I Sem
Paper 1 CH 101 (INORGANIC CHEMISTRY)
Course Outcome
1. Students understand the symmetric operations,symmetric elements of molecules and molecular point groups
2. Students learn the crystal field theory,d-orbitals splitting,CFSE calculation and magnetic behaviour of co-ordination complexes
3. Students learn the types of stability constants, influencing factors and determination methods
4. Students learn 18 valence electron rule for metal carbonyls and metal nitrosyls
IC-01: Symmetry of Molecules: 15 hrs Marks-80
Concept of Symmetry in Chemistry – Symmetry Operations – Symmetry Elements:
Rotational Axis of Symmetry and Types of Rotational Axes, Plane of Symmetry and types of Planes, Improper Rotational Axis of Symmetry , Inversion Center and Identity Element – More about Symmetry Elements – Molecular Point Groups: Definition and Notation of Point Groups, Classification Molecules in to C1, Cs, Ci, Cn,Cnv, Cnh, C∞v, Dn, Dnh, Dnd, D∞h, Sn (n=even), Td, Oh, Ih, Kh Groups. Descent in Symmetry with Substitution – Exercises in Molecular Point Groups – Symmetry and Dipole moment – Symmetry criteria for Optical activity.
IC – 02: Bonding in metal complexes – I: 15 hrs
Crystal Field Theory: Salient features of CFT. d-orbital splitting patterns in regular Octahedral, tetragonally distorted octahedral, Jahn-Tellar theorem , trigonal bipyramidal, trigonal planar, Pentagonal bipyramidal, and linear geometries. Concept of weak field and strong fields. - Calculation of crystal field stabilization energies (CFSE’s) in six and four coordinate complexes. Types of magnetic behaviour – magnetic susceptibility – calculation of magnetic moment from magnetic susceptibility spin only formula ,- Quenching of orbital angular momentum – Determination of magnetic moment from Guoy’s method.. Applications of magnetic moment data for the determination of oxidation states, bond type and stereochemistry. Spin crossover: High spin, low spin cross over phenomenon in [Fe(Ophen)2(NCS)2] and [Fe(R2NCS2)3]. Spinels.
IC-03: Coordination Equilibria: 15 hrs
Solvation of metal ions- Metal complex formation in solution-Binary metal complexes. Stability constants (types and relationships between them). – Factors influencing the stability constants: (i) Metal ion effects (charge/size, IP, crystal field effect, John-Teller effect, Pearson theory of hard and soft acids and bases (HSAB), elecronegativity and hardness and softness, symbiosis. (ii) Ligand effects (Basicity , Substituent effect , Steric , Chelate(size and number of chelate rings), Macrocyclic and Cryptate effects- crown ethers , crypton, size match selectivity or concept of hole size, limitations, Macrocycles with pendent groups– Methods used for the determination of Stability constants (Basic Principles only): pH metric, Spectrophotometric and Polarographic methods.Ternary Metal Complexes – definition – Formation of ternary metal complexes – Step-wise and simultaneous equilibria with simple examples.
IC – 04: Ligational Aspects of Diatomic molecules 15 hrs
Metal Carbonyls:- Carbon monoxide as a ligand – Molecular orbitals of CO - Donor and Acceptor molecular orbitals of CO; Bonding modes of CO- Terminal and Bridging; Evidence for multiple bonding from Bond lengths and Stretching frequencies; 18 Valence electron rule and its application.
Metal Nitrosyls: - NO as a ligand – Molecular orbitals of NO – Donor and Acceptor components; Bonding modes of NO – Terminal (Linear, Bent) and Bridging; Structural aspects of [IrCl(PPh3)2(CO)(NO)]+ and [RuCl(PPh3)2(NO)2]+.
Stereo chemical control of valence in [Co(diars)2(NO)]2+ and [Co(diars)2(NO)(SCN)]+.
Metal Dinitrogen complexes: - N2 as aligand – Molecular orbitals of N2; Bonding modes – Terminal and Bridging; Stretching frequencies; Structures of Ru (II) and Os(II) dinitrogen complexes; Chemical fixation of dinitrogen.
