stationary current, potential curves at a dropping mercury electrode,
polarography, half wave potential, application in qualitative and quantitative analysis. Butler-Volmer
equation, Tafel equation (No derivation). [15 hrs]

UNIT – I
Quantum Chemistry: Planck’s concept of quantization, Wave-particle duality of material particles,
de
Broglie equation, Heisenberg Uncertainty principle, Concept of operators (operator–operand),
Algebra of operators, commutative and non-commutative operators, linear operator, Laplacian
operator, Hamiltonian operator, Eigen value, Eigen function, class Q function, Hermitian operator.
Schrodinger wave equation for particles, Eigen values and Eigen functions, postulates of quantum
mechanics. Application of Schrodinger equation to a free particle (one dimension and three
dimensions). Degeneracy, Wave equation for H-atom, Physical interpretation of wave function,
separation and solution of R, ф and θ equations. Orbital and spin momentum interpretation. Particle
in a box, Application of Schrodinger equation to rigid rotator and harmonic oscillator. Approximate
methods – approximate methods, perturbation method, the theory of perturbation method – first
order and second order corrections, application to He-atom (first order correction only) – calculation
of first ionization potential and binding energy. Variation theorem: statement and proof. Orbitals
shapes and electron density distribution, quantum mechanics in periodic properties,
MO formation, Quantum tunneling.

Unit II
Symmetry elements and symmetry operations, point groups, examples. Group theory: Concept of
a group, definition of a point group, procedure for classification of molecules into point groups.
Subgroups. Schoenflies and Hermann-Maugin symbols for point groups. Multiplication tables for the
symmetry operations of simple molecules. Matrix notation for the symmetry elements and for
geometric transformations. Class of a group and similarity transformation.

Representation of groups: Reducible and irreducible representations. Labeling of irreducible

representations. Group theory and hybrid orbitals to form bonds. Character tables (Cs, Ci, C 2, C2v,
C2h), GOT.

Applications of group theory: Symmetries of Molecular orbitals, Basic MOT, orbital symmetries,
Applications of group theory to crystal field, Symmetry and dipole moments, symmetry and optical
activity, crystallography.

UNIT – III
Microwave spectroscopy: Rotation spectra of diatomic Molecules - rigid and non-rigid rotator
model. Rotational quantum number and selection rule. Effect of isotopic substitution on rotation
spectra. Classification of polyatomic molecules based on moment of inertia - Linear, symmetric top,
asymmetric top and spherical molecules.

Rotation spectra of polyatomic molecules, Moment of inertia expression for linear tri-atomic
molecules.
Applications - Principles of determination of Bond length and moment of inertia from rotational
spectra. determination of dipole moments.

Vibration spectroscopy:Vibration of diatomic molecules, vibrational energy curves for simple

harmonic oscillator. Effects of anharmonic oscillation. Vibration - rotation spectra of carbon
monoxide. Expressions for fundamental and overtone frequencies. Vibration of polyatomic
molecules – The number of degrees of freedom of vibration and their symmetry. Parallel and
perpendicular vibrations (CO2 and H2O). Fundamental, overtone, combination and difference bands.
Fermi resonance. Force constant and its significance. Theory of infrared absorption and theoretical
group frequency. Intensity of absorption band and types of absorptions. Structures of small
molecules: XY2. Factors affecting the group frequency –
Physical state, vibrational coupling, electrical effect, hydrogen bonding, steric effect and ring strain.

UNIT – IV
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. Comparison
of Raman and IR spectra, rule of mutual exclusion principle.
Electronic Spectroscopy: Franck-Condon principle, Transition moments, assignment of electronic
transitions of N2, H2O and formaldehyde using group theory, solvent effect,

Introduction to NMR:- Origin of magnetic moments in matter, electronic and nuclear moments,
interaction with magnetic field, Larmor equation - conditions for magnetic resonance absorption,
relaxation times, line widths and line shapes, chemical shifts, ring currents, diamagnetic anisotropy,
solvent effect, Hydrogen bonding effect, spin-spin splitting, Coupling constant, high resolution
NMR spectra of simple molecules, first and second order treatment of AB systems - FT techniques.
C13NMR introduction, problems and structure solution.

Other Resonance Spectroscopy Methods:- EPR, Electron spin resonance: g value, hyperfine and
fine structure, ESR of organic free radicals, ESR of solids, ESR of inorganic ions, ESR of simple
free radicals in solutions.

ORGANIC SPECTROSCOPY

UNIT-I
UV AND Visible Spectroscopy: Introduction to EMR, principle and instrumentation, Terminology,
classification of electronic transitions. Effect of substituent and conjugation on the spectra of
alkenes. Electronic spectra of carbonyl compounds. Effect of solvent on π – π* and n – π*
transitions. Woodward’s rules for calculating absorption maximum in dienes, carbonyl compounds,
Applications and structure analysis.

