PAPER I- INORGANIC CHEMISTRY
Time: 3 Hours & Max Marks:50
Note : Each paper is divided into three independent units. The question paper is divided into three parts Part – A, Part-B and Part-C.
Part A (10 marks) is compulsory and contains 10 questions (50words each).Each question is of one mark.
Part-B (10 marks) is compulsory and contains five questions at least one from each unit. Candidate is required to attempt all five questions. Each question is of two marks (100 words).
Part-C (30 marks) contains six questions two from each unit. Candidate is required to attempt three questions one from each Unit. Each question is of ten marks (400 words.).
Unit I
(a) Stereochemistry and Bonding in Main Group Compounds
VSEPR, Irregular Geometry of molecules, 𝑑𝜋-p𝜋 bonds, Bent rule and energetics of hybridization, some simple reactions of covalently bonded molecules.
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(b) Metal Clusters
Higher boranes, carboranes, metalloboranes and metallocarboranes.
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Unit II
Fundamentals of Transition Metal Complexes :
Energy profile of reaction, reactivity of metal complexes, inert and labile complexes, kinetic application of valence bond and crystal field theories, kinetics of octahedral substitution, acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidences in favor of conjugate mechanism.
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Unit III
Reaction Mechanismof Transition Metal Complexes :
Anation reactions, reactions without metal ligand bond cleavage, Substitution reactions in square planar complexes, the trans effect, mechanism of the substitution reaction, Redox reaction, electron transfer reactions, mechanism of one electron transfer reactions, outer-sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions.
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Suggested Book -
Selected topics in inorganic chemistry MTM
PAPER II- REACTION MECHANISM-I
Unit I
(a) Nature of Bonding in Organic Molecules :
Delocalized chemical bonding-conjugation, cross conjugation, resonance, hyperconjugation, bonding in fullerenes, tautomerism, Aromaticity in benzenoid and non-benzenoid compounds, alternant and non-alternant hydrocarbons, Huckel’s rule, energy level of π-molecular orbitals, annnulenes, anti aromaticity, homo-aromaticity, PMO approach. Bonds weaker than covalent – addition compounds, Crown ether complexes and cryptands, inclusion compounds.
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(b) Reaction Mechanism :
Structure and Reactivity, Types of mechanisms, types of reactions, thermodynamic and kinetic requirements, kinetic and thermodynamic control, Hammond’s postulate, Curtin-Hammett principle. Potential energy diagrams. Generation, structure, stability and reactivity of carbocations, carbanions free radicals, carbenes and nitrenes.
Effect of structure on reactivity-resonance and field effects, steric effect,the Hammett&Taft equation- linear free energy relationship., substituent and reaction constants.
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Unit II
(a) Aliphatic Nucleophilic substitution
The SN2 SN1, mixed SN1 and SN2 and SET mechanism
(b) Aromatic Nucleophilic Substitution
The ArSN1, ArSN2, benzyne and SRN1 mechanism.Reactivity-effect of substrate structure, leaving group and attacking nucleophile. The von Richter, Sommelet-Hauser andSmiles rearrangements.
(c)Aliphatic Electrophilic Substitution.
Bimolecular mechanism-SE2 and SEi. The SE1 mechanism, electrophilic substitution accompanied by double bond shifts. Effect of substrates, leaving group and the solvent polarity on the reactivity.
(d) Aromatic Electrophilic Substitution
The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso attack, orientation in other ring system.quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling, Vismeir reaction, Gattermann-koch reaction.
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UNIT – III
Free Radical Reactions :
Types of free radical reactions, free radical substitution mechanism, mechanism at an aromatic substrate, neighbouring group assistance, Reactivity for aliphatic and aromatic substrates at a bridgehead, Reactivity in the attacking radicals, The effect of solvent on reactivity, Allylic halogenations (NBS), oxidation of aldehydes to carboxylic acids, auto-oxidation, coupling of alkynes and arylation of aromatic compounds by diazonium salts, Sandmeyer reaction, Free radical rearrangement, Hunsdiecker Reaction.
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PAPER III – PHYSICAL CHEMISTRY- I
Unit I
(a) Quantum Chemistry :
Schrodinger equation to some model systems viz., harmonic oscillator, the rigid rotor, the hydrogen atom. Applications of variation method and perturbation theory to the Helium atom.
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(b) Molecular Orbital Theory :
Huckel theory of conjugated systems, bond order and charge density calculations. Applications to ethylene, butadiene, cyclopropenyl radical, cyclobutadiene etc.
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Unit II
Thermodynamics :
Concept of fugacity and determination of fugacity. Non-ideal systems, Excess functions for non-ideal solutions, Activity, Activity coefficient, Debye Huckel theory for activity coefficient for electrolytic solution; determination of activity and activity coefficient; ionic strength. Application of phase rule to three component system – acetic acid + chloroform + water.
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Unit III
A. Chemical Dynamics :
Collision theory of reaction rates, steric factor, activated complex theory, ionic reactions, kinetic salt effects, steady state kinetics, kinetic and thermodynamic control of reactions, methods of determining mechanism, isotope effects.