Suggested References:
1. Symmetry and Group theory in Chemistry, Mark Ladd, Marwood Publishers, London (2000).
2. Molecular Symmetry and Group Theory, Robert L.Carter, John Wiley & Son (1998).
3. Symmetry and Spectroscopy of Molecules. K.Veera Reddy, New Age International (P) Limited (1999).
4. Advanced Inorganic Chemistry. F.A.Cotton, G.Wilkinson, C.A.Murillo and M.Bochmann, 6th Edition, Wiley Interscience, N.Y (1999
5. Inorganic Chemistry, J.E. Huheey, K.A.Keiter and R.L.Keiter 4 th Edition Harper Cottens College Publications (1993).
6. Homogeneous Catalysis by Metal complexes Vol I, M M Taqui Khan and A E Martell, Academic Press NY (1974).
7. Inorganic Chemistry, Keith F.Purcell and John C.Kotz, Holt-Saunders International Editions, London (1977).
Paper-II: CH 102 T (Organic Chemistry)
Course Outcome
1.Students learn the molecular representations,molecular symmetry, ,chirality and configuations(R&S ; E&Z)
2.Students learn the mechanisms of reactions involving electrophilic addition to carbon-carbon double bond
3.Study of conformations of alkanes and unsaturated hydrocarbons along with factors affecting conformational stability and conformational equilibrium
4.Students learn the nomenclature,synthesis and reactivity of heteocyclic compounds along with the impotance of natural products as drugs
OC-01: Stereochemistry 15 hrs
Molecular representations: Wedge, Fischer, Newman and Saw-horse formulae, their description and interconversions.
Molecular Symmetry & Chirality: Symmetry operations and symmetry elements (Cn & Sn). Criteria for Chirality. Desymmetrization.
Axial, planar and helical chirality: Axially chiral allenes,spiranes,alkylidene cycloalkanes, chiral biaryls, atropisomerism, planar chiral ansa compounds and trans- cyclooctene, helically chiral compounds and their configurational nomenclature
Relative and absolute configuration: Determination of configuration by chemical correlation methods.
Racemisation and resolution techniques: Racemisation, resolutions by direct crystallization, diastereoisomer salt formation chiral chromatography and asymmetric transformation.
Determination of configuration in E, Z-isomers: Spectral and Chemical methods of configuration determination of E,Z isomers. Determination of configuration in aldoximes and ketoximes.
OC-02: Reaction mechanism-I 15 hrs
Electrophilic addition to carbon carbon double bond: Stereoselective addition to carbon carbon double bond; anti addition- Bromination and epoxidation followed by ring opening. Syn addition of OsO4 and KMnO4.
Elimination reactions Elimination reactions E2, E1, E1CB mechanisms. Orientation and stereoselectivity in E2 eliminations. Pyrolytic syn elimination and α-elimination, elimination Vs substitution.
Determination of reaction mechanism: Determination of reaction mechanism: Energy profiles of addition and elimination reactions, transition states, product isolation and structure of intermediates, use of isotopes, chemical trapping and crossover experiments. Use of IR and NMR in the investigation of reaction mechanism.
OC-03: Conformational analysis (acyclic systems) 15 hrs
Conformational isomerism: Introduction to the concept of dynamic stereochemistry. Conformational diastereoisomers and conformational enantiomers .Study of conformations in ethane and 1,2-disubstituted ethane derivatives like butane, dihalobutanes, halohydrin, ethylene glycol, butane-2, 3-diol amino alcohols and 1,1,2,2-tetrahalobutanes. Klyne-Prelog terminology for conformers and torsion angles
Conformations of unsaturated acyclic compounds: Propylene, 1-Butene, Acetaldehyde Propionaldehyde and Butanone.
Factors affecting the conformational stability and conformational equilibrium: Attractive and repulsive interactions. Use of Physical and Spectral methods in conformational analysis.
Conformational affects on the stability and reactivity of acyclic diastereoisomers: Steric and stereoelectronic factors-examples.Conformation and reactivity. The Winstein-Holness equation and the Curtin – Hammett principle
OC-4: Heterocyclic compounds &Natural products 15 hrs
Heterocyclic compounds: Introduction, Nomenclature Synthesis and reactivity of indole, quinoline, isoquinoline, carbazole and acridine
Natural products : Importance of natural products as drugs.