Infrared Spectroscopy: Principle and instrumentation, types of IR vibrational bands, Characteristic

vibrational frequencies of alkanes, alkenes, alkynes, aromatic compounds, alcohols, ethers, phenols
and amines. Detailed study of vibrational frequencies of carbonyl compounds (ketones, aldehydes,
esters, amides.). Effect of solvent, Electronic effects and hydrogen bonding on the vibrational
frequencies in

alcohols. Applications and structure analysis. [15 hrs]

UNIT-II
H1-NMR Spectroscopy: Introduction, basic principles and instrumentation of NMR spectroscopy.
The chemical shift and shielding. Factors affecting chemical shift. Magnetic anisotropy, electronic
effects, hydrogen bonding. Relaxation processes. Spin – spin coupling and splitting of NMR signals.
Spin – spin interactions – AX, AX2, AX3, AMX and AB types. The coupling constant. Intensities of
multiplets – Pascal’s triangle. Equivalence of protons – chemical and magnetic equivalence. Low
and high-resolution spectra of ethanol – chemical exchange. Geminal and vicinal coupling. Karplus
equation and Karplus curve.

Effect of hindered rotation on the NMR spectrum.

C13-NMR Spectroscopy: The carbon – 13 nucleus, carbon – 13 chemical shift. Proton coupled and
proton decoupled carbon – 13 spectra. NOE, COSY, HETCOR, Problems with integration in carbon
-13 spectra. Off resonance decoupling. Applications in structural elucidation. [15 hrs]

UNIT-III
Mass Spectrometry: Introduction, principle and instrumentation. Ion production electron impact,
chemical ionization, field desorption and fast atom bombardment, APCI, MALDI techniques. High
resolution mass spectrometry base peak, molecular ion, parent ion, fragmentation ion, metastable and
isotopic peaks. Factors affecting fragmentation, ion analysis and ion abundance. Mass spectral
fragmentation of organic compounds (hydrocarbons, aromatic compounds, alcohols, carbonyl
compounds). McLafferty rearrangement, ortho-effect. Determination of molecular weight and
molecular formula. Structuralelucidation. [15 hrs]

UNIT-IV
Electron Spin Resonance Spectroscopy: Theoretical principle and Instrumentation, ‘g’ factor,
hyperfine splitting, Kramers degeneracy. Illustration of hyperfine splitting using examples,
cyclopentadienyl radical, radical anions of benzene, naphthalene, p-benzosemi Quinone. Isotropic
spectra of some transition metal complexes and compounds, bis(salicylaldimine) Cu(II),
[VO(glycolate)2]-2, [(NH3)5Co-O-OCo(NH3)5]5+, Mn2+ as a substitution impurity in MgO.
Structuralelucidation of different organic compounds by using the spectral data. [15 hrs]

ANALYTICAL CHEMISTRY -I
UNIT – I
Errors and data analysis: Introduction to analytical techniques, factors affecting choice of
techniques. Basic definitions, Way of expressing accuracy, Errors: determinateand indeterminate and
their minimization. Distribution of random errors and explanation using the normal distribution
curve (Gaussian distribution). Propagation of determinant and indeterminate errors (problems),
Statistical treatment of finite samples; standard deviation and variance. Student’s t-test, confidence
interval of mean. Testing for significance - comparison of two standard deviations, Comparison of
two means, Comparison of an experimental mean and a true mean, rejection of a result - Q-test.

How to plot best fitting straight line; the least squares methods, standard deviations of the slope and
intercept, correlation between two variables, detection limit, statistics of sampling - sample size,
minimum sample size, and minimum number of samples. [15 hrs] UNIT – II

Titrimetric analysis: Acid-base titrations in non-aqueous media - Introduction to aqueous acid –

base titration, Role of non-aqueous solvent in acid-base titrations, differentiating ability of a solvent,
levelling effect, selected solvents, titration curves, determining the equivalence point, typical
applications - determination of carboxylic acids, phenols and amines.

Precipitation titrations: Principles of precipitation, common-ion effect, salt effect, Titration curves,
feasibility of precipitation titrations, factors affecting shape - titrant and analyte concentration,
completeness of the reaction, titrants and standards, indicators for precipitation titrations involving
silver nitrate, the Volhard, the Mohr and the Fajan’s methods, typical applications.

Complexometric titrations: Complex formation reactions, stability of complexes, role of metal

ions and ligands, stepwise formation constants, chelating agents, EDTA - acidic properties,
complexes with metal ions, equilibrium calculations involving EDTA, conditional formation
constants, EDTA titration curves, factors affecting the shape of titration curves - completeness of
reaction, indicators for EDTA titrations - theory of common indicators, titration methods employing
EDTA - direct, back and displacement titrations,
indirect determinations. [15 hrs]

UNIT-III
Introduction to electro-analytical techniques: an over view of electrochemistry – electrochemical
cells and reactions, electrode processes – faradaic and non-faradaic processes, brief description of
electrical double layer and double-layer capacitance and charging current in electrochemical
measurements, introduction to mass-transfer-controlled reactions, mechanism of mass transport,
various currents in electrochemical cells – charging, residual current, migration, diffusion and
convection currents, The current response to applied potential (in terms of Fermi and molecular
orbitals)

Electrogravimetry,Coulometry, and Coulometric titrations, Amperometry, Polarography a

voltammetric technique at a dropping mercury electrode (DME): Review of the principles of normal
dc polarography, types of currents obtained at a DME,Ilkovic equation and its application, current-
potential relation for a cathodic process – half-wave potential, basic aspects of electron transfer
across the electrode–electrolyte interface, reversible and irreversible polarographic process, criteria
for diffusion current and reversibility in polarography, electron transfer tests for the reversibility of a
process – irreversible processes at a DME,

a brief introduction to cyclic voltammeter. [15

hrs]

UNIT-IV
Chromatographic and Thermal methods: Basic theory of chromatography - Definition,
principles of separation, classification of chromatographic techniques. General descriptions of
column chromatography - frontal analysis, displacement analysis and elution analysis. General
theory of column chromatography: characterizing a chromatogram - retention time, retention volume
and baseline width.

Chromatographic resolution, capacity factor, column selectivity. Column efficiency – band

broadening, rate theory and plate theory. Peak capacity, non-ideal behavior. Optimizing
chromatographic separations using capacity factor, column selectivity and column efficiency - Van
Demeter equation, Golay and HuberKnox equations (only equations and terms involved).

Gas chromatography (GC): Principle, instrumentation - mobile phase, chromatographic columns,

stationary phases, sample introduction, temperature control, and detectors for gas chromatography
(naming of detectors) and applications.

High performance liquid chromatography (HPLC): Principle, instrumentation – columns

(analytical and guard columns), examples for stationary phases, mobile phases used in HPLC,
introduction to isocratic vs gradient elution process, detectors for HPLC (naming of detectors) and
applications.

Thermal Methods
Thermogravimetric analysis - TGA, DTA and DSC, principle, instrumentation, and factors affecting
the results, difference between TG and DTA, study of thermal stability of CuSO4.5H2O

and Ca2C2O4 2H2O by TGA.

UNIT - I: Liquid chromatographic techniques
(i) Reversed phase chromatography: Objectives, mechanism of reversed phase HPLC, applications
of reversed phase HPLC, analyte, retention in reversed phase HPLC, retention order in reversed
phase HPLC, reversed phase mobile phase solvents, solvent properties, mobile phase strength and
retention, role of organic modifier, eluotropic Series, selecting reversed phase columns, buffers for
reversed phase HPLC. (ii) Normal phase Chromatography: Objectives, mechanism of normal phase
chromatography, retention and Selectivity in normal Phase chromatography, separation of isomers
using normal phase chromatography, mechanism of isomer recognition in normal phase HPLC,
stationary phases for normal phase HPLC, typical mobile phases HPLC, controlling retention,
mobile phase optimisation, problems with Water in the mobile Phase

(iii) Ion Exchange chromatography- ion exchangers, ion exchange resins, ion exchange selectivity
and selectivity coefficient, Donnan equilibrium, conducting ion exchange chromatography,
applications (vi) Affinity chromatography – working principle, components - Matrix, ligand, spacer
arm and their required for efficient and effective chromatographic, matrix-partial structure of
agarose-Types of ligands- need of spacer arm. Immobilized metal affinity chromatography.

(v) Introduction to UPLC: Basic principle, difference between HPLC and UPLC, Instrumentation –
sample injection, columns, detectors, applications, advantages and dis advantages. [8 hrs]

UNIT-II
Gas Chromatography: Separation process in gas chromatography with schematic diagram, open
and closed tubular columns and comparison, effect of column inner diameter and length of the
Column, choice of liquid stationary phase, chiral phases for separating optical isomers, molecular
sieves as stationary phase, retention index, temperature and pressure programming, role of Van -
Deemter principle in carrier gas selection, types of columns in HPLC - Guard columns and retention
gaps, mode of sample injections - split injection, split less injection, and on column injection,
detector characteristics-signal to noise ratio, detection limits, Linearity.

Detectors-thermal conductivity detector, flame ionisation detector, electron capture detector, naming
of other detectors,GC- MS-Element specific plasma detectors, Sample preparation-solid phase micro
extraction, purge and trap, derivatisation in GC, method development in GC. [7 hrs]

UNIT-III
High-Performance Liquid Chromatography: The chromatographic process-effect of small
particles, scaling relation between columns, relation between number of theoretical plates and
particle size, column pressure, stationary phase and bonded stationary phases, monolithic silica
columns, The elution process - isocratic and gradient elution, selecting the separation mode,
maintaining symmetric band shape, dead volume, Injection and detection in HPLC, Detector
characteristics, signal to noise ratio, detection limits, Linearity, detectors - Spectro-photometric
detectors, refractive index detector, Evaporative Light scattering detector, Method development in
reverse phase separation, criteria for adequate separation, solvent optimisation - optimisation with
one organic solvent, optimization with two or three different organic solvents, choosing a stationary
phase, Gradient separations- Dwell volume and Dwell time, Chiral separation techniques.
[7 hrs]

UNIT-IV Electrodes and voltammetric techniques

Electrodes:Baisc principles,Reference electrodes, metallic indicator electrodes- electrodes of first
and second kind, redox electrodes, membrane electrodes-membrane potential, selectivity of
membrane, glass ion selective electrodes- Composition and structure of glass membrane,
Hygroscopicity of glass membrane, membrane and boundary potential and expression for Eb,
alkaline error, crystalline membrane electrode, conductivity of a crystalline membrane, solid state
ion selective electrode, liquid based ion selective electrodes, gas sensing electrodes, potentiometric
biosensors- enzyme electrodes.

Voltammetric techniques:Introduction, Objectives, Common Voltammetric Methods, Direct

Methods - Linear Sweep Voltammetry, Sampled DC Polarography, Hydrodynamic Voltammetry,
Pulse Methods Normal Pulse Voltammetry, Differential Pulse Voltammetry, Square Wave
Voltammetry, Cyclic Voltammetry - Principle of cyclic Voltammetry, cyclic voltammogram of
K3[Fe(CN)6], criteria of reversibility of electrochemical reactions, quasi- reversible and irreversible
processes, Stripping Methods -

Anodic Stripping Voltammetry, Cathodic Stripping Voltammetry, Adsorptive Stripping Voltammetry,

Alternating Current Methods - Voltammetry-Instrument.

HETEROCYCLIC CHEMISTRY
AND CHEMISTRY OF BIOMOLECULES

UNIT-1
Synthesis and reactivity of pyrrole, furan and thiophene. Basicity of pyrrole and pyridine.
Small ring heterocycles-Three and four membered heterocycles- synthesis and reactions of
aziridines, oxiranes, oxitanes, thietane. Five membered heterocycles containing two/three
heteroatoms- synthesis and reactions of imidazoles, thiazoles. Synthesis and reactions of benzo
pyrrole, benzo furans and benzo thiophene. [7 hrs]

UNIT-II
Six membered heterocycles with one heteroatom: Synthesis and reactions of pyrylium, pyridinium
and thiopyrylium salts. Six membered heterocycles with two and more heteroatoms-Synthesis and
reactions of diazine (pyrazine, pyridazine, oxazine, thiazine) & triazine (1, 2, 3, and 1, 2, 4). Seven
membered heterocycles –Synthesis,and reactions of azepine, oxepine & thiepine. [8 hrs]

UNIT-III
Introduction of biomolecules: Examples of biomolecules and building blocks of biopolymers.
Nucleic Acids-Purine and pyrimidine bases. Structure and synthesis of nucleosides and nucleotides.
(DCC, phosphor tri ester approach Properties of nucleic acids in solution. Base pairing, forces
stabilizing nucleic acid structure. Methods used in nucleic acid separation and characterization.
Hydrolysis of nucleic acids by acid and base. Enzymatic hydrolysis, Nuclease specificity and
restriction endonucleases.

Prostaglandins-General study, nomenclature, classification, structure and biological role of PGE1,

PGE2
and PGE3. [8 hrs]

UNIT-IV
Biochemical mechanisms
Introduction. The mechanistic role of the following in living systems.
1. Thiamine pyrophosphate (TPP) in decarboxylation of α-ketoacids and in the formation of
αketols.
2. Pyridoxal phosphate (PLP) in transamination, decarboxylation, dealdolisation and
elimination reactions of amino acids.
3. Lipoic acid in the transfer of acyl group reactions.
4. Coenzyme A (CoASH) in the transfer of acyl group.
5. Tetrahydrofolic acid (H4F) in one-carbon transfer reactions.
6. Vitamin B12 coenzymes in molecular rearrangement reactions and in the synthesis of
methionine and methane.
7. Nicotinamide and Flavin coenzymes in biological redox reactions. [7hrs]