Dynamic chain (hydrogen-bromine reactions, pyrolysis of acetaldehyde, decomposition of ethane), photochemical (hydrogen-bromine reaction), acid base catalysis, kinetics of enzyme reactions, general features of fast reactions, study of fast reactions by flow method, flash photolysis, dynamics of unimolecular reactions (Lindemann Theory, Hinshelwood Modifications).
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Books Suggested -
Principles of physical Chemistry by PSP
PAPER IV : COMPUTER AND DIFFRACTION METHODS
Unit I
(a) Introduction to Computers and Computing :
Basic structure and functioning of computers with a PC as an illustrative example.Memory, I/O devices.Secondary Storage.Computer language.Operating systems with DOS as an example.Introduction to UNIX and WINDOWS. Data Processing, principles of programming. Algorithms and flow-charts.
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(b) Computer Programming in C :
Overview of C, Constants., Variable and Data Types, Operators and Expression, Managing Input and output Operators, Decision Making and Branching, IF statement, IF….ELSE statement, GO TO statement, Decision Making and Looping, WHILE statement, DO statement and FOR Statement, Jumps in loop.
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Unit-II
(a) Programming in Chemistry :
Development of small computer codes involving simple formulae in chemistry, such as Vander waals equation, titration, kinetics, radioactive decay. Evaluation of lattice energy and ionic radii from experimental data.
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(b) Electron Diffraction :
Scattering intensity Vs. scattering angle, Wierl equation, measurement technique, elucidation of structure of simple gas phase molecules, Low energy electron diffraction and structure of surfaces.
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(c) Neutron diffraction :
Scattering of neutrons by solids and liquids, magnetic scattering, measurement techniques.Elucidation of structure of magnetically ordered unit cell.
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Unit - III
X-ray Diffraction :
Debye-Scherrer method of X-ray structural analysis of crystal, index reflections, identification of unit cells from systematic absences in diffraction pattern.
Structure of simple lattices and X-ray intensities, structural factor and its relation to intensity and electron density, phase problem.Description of the procedure for an X-ray structure analysis, absolute configuration of molecules.Ramchandran diagram.
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PAPER V : Chemistry Practicals
Time : 07 Hours & Max Marks-100
A. INORGANIC
PREPARATIONS (At least seven preparations)
(1)Tris(thiourea)copper (II)sulphate.
(2)Cis –Potassium Dioxalatediaquachromate(III).
(3)SodiumDiamminetetrathiocynatochromate(III)
(4) Trans-potassium dioxalatediaquachromate(III)
(5)Potassium Trioxalatoferrate(III)hydrate
(6) Potassium trioxalato chromate (III) trihydrate
(7)Purssian Blue.
(8)Hexamminecobalt(III) hexanitrocobaltate(III).
(9)Dichloridebis(pyridine)cobalt(II).
(10)Hexamminenickle(II) chloride.
(11)Bis(dimethylglyoximato)nickel (II).
(12)Tetramminecopper(II) sulphate monohydrate
(13) Mercury tetrathiocyanatocobaltate (II)
(14)Cis[Co(trien)(NO2)2]Cl.H2O
B. ORGANIC
(a)QUALITATIVE ANALYSIS (At least seven mixtures)
Separation, purification and identification of compounds of binary mixture (two solids) by water, ether, NaHCO3 and NaOH. Prepare derivative(s) where possible.
(b) QUANTITATIVE ANALYSIS (At least five)
(i) Estimate amines by acetylation method.
(ii) Estimate phenols using acetylation method.
(iii) Determine Iodine Value of an oil sample.
(iv) Determine Saponification Value of a fat or oil sample.
(v) Determine Saponification equivalent of an ester
(vi) Determine Acid Value of a fat or oil sample
(vii) Determine Aniline Point of an oil sample.
(viii) Determine the number of hydroxyl groups in an organic compound by acetylation method.
(ix) Determine the neutralization equivalent of the given carboxylic acid.
(C) PHYSICAL CHEMISTRY (Perform at least seven experiments)
1.Determination of the effect of change of temperature on the velocity constant of hydrolysis of an ester.
2.Determination of the effect of change of concentration of reactants and catalyst on the velocity constant of hydrolysis of an ester
3.Determination of the effect of Ionic strength on the velocity constant of hydrolysis of an ester
4.Determination of strength of strong acid in gm/l conductmetrically by titrating with strong base.
5.Determination of strength of strong acid in gm/l conductmetrically by titrating with weak base.
6.Determination of strength of weak acid in gm/l conductmetrically by titrating with strong base.
7.Determination of strength of weak acid in gm/l conductmetrically by titrating with weak base.
8.Determination of strength of strong and weak acid in gm/l in a given mixture conductmetrically by titrating against a strong base.
9.Determination of strength of strong and weak acid in gm/l in a given mixture conductmetrically by titrating against a weak base.
10.Determination of the dissociation constant of monobasic/ dibasic acid.
11. To find the relative and absolute viscosity of given liquid at room temperature using Ostwald’s Viscometer.
12. To determine the composition of the given mixture consisting of two miscible liquids A and B by viscosity measurement.
13. To determine the parachor of carbon and hydrogen atoms by drop weight method using stalagmometer.
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Previous Year Question Papers
PAPER I- INORGANIC CHEMISTRY
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PAPER II- REACTION MECHANISM-I
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PAPER III – PHYSICAL CHEMISTRY- I
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PAPER IV : COMPUTER AND DIFFRACTION METHODS
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