(Syllabus) Ed.CET-2011 Entrance Test "Physical Science - Chemistry" Syllabus

Ed.CET-2011 Entrance Test Syllabus
Physical Science: Chemistry (Marks: 50)

Inorganic Chemistry

1. Atomic Structure and Elementary Quantum Mechanics

Black Body radiation, Plack's Radiation law, Photoelectric effect, heat capacity of solids, Comption effect. De Broglie's hypothesis, Heisenberg's uncertainty principle, Sinusoidal wave equation, Hamiltonian operator, Schordinger's wave equation and its importance, physical interpretation of the wave function

2. Chemical Bonding

Lonic solids - lattice and salvation energy, solubility of ionic solids rule, power and oplarisability of ions, covalent nature of ionic bond covalent bond - Stereochemistry of inorganic molecules - common hybridization and shapes of molecules Molecular orbital theory - Shapes and sign convention of atomic orbital, modes of overlapping, concepts of sigma and pi bonds, criteria for forming molecular orbital from atomic orbital, LCAO - concept, types of molecular orbital - bonding, antibonding and non-bobding, electron density distribution diagram for H2 +, MOED of homonuclear - H2, He2+, B2, C2, N2, O2, F2 and their ions (unhybridised diagrams only) and heteronuclear diatomic molecules CO, CN-, NO, NO- and HF. Bond order and magnetic properties.

3. Periodic properties

Review of trends in atomic and ionic radii - covalent radii - single, double and triple bond covalent radii, van der Waal radii, radii of cations, anions isoelectronic ions, ionization energy, Electropositivity, basic nature, reducing behavior, electron affinity and electro negativity - Methods of determination and evaluation - Pauling's and Mulliken's approach, application in predicting and explaining chemical behavior - nature of bond, bond length and bond angles, diagonal relationship.

4. s-block and p-block elements

Comparative study, salient feature of hydrides - ionic and covalent, ploynuclear, complex hydrides, reducing properties. Oxides - monoxide, peroxide and super oxide - basicity, oxidizing nature. Complexation tendencies.

Comparative study of group 13-17. Hydrides - Classification - ionic, covalent, metallic and complex hydrides. Synthesis of each class of hydrides. Structure of (a) covalent hydrides, electron deficient hydrides. Diborane, decaborane. (b) complex hydrides - borohydrides. Reactivity - stability, hydrolysis and reducing properties. Oxides - Classification - a) Normal - acidic, basic amphoteric and neutral, b) mixed, c) sub oxide, d) peroxide, e) super oxide. Structure of oxides of C, N, P, S and Cl. Reactivity - thermal stability, hydrolysis. Halides - Classification - ionic, covalent and complex halides. Structure of halides of B, C, Si, N, P, S. Reactivity - stability, hydrolysis. Lewis acid nature of boron trihalides. Oxy - acids - Oxy - acids of B, C, N, P, S and Cl - structure and acidic nature. Carboranes - Nomenclature, classification - closo, niod and arachno -*  preparation and structure. Borazole - Preparation, properties and structure.
Carbomyls - Classification - mono and ploynuclear, general preparation, structure and bonding in Ni(CO4), Fe(CO)5 and Co2(CO)8.

5. d - block elements

Chemistry of elements of First Transition series - electronic configuration, metallic nature, atomic and ionic radii, ionization potential - Oxidation state - relative stability of various oxidation states, ionic and covalenet character, acidic and basic nature, oxidizing and reducing nature of various oxidation states, redox potential - Frost and Latimer diagrams - stability, disproportionation and comproportionation of different oxidation states. Colour - d-d transition, colour and spectral behaviour of transition metal ions with respect of d1-d2 configuration. Magnetic behavior - determination of magnetic moment, Gou's balance, paramagnetism, diamagnetism. Complexation behaviour, stability of complexes - oxidation states, pi complexes, class-a, class-b and class-a/b acceptors. Catalytic properties - important examples.
Chemistry of elements of Second and Third Transition series - comparative treatment with their 3d analogues with respect to oxidation state, magnetic behavior, spectral properties. Study of Ti, Cr and Cu triads - Titanium triad - electronic configuration, reactivity of +III and +IV states - oxides, halides. Chromium triad - reactivity of +III and +VI states. Copper triad - reactivity of +l, +II, and +III states.

6. f- block elements

Chemistry of Lanthanides - electronic structure, position in periodic table, oxidation state, Atomic and ionic radii, Lanthanide contraction - cause and consequences, anomalous behaviour of post lanthanides, basicity, Complexation - type of donor ligands preferred, agnetic properties - paramagnetism. Colour and spectra - f-f transition. Occurrence and separation - ion exchange method, solvent extraction.
Chemistry of Actinides - General features - electronic configuration, oxidation state, actinide contraction, and colour and complex formation. Comparison with lanthanides.