Terpenoids : General methods in the structure determination of terpenes. Isoprene rule. Structure determination and synthesis of β-carotene, α-terpeniol and camphor.
Alkaloids: General methods of structure determination of alkaloids. Structure determination and synthesis of papaverine
References:
1.Stereochemistry of carbon compounds by Ernest L.Eliel and Samuel H. Wilen
2. Stereochemistry of organic compounds- Principles and Applications by D. Nasipuri
3.Heterocyclic Chemistry, T.L. Gilchrist, Longman UK Ltd, London (1985).
4.Benzofurans A. Mustafa, Wiley-Interscience, New York (1974).
5.Heterocyclic Chemistry, 3rd Edn J.A.Joule, K.Mills and G..F.Smith, Stanley Thornes Ltd,UK, (1998)
6.The Chemistry of Indole, R.J. Sunderberg, Academic Press, New York (1970).
7.An introduction to the chemistry of heterocyclic compounds, 2nd Edn.R.M.Acheson, Interscience Publishers, New York, 1967.
8.Advanced Organic Chemistry by Jerry March
9.Mechanism and Structure in Organic Chemistry S. Mukerjee
Paper CH 103 ( PHYSICAL CHEMISTRY)
Course Outcome
1.Students understand three laws of Thermodynamics and evaluation of entropy changes in various thermodynamic processes
2. Students learn the emf calculations and their applications
3. Students learn the various operators and their operations on Wave functions
4. Students understand kinetics of complex reactions and effect structure on reactivity of substances
PC-01: Thermodynamics-I 15 hrs
Concept of Entropy, Entropy as a function of V and T, Entropy as a function of P and T. Entropy change in isolated systems- Clausius inequality. Entropy change as criterion for spontaneity and equilibrium. Third law of thermodynamics. Evaluation of absolute entropies from heat capacity data for solids, liquids and gases. Standard entropies and entropy changes of chemical reactions. Thermodynamic relations. Gibbs equations. Maxwell relations. Gibbs equations for non-equilibrium systems. Material equilibrium. Phase equilibium. Clausius-Clapeyron equation .Conditions for equilibrium in a closed system. Chemical potential of ideal gases. Ideal-gas reaction equlibrium-derivation of equilibrium constant. Temperature dependence of equilibrium constant-the van’t Hoff equation.
Solutions: Specifiying the Solution composition. Partial molar poperties-significance. Relation between solution volume and partial molar volume. Measurement of partial molar volumes- slope and intercept methods. The chemical potential. Variation of chemical potential with T and P. Gibbs-Duhem equation-derivation and significance.
PC-02: Electrochemistry- I 15 hrs
Electrochemical Cells: Derivation of Nernst equation – problems. Chemical and concentration cells (with and without transference). Liquid junction potential (LJP) – derivation of the expression for LJP – its determination and elimination. Types of electrodes. Applications of EMF measurements: Solubility product, potentiometric titrations, determination of pH using glass electrode, equilibrium constant measurements.
Decomposition potential and its significance. Electrode polarization – its causes and elimination. Concentration over-potential.
Concept of activity and activity coefficients in electrolytic solutions. The mean ionic activity coefficient. Debye-Huckel theory of electrolytic solutions. Debye-Huckel limiting law (derivation not required). Calculation of mean ionic activity coefficient. Limitations of Debye-Huckel theory. Extended Debye-Huckel law.
Theory of electrolytic conductance. Derivation of Debye-Huckel-Onsager equation – its validity and limitations.
Concept of ion association – Bjerrum theory of ion association (elementary treatment)-ion association constant – Debye-Huckel-Bjerrum equation.
PC-03: Quantum Chemistry- I 15 hrs
A brief review of Black body radiation-Planck’s concept of quantization-Planck’s equation, average energy of an oscillator (derivation not required), Wave particle duality and uncertain principle-significance of these for microscopic entities. Emergence of quantum mechanics. Wave mechanics and Schrödinger wave equation.
Operators- Operator algebra. Commutation of operators, linear operators. Complex functions. Hermitian operators. Operators Ñ and Ñ2 .Eigenfunctions and eigenvalues. Degeneracy. Linear combination of eigenfunctions of an operator. Well behaved functions. Normalized and orthogonal functions.
Postulates of quantum mechanics: Physical interpretation of wave function. Observables and Operators. Measurability of operators. Average values of observables. The time dependent Schrodinger equation. Separation of variables and the time-independent Schrodinger equation. Theorems of quantum mechanics. Real nature of the eigen values of a Hermitian operator-significance. Orthogonal nature of the eigen values of a Hermitian operator-significance of orthogonality. Expansion of a function in terms of eigenvalues. Eigen functions of commuting operators-significance. Simultaneous measurement of properties and the uncertainty principle. Particle in a box- one dimensional and three dimensional. Plots of y and y2-discussion. Degeneracy of energy levels. Calculations using wave functions of the particle in a box-orthoganality, measurability of energy, position and momentum, average values and probabilities. Application to the spectra of conjugated molecules.
PC-04: Chemical Kinetics- I
Theories of reaction rates: Collision theory, steric factor. Transition state theory. Thermodynamic formulation of transition state theory. Potential energy surface diagram, Reaction coordinate, Activated complex. Activation parameters and their significance. The Eyring equation. Unimolecular reactions and Lindamann’s theory.
Complex reactions- Opposing reactions, parallel reactions and consecutive reactions (all first order type). Chain reactions-general characteristics, steady state treatment. Example- H2-Br2 reaction. Derivation of rate law.
Effect of structure on reactivity- Linear free energy relationships. Hammett and Taft equations-substituent (s and s*) and reaction constant (ρ and ρ*) with examples. Deviations from Hammett correlations, reasons- Change of mechanism, resonance interaction. Taft four parameter equation. Correlations for nucleophillic reactions. The Swain – Scott equation and the Edward equation. Reactions in solutions: Primary and secondary salt effects.
The reactivity-selectivity principle – Isokinetic temperature -Isoselectivty rule, Intrinsic barrier and Hammond’s postulate.
References:
1. Atkin’s Physical Chemistry, Peter Atkins and Julio de Paula, Oxford University press
2. Physical Chemistry, Ira N. Levine, McGraw Hill
3. Physical Chemistry-A Molecular approach, D.A. McQuarrie and J.D. Simon, Viva Books Pvt. Ltd
4. Molecular Thermodynamics, D.A. McQuarrie and J.D. Simon, University Science Books
5. Quantum Chemistry, Ira N. Levine, Prentice Hall
6. Introduction to Quantum Chemistry, A.K. Chandra, Tata McGraw Hill
7. Chemical Kinetics, K.J. Laidler, McGraw Hill
8. Kinetics and Mechanism of Chemical Transformations, J. Rajaraman and J. Kuriacose, McMillan
9. Introduction to Electrochemistry, S. Glasstone
10. Modern Electrochemistry, J. O. M. Bockris & A. K. N. Reddy, Plenum
11. Principles of physical chemistry, Samuel H. Maron and Carl F. Prutton, Oxford& IBH
12. The Physical Basis of Organic Chemistry by Howard Maskill, Oxford University Press (New York)
13. Chemical Kinetics and Reaction Mechanisms, J. H. Espenson, McGraw Hill
14. Physical Organic Chemistry, N. S. Isaacs, ELBS
15. Elementary Quantum Chemistry, F. L. Pilar, McGraw Hill.
16. Quantum Chemistry – D.A. Mcquarri Viva Publications.
Paper-IV: CH 104 (ANALYTICAL TECHNIQUES and SPECTROSCOPY- I)
Course Outcome
1.Students learn the principle and instrumentation of chromatography techniques
2. Students learn the proton NMR principle and identification of equivalent and non equivalent sets of protons
3.Students learn the rotational and vibrational transitions and energies of molecular systems along with the harmonic and anharmonic transitions
4.Students study the UV spectra of chromophores,hetero cyclic,poly nuclear compounds and cis-trans isomers
ASP-01: Techniques of Chromatography 15 hrs
i. Introduction, Classification of chromatographic techniques, differential migration rates, partition ratio, retention time, relation between partition ratio and retention time, capacity factor, selectivity factor. Efficiency of separation- resolution, diffusion, plate theory and rate theory.
ii. GC: Principle, instrumentation, detectors- TCD, FID, ECD. Derivatisation techniques, PTGC.
iii. HPLC: Principle, instrumentation, detectors- UV detectors, Photodiode array detector, fluorescence detector.
iv. Applications: Methods of quantitation for GC and HPLC: GC analysis of hydrocarbons in a mixture, GC assay of methyl testosterone in tablets, atropine in eye drops. HPLC assy of paracetamol and asprin in tablets.
ASP 02: NMR spectroscopy-I (1H NMR ) 15 hrs
1H NMR spectroscopy: Magnetic properties of nuclei, Principles of NMR Instrumentation, CW and pulsed FT instrumentation, equivalent and non equivalent protons, enantiotopic and diastereotopic protons, Chemical shifts, factors affecting the chemical shifts, electronegativity and anisotropy, shielding and deshielding effects, Signal integration, Spin-spin coupling: vicinal, germinal and long range, Coupling constants and factors affecting coupling constants.
Applications of 1H NMR spectroscopy: Reaction mechanisms (cyclic bromonium ion, electrophilic and nucleophilic substitutions, carbocations and carbanions), E, Z isomers, conformation of cyclohexane and decalins, keto-enol tautomerism, hydrogen bonding, proton exchange processes (alcohols, amines and carboxylic acids), C-N rotation. Magnetic resonance imaging (MRI). 1H NMR of organic molecules and metal complexes: ethyl acetate, 2- butanone, mesitylene, paracetamol, asprin, ethylbenzoate, benzyl acetate, 2-chloro propionic acid, [HNi(OPEt3)4]+, [HRh(CN)5] (Rh I=1/2), [Pt(acac)2].
ASP 03: Rotational, Vibrational and Raman spectroscopy 15 hrs
a). Microwave Spectroscopy: Classification of molecules based on moment of inertia. Diatomic molecule as rigid rotator and its rotational energy levels. Selection rules (derivation not required). Calculation of bond lengths from rotational spectra of diatomic molecules. Isotope effect on rotational spectra. Calculation of atomic mass from rotational spectra. Brief description of microwave spectrometer.
b). Vibrational Spectroscopy. Vibrational energy levels of diatomic molecules, selection rules (derivation not required). Calculation force constant from vibrational frequency. Anharmonic nature of vibrations. Fundamental bands, overtones and hot bands, Fermi Resonance. Vibrationrotation spectra diatomic molecules. Vibrations of poly atomic molecules. Normal modes of vibration, concept of group frequencies. Characteristics of vibrational frequencies of functional groups; Stereochemical effects on the absorption pattern in carbonyl group, cis-trans isomerism and hydrogen bonding. Isotopic effect on group frequency. IR spectra of metal coordinated NO3-, SO42- and CO32- ions.
c) Raman Spectroscopy- Classical and Quantum theories of Raman effect. Rotational Raman and Vibrational Raman spectra, Stokes and anti- Stokes lines. Complementary nature of IR and Raman spectra.
ASP 04:Electronic spectroscopy 15 hrs
Electronic spectroscopy: Electronic spectra: Elementary energy levels of molecules-selection rules for electronic spectra; types of electronic transitions in molecules. Chromophores: Congugated dienes, trienes and polyenes, unsaturated carbonyl compounds, Benzene, mono substituted derivative (Ph-R), di substituted derivative (R-C6H4-Rʹ) and substituted benzene derivatives (R-C6H4-CORʹ), Woodward-Fieser rules. Polynuclear aromatic compounds (Biphenyl, stilbene, naphthalene, anthracene, phenanthrene and pyrene). Heterocyclic systems. Absorption spectra of charge transfer complexes. Solvent and structural influences on absorption maxima, stereochemical factors. Cis-trans isomers, and cross conjugation. Beer’s law application to mixture analysis and dissociation constant of a weak acid.
References:
1. Fundamentals of Molecular Spectroscopy, Banwell and McCash.
2. Introduction to Molecular Spectroscopy, G.M. Barrow.
3. Absorption Spectroscopy of Organic Compounds, J.R. Dyer.
4. Biochemistry: Hames and Hooper.
5. Introduction to Spectroscopy, Pavia Lampman Kriz.
6. Pharmaceutical analysis, Watson
7. NMR in Chemistry- A multinuclear introduction, William Kemp.
8. Organic Spectroscopy, William Kemp.
9. Spectroscopy of organic compounds, P.S. Kalsi.
10. Structural methods n Inorganic chemistry, E.A.V Ebsworth.
11. Organic Spectroscopy, LDS Yadav
12. Organic Spectroscopy, Y.R. Sharma
13. Molecular Spectroscopy – Arhuldas
14. Vibrational spectroscopy – D.N. Satyanarayana
Practicals:
Paper CH 151:
Inorganic chemistry practicals: 6 hrs/week
I. Calibrations:
(i) Calibration of weights.
(ii) Calibration of pipettes.
(iii) Calibration of standard flasks.
(iv) Calibration of burette.
II. EDTA back-titrations:
(i) Estimation of Ni2+.
(ii) Estimation of Al3+.
III. EDTA substitution titrations: Estimation of Ca2+.
IV. Redox Titrations
(i) Estimation of Ferrocyanide and Ferricyanide in a mixture
V. Preparation of complexes:
(i). Hexaammine nickel (II) chloride. (ii). Tris (acetylacetanato) manganese.(iii). Tris (ethylenediamine) nickel (II) thiosulphate. (iv). Mercury tetrathiocyanato cobaltate (II). (v). Chloro pentaammine cobalt (III) chloride (vi). Tetrammine copper (II) sulphate and estimation of NH3 and calculation of % purity. (vii) One component gravimetric estimations
(i) Estimation of Zn2+(ii) Estimation of Ba2+ (as BaSO4)
Paper CH 152 Organic Chemistry Lab course 6 hours/ week
Synthesis of the following compounds:
p-Bromoacetanilide, p- Bromoaniline, 2,4,6-tribromoaniline, 1,3,5-tribromobenzene, aspirin, tetrahydrocarbazole, 7-hydroxy-4-methyl coumarin, m-dinitrobenzene, m-nitroaniline, hippuric acid, azlactone,anthracene-maleic anhydride adduct, Phthalimide, 2,4-dihydroxyacetophenone
References.
1. Text book of practical organic chemistry, Vogel
2. Text book of practical organic chemistry, Mann and Saunders.
Paper 153 Physical Chemistry Lab course: 6 hrs / week
Physical properties:
Data analysis I: Significant figures, Precision and accuracy
Distribution:
Distribution of acetic acid between n-butanol and water Distribution of iodine between hexanes and water
Chemical kinetics:
Acid-catalyzed hydrolysis of methyl acetate
Peroxydisulphate- I- reaction (overall order)
Oxidation of iodide ion by hydrogen peroxide- iodine clock reaction
Conductometry:
Titration of strong acid vs strong base
Titration of weak acid vs strong base
Determination of cell constant
Determination of dissociation constant of a weak acid
Potentiometry:
Titration of strong acid vs strong base
Titration of weak acid vs strong base
Determination of dissociation constant of a weak acid
Determination of single electrode potential
Polarimetry:
Determination of specific rotation of sucrose Acid-catalyzed hydrolysis of sucrose (inversion of sucrose)
Adsorption and others:
Adsorption of acetic acid on animal charcoal or silica gel
Determination of critical solution temperature of phenol-water system
Effect of added electrolyte on the CST of phenol-water system
Determination of molecular weight o f a polymer by viscometry.
References:
1. Senior Practical Physical Chemistry: B.D. Khosla, V.C. Garg and A. Khosla
2. Experimental Physical Chemistry: V. Athawale and P. Mathur.
3. Practical Physical Chemistry: B. Vishwanathan and P.S. Raghavan.
4. Practical in Physical Chemistry: P.S. Sindhu
5. Advanced Practical Physical chemistr: J.B.Yadav
6. Vogel Text book of Quantitative Analysis, 6th edition, Pearson education Ltd. 2002.