M.Sc. (Previous) DEGREE EXAMINATION, MAY First Year Chemistry Paper - I : GENERAL CHEMISTRY. Time : 03 Hours Maximum Marks : 80

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1 Paper - I : GENERAL CHEMISTRY (DCHE 01) NR Part - A (4 8 = 32) 1) Explain the allowed transitions between rotational energy levels in Microwave spectroscopy. 2) Discuss the types of molecular spectroscopy. Giving suitable examples. 3) Explain the vibrational structure of an electronic transitions in visible spectroscopy. 4) Write about radiation sources and detectors used in different regions of Infra Red (IR) spectroscopy. 5) Explain the method of least squares. 6) Write the techniques involved in the collection of solid samples for analysis. 7) Make a comparison between micro computer and super computer. 8) Explain DO statements with one inner loop in Fortran. Part - B (4 12 = 48) Answer All questions 9) a) i) Discuss the microwave spectra of non-rigid rotor. ii) Explain the basic principle of NMR spectroscopy. b) i) Discuss the microwave spectra of linear molecules. ii) Explain the vibrational spectra of diatomic molecules in Infra Red Spectroscopy. 10) a) i) Discuss the rotational fine structure of electronic vibrational transitions of UV - visible spectroscopy. ii) Explain the basic principle of ESR spectroscopy. b) i) By taking suitable examples, explain diatomic vibrating rotator in IR spectroscopy. ii) Write the analytical applications of UV-visible spectroscopy. 11) a) i) Explain the sampling techniques in the collection of gaseous samples for analysis. ii) Explain the storage of samples in the laboratory before analysis.

2 b) i) Explain regression analysis. ii) Write about minimization of propagation of errors in analytical experiments. 12) a) Write a flow chart and Fortran programme to calculate the rate constant of a first order reaction. b) Write a flow chart and Fortran programme to solve Vander Waal s equation.

3 Paper - II : INGANIC CHEMISTRY (DCHE 02) NR Part - A (4 8 = 32) 1) Explain the interpretation of and Heisen-berg s in certainty principle. 2) Explain spin and orbital angular momentum. 3) What are the bond orders of CN -, CN and CN +? Which of these species will have the shortest bond length? Explain. 4) Explain ion formation and types of ions giving suitable examples. 5) Discuss the magnetic properties of transition metal ions. 6) Draw and explain orgel diagram and spectrum of d2 ion. 7) Describe the classification of labile and inert complexes according to valence bond theory with examples. 8) Write the preparation and properties of Silicates. Part - B (4 12 = 48) Answer all questions 9) a) Explain variation method and its application to determine ground state energy of hydrogen atom. b) Discuss the schrodinger wave equation for an electron in a box. 10) a) State and explain the important postulates of Molecular orbital theory. Draw and explain M.O energy diagram of O2. b) Discuss the types of crystals with suitable examples. 11) a) Describe the factors affecting the stability of metal complexes with relevant examples. b) Define crystal field stabilization energy (CFSE). Discuss the crystal field splitting of d orbitals in octahedral complexes with examples. 12) a) Discuss the ligand substitutions of SN1 and SN2 in square planar complexes with suitable examples. b) Write the preparation, properties and structures of carboranes.

4 Paper - III : GANIC CHEMISTRY (DCHE 03) NR Part - A (4 8 = 32) 1) a) What is meant by hyper conjugation? Why is it also termed as no- bond resonance? b) Write a note on tautomerism give examples. 2) Write a note on: a) Huckel s rule. b) Anti-aromaticity. 3) Explain the following: a) Isotopic effects. b) Steric effects. 4) Write a note on: a) Anchimeric assistance. b) SNi reaction. 5) a) Discuss the general mechanism and draw an energy profile diagram of aromatic electrophilic substitution reactions. b) Give the mechanism of Sandmayer reaction give examples. 6) Explain the terms regio and chemo-selectivity give examples. 7) a) Write the mechanism of Metal hydride reduction of Saturated Carbonyl Compounds give examples. b) Give the Mechanism Stobbe reaction. 8) Discuss the mechanism and stereochemical evidence of E2 elimination reaction. Part - B (4 12 = 48) UNIT I 9) a) i) Explain annulenes and homo aromaticity. ii) Explain why aromatic amines are weaker bases than aliphatic amines?

5 b) i) Discuss the factors affecting relative Stability of Conformations. ii) Draw Newman projection formulae for the chair and boat form of cyclohexane? Which form is more stable and why? UNIT II 10) a) i) What are Carbonions? Discuss their characteristics, structure and stability? ii) Explain kinetic and thermodynamic control reactions give examples. b) Explain the following: i) Nucleophilic substitution at an allylic carbon. ii) Ambident nucleophiles. iii) Non classical Carbocation. UNIT III 11) a) i) Discuss the orientation and reactivity of aromatic electrophilic substitution reactions. ii) Explain free radical rearrangements give examples. b) Write the mechanism and stereochemical aspects of addition reactions involving electrophile, nucleophile and free radical reactions on Carbon-Carbon multiple bonds give examples. 12) a) Explain the following: i) Mannich reaction. ii) Aldol condensation. iii) E1CB reaction. UNIT IV b) i) Discuss various factors which effect the extent of E1 and E2 eliminations. ii) Explain hydrolysis of esters and amides give examples.

6 Paper - IV : PHYSICAL CHEMISTRY (DCHE 04) NR 1) Derive Thermodynamic phase rule. Section - A (4 8 = 32) 2) State and explain second law of Thermodynamics and write its applications. 3) Explain radiocarbon dating and isotope dilution analysis. 4) What are conductors, semiconductors and insulators? Write their applications. 5) How do you determine surface area of solids by BET method? 6) How do you explain the anamolous behaviour of strong electrolytes? 7) Distinguish between homogeneous and heterogeneous catalysis with suitable examples. 8) Write and explain photochemical reaction and mechanism of Hydrogen and Bromine. 9) a) Explain Maxwell partial relation-ships b) Write about : i) Partial molar quantities. Section - B (4 12 = 48) Answer All questions ii) Vant Hoff reaction isotherm. 10) a) Explain Bragg s equation, Bravais lattices and Miller indices. b) Describe compound nucleus theory. 11) a) Derive an equation for EMF of a cell without transference. b) Define standard electrode potential and write its determination. Add a note on concentration cells.

7 12) a) Discuss the mechanism of acid base catalysis and primary salt effect. b) Write note on : i) Photosensitization. ii) Photochemical chain reactions.