7. Metals

Theories of bonding in metals - Free electron theory - thermal and electrical conductivity of metals, drawbacks. Valence bond theory - explanation of metallic properties and its limitations. Band theory - explanation of metallic properties, conductors, semi conductors and insulators. General methods involved in extraction of metals - minerals and ores, ore concentration - electromagnetic separation, gravity separation - wilfley table, hydraulic classifier, leaching, froth flotation, Calcination and roasting. Acid and alkali digestion. Reduction of oxides, carbonates, halides, sulphides, sulphates - smelting, flux, auro reduction, alumino - thermic reduction, hydrometallurgy, electrolytic reduction.

Purification of impure metals - liquation, fractional distillation, zone refining, oxidative processes - cupellation, bassemerisation, puddling, poling, thermal decomposition, Amalgamation, Electrolysis. Alloys - Classification, substitutional solid solutions, interstitial solid solutions, intermetallic compounds, Hume - Rothery rules. Preparation of alloys - fusion, electro deposition, reduction and compression Uses ferrous and non-ferrous alloys.

8. Co-ordination compounds

Nomenclature of inorganic molecules and complex compounds - A. Simple inorganic molecules - multiplying affixes, structural affixes (i) cations - monatomic homopolyatomic, (ii) anions - monoatomic, homopolyatomic, heteropolyatomic (iii) radicals (iv) isopolyanions (v) heteropolyanions (vi) salts and salt like compound (vii) addition compounds. B. Complex compounds - Werner's theory - postulates, experimental evidences. Sidwick's theory - calculation of BAN, limitations. Metai Ligand bonding in Transition metal complexes - Valence bond theory - postulates, geometries of coordination number 4 - tetra hedral and square planer and 6 - octahedral. Limitations.

Crystal field theory - features,

splitting of d - orbitals in octahedral, tetrahedral and square planar complexes, crystal field stabilization energy, (elementary treatment -diagrams only). Magnetic properties of Transition metal complexes. Types of magnetic behavior, spin only formula, calculation of magnetic moments. Electronic spectra of metal complexes - d-d transitions, spectrochemical series. Determination of composition of complexes, Job's method and mole ratio method, Stability constants, factors affecting stability of complexes. Isomerism in co-ordination compounds - Structural - ionization, hydrate, linkage, coordination, coordination position and polymerization isomerism. Stereoisomerisms - geometrical and optical isomerism.

Hard and soft acids and bases

Classification, Pearson's concept of hardness and softness, application of HSAB principles - stability of complexes, predicting the feasibility of a reaction. Organic chemistry -1

9. Stereochemistry of carbon compounds

Molecular representations: Wedge, Fischer, Newman and Saw-horse formulae. Isomeris: Definition of homomers and isomers. Classification of isomers; Constitutional and Stereosiomers - definition and examples. Constitutional isomers: chain, functional, positional isomers and metarerism. Stereoisomers: enantiomers and diastereomers - definitions and examples. Conformational and Configurational isomerism - definition.

10. Structural theory in Organic Chemistry

Brief review of structural theory of organic chemistry, Hybridization, Bond length, bond angle, bond energy, curved arrow notation, drawing electron movements with half headed and double headed arrow. Types of bond fission and organic reagents (Electrophilic, Nucleophilic, and free radical reagents including neutral molecules like H2O2, BF3, NH3 & AICI3.

Bond polarization: Factors influencing the polarization of covalent bonds, electro negativity - inductive effect. Application of inductive effect, (a) Basicity of amines(b) Acidity carboxylic acids (c) Stability carbonim ions. Resonace or Mesomere effect, application to (a) acidity phenol, (b) acidity of carboxylic acides. Hyper conjugation and its application to stability to stability of carbonium ions, Free radicals and alkenes.
Types of organic reactions: Addition - electrophilic, nucleophilic and free radical. Substitution - electrophilic, nucleophilic and free radicium. Elimination - Examples (mechanism not required).

11. Acyclic Hydrocarbons:

Alkanes - IUPAC Nomenclature of Hydrocarbons. Method of preparation: Hydrogenation of alkynes and alkenes, Wurtz reaction, Keibe's electrolysis, Corey-House reaction. Chemical reativity - inert nature, free radical substitution mechanism. Halogenation examples - reactivity, selectivity and orientation. Conformational analysis of ethane and n-butance.

Alkene - Preparation of alkenes (a) by dehydration of alcohols (b) dehydrohalogenation of alkyl halides (c) by dehalogenation of 1, 2 dihalides (brief mechanism), Zaitsev's rule. Properties: Addition of Hydrogen - heat of hydrogenation and stability of alkenes. Addition of halogen and its mechanism. Adition of HX, Markonikov's rule, addition of H2O' HOX, H2SO4 with mechanism and addition of HBr in the presence of peroxide (anti - Markonikv's addition).

Oxidation - hydroxylation by KMnO4, OSO4 Peracids (Via epoxidation), nydroboration, ozonolysis - location of double bond. Dienes - Types of dienes, reactions of conjugated dienes- 1, 2 and 1, 4 addition of HBr to 1,3- butadiene and Diel's - Alder reaction.

Alkynes - Preparation by dehydrohalogenation of dihalides, dehalogenation of tetrahalides acetylene from CaC2. Properties: Acidity of acetylenic hydrogen (formation of metal acetylides). Preparation of higher acetylenes, metalammonia reductions. Physical properties. Chemical reactivity - electrophilic addition of X2, HX, H2O (taoutomerism), Oxidation (formation of enediol, 1, 2 diones and carboxylic acids), reduction and polymerization reaction of acetylene

12. Benzene and its reactivity

Molecular formula of Benzene, structure of Benzene - open chain structure not possible, proposition of cyclic structure by kekule, dynamic equilibrium, evidence based on ozonolysis experiment, concept of resonance, resonance energy. Heat of hydrogenadon, heat of combustion of Benzene, mention of C-C bond lengths and orbital picture of Benzene.

Concept of aromaticity - aromaticity (definition), Huckl's rule - application to Benzenoid (Benzene, Napthalene, Anthracene and Phenanthrace) and Non- Benzenoi compounds (cyclopropenyl cation, cyclopentadienyl anion and tropylium cation).

Reactions General mechanism of electrophilic substitution mechanism of nitration and sulfonation. Mechanism of halogenatton, Friedel craft's alkylation and acylation. Orientation of aromatic substitution - Definition ortho, para and meta directing groups. Ring activating and deactivating group with examples (Electronic Interpretation of various groups like NO2 and Phenolic). Orientation: (i) Amino methoxy and methyl groups, (ii) Carboxy, nitro mitrile, carbonyl and

sulfonic acid groups, (iii) Halogens (Explanation by taking minimum of one example from each type).

13. Areness and polynuclear aromatic hydrocarbons

Polynuclear hydrocarbons - Structure of naphthalene and anthracene (Molecular Orbital diagram and resonance energy) Reactivity towards electrophilic substitution. Nitration and sulfonation as examples.

Hydroxy compounds

Nomenclature and classification of hydroxyl compounds. Preparation: from carbonyl compounds. Aryl carbinols by hydroxyl methylation. Phenols - (a) by diazotization (b) from sulfonic acid (c) from cumene (d) by hydrolysis of halobenzene. Physical properties - Hydrogen bonding (inter molecular and intramolecular) effect of hydrogen bonding on boiling point and water solubility Chemical properties (a) acidic nature of Phenols (b) Formation of aloxide/phenoxides and their reaction with RX (c) replacement of OH by X using PCI5, PBr3, SOCI2 and with HX/ZnCI2. Esterification by (a) acid halides, anhydrides and acids (mechanism) (b) Esters of inorganic acids (c) dehydration of alcohols. Oxidation of alcohols by CrO3l KMnO4. Special reactions of phenols - (a) Bromination, (b) Kolbe - Schmidt reaction (c) Riemer Tiemann (d) Azo coupling. Identification of alcohols by oxidation - KmnO4, Ceric ammonium nitrate - Lucas reagent; Phenols by reaction with FeCIs, and by the solubility in NaOH. Polyhydroxyl compounds - Pinacol - Pinacolone rearrangement, Oxidative cleavage (Pb(OAc)4 & HIO4).

Carbonyl compounds

Nomemclature of aliphatic and aromatic carbonyl compounds and isomerism. Synthesis of aldehydes & ketones from acid chloride by using 1,3-dithianes,  nitriles and from carboxylic acids. Base catalysed reactions - with particular emphasis on Aldol, Cannizaro reaction, Perkin reaction, Benzoin condensation, haloform eaction, Knoevengeal condensation. Oxidation reactions - KMnO4 oxidation and auto oxidation, reduction - catalytic hydrogenation, Clemmenson's reduction, Wolf-kishner reduction, MPV reduction, reduction with LAH, NaBH4. Analysis - 2,4 - DNP test, Tollen's test, Fechlings test, Scihffs test, haloform test (with equations). Introduction to ap-unsaturated carbonyl compounds.

Nitrogen compounds

Nitro hydro carbons: Nomenclature and classification - nitro hydrocarbons - structure. Tautomerism of nitroalkanes leading to acid and keto form. Preparation on Nitroalkanes. Reactivity - halogenation, reaction with HONO (Nitrous acid), Nef reaction and Mannich reaction leading to Michael addition
and reduction. Aromatic Nitro hydrocarbons: Nomenclature, Preparation of

Nitrobenzene by Nitration (mechanism), from diazonium salts. Physical properties, chemical reactivity - orientation of electrophonic substitution on nitrobenzene. Reduction reaction of Nitrobenzenes in different media. Amines (Aliphatic and Aromatic): Nomenclature, classification into 1°, 2°, 3° Amines and Quaternary ammonium compounds. Preparative methods - 1. Ammonolysis of alkyl halides 2. Gabriel synthesis 3. Hoffman's bromamide reaction (mechanism). Reduction of Amides and Schmidt reraction.

Chemical Properties: (a) Alkylation (b) Acylation (c) Carbylamine reaction (d) Hinsberg separation. