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SYLLABUS

Unit - 1

INORGANIC Chemistry 1. Inorganic Reaction Mechanisms Labile and inert complexes, Thermodynamic and kinetic stability based on VBT and CFT: Ligand substitution reactions – SN1 and SN2 in Octahedral complexes; substitution reactions of square planar complexes – Trans effect and applications of trans effect. Reactions of tetrahedral complexes – Hydrolysis of silicon halides and phosphorous oxides. 2. Bioinorganic Chemistry Essential elements, biological significance of Na, K, Mg, Ca, Fe, Co, Ni, Cu, Zn and chloride (Cl–). Toxic metal ions As, Hg & Pb. Oxygen transport and storage – structure of hemoglobin, binding and transport of oxygen. Fixation of CO2 in photosynthesis - overview of light and dark reactions in photosynthesis. Structure of chlorophyll and coordination of magnesium, Electron transport in light reactions from water to NADIp+ (Z-Scheme). 3. Hard and Soft Acids Bases (HSAB) Classification, Person’s concept of hardness and softness, application of HSAB principles – Stability of compounds/complexes predicting the feasibility of reaction.

Unit - 2

Organic Chemistry 1. Carbohydrates Introduction: Classification and nomenclature – Classification into mono, oligo and polysacchrides, into pentoses, hexoses etc., into aldoses and ketoses. Monosaccharides: All discussion to be confined to (+) glucose as an example of aldo hexoses and (–) fructose as example of ketohexoses Chemical properties and structural elucidation: Evidences for straight chain pentahydroxy aldehyde structure (Acetylation, reduction to n-hexane, cyanohydrin formation, reduction of Tollen’s and Fehling’s reagents and oxidation to gluconic and saccharic acids). Number of optically active, isomers possible for the structure, configuration of glucose based on D-glyceraldehyde as primary standard (No proof for configuration is required). Evidence for cyclic structure of glucose (some negative aldehyde tests and mutarotation). Cyclic structure of glucose. Proposition of cyclic structure (Pyranose structure, anomeric carbon and anomers). Proof for the ring size (methylation, hydrolysis and oxidation reactions). Different ways of writing pyranose structure (Haworth formula and chair conformational formula). Structure of fructose: Evidence of 2-ketohexose structure (formation of penta acetate, formation of cyanohydrin its hydrolysis and reduction by HI to give 2-carboxy-n-hexane) Same osazone formation from glucose and fructose, Hydrogen bonding in osazones, cyclic structure for fructose (Furanose structure, Haworth formula). Inter Conversion of Monosaccharides. Aldopentose to aldo hexose – eg: Arabinose to D-glucose, D-mannose (kiliani – Fischer method). Epimers, Epimerisation – Lobry de bruyn van Ekenstein rearrangement. Aldohexose – Aldopentose eg: D-glucose to D-arabinose by Ruff’s degradation. Aldohexose (+) (glucose) to ketohexose (–) (fructose) and Ketohexose (Fructose) to aldohexose (Glucose). Syllabus 2. Amino Acids and Proteins Introduction: Definition of amino acids, classification of amino acids into alpha, beta and gama amino acids. Natural and essential amino acids – Definition and examples, classification of alpha amino acids into acidic, basic and neutral amino acids with examples. Methods of synthesis: General methods of synthesis of alpha amino acids (specific examples – Glycine, Alanine, valine and Leucene) by following methods: (a) From halogenated Carboxylic acid (b) Malonic ester synthesis (c) Strecker’s synthesis. Physical properties: Optical activity of naturally occurring amino acids: L – configuration, irrespective of sign of rotation. Zwitter ion structure – salt like character, solubility, melting points, amphoteric character, definition of isoelectric point. Chemical properties: General reactions due to amino and carboxyl groups – Lactams from gamma and delta amino acids by heating peptide bond (amide linkage). Structure and nomenclature of peptides and proteins, peptide synthesis.

Unit - 3

Physical Chemistry Thermodynamics-I Abrief review of – Energy, work and heat units, mechanical equivalent of heat, definition of system, surroundings. I law of thermodynamics statement – various forms mathematical expression. Thermodynamic quantities – extensive properties and intensive properties, state function, path functions energy as a state function, and exact differential. Work of expansion and heat absorbed as path function. Expression for work of expansion, sign convention problems on I law. Heat changes at constant pressure and heat changes at constant volume. Enthalpy. Heat capacities at constant pressure and constant volume. Derivation Cp-Cv = R. Isothermal adiabatic processes, Reversible and irreversible processes. Reversible change and maximum work. Derivation of expression for maximum work for isothermal reversible process. Problems. Internal energy of an ideal gas. Joules experiment and Joule-Thompson coefficient. Adiabatic changes in ideal gas derivation of equation, PVg = constant. P-V curves for isothermal and adiabatic processes. Heat of a reaction at constant volume and at constant pressure, relation between DH and DV. Variation of heat of reaction with temperature. Kirchoff’s equation and problems. Limitations of I law and need for II law. Statement of II law of thermodynamics. Cyclic process. Heat engine, Carnot’s theorem, Carnot’s cycle. Derivation of efficiency of heat engine problems. Thermodynamic scale of temperature.

Unit - 4

Proton Magnetic Resonance Spectroscopy 1. Principles of nuclear magnetic resonance, equivalent and non-equivalent protons, position of signals. Chemical shift, NMR splitting of signals – spin-spin coupling, representation of proton NMR spectrum – Integrations. 1 H NMR spectrum of – ethyl bromide, acetaldehyde, 1,1,2-tribromo ethane, ethyl acetate and acetophenone. 2. Mass Spectrometry Electron Impact Mass: Basic principles, Nitrogen rule, types of ions: Molecular ion, fragment ion and isotopic ions, representation of mass spectrum, types of peaks (molecular ion, fragment and isotopic ion peaks). Determination of molecular weight. Mass spectrum of ethyl chloride, ethyl bromide and acetophenone. 3. Thermodynamics-II Entropy: Definition from Carnot’s cycle. Entropy as a state function. Entropy as a measure of disorder. Sign of entropy change for spontaneous and non-spontaneous processes & equilibrium processes, Entropy changes in (i) Reversible isothermal process, (ii) Reversible adiabatic process, (iii) Phase change (iv) Reversible change of state of an ideal gas. Problems, Entropy of mixing inert perfect gases. Free energy Gibb’s function (G) and Helmholtz’s function (A) as thermodynamic quantities. Concept of maximum work and net work DG as criteria for spontaneity. Derivation of equation DG = DH – TDS Significance of the equation. Gibb’s equations and the Maxwell relations. Variation of G with P, V and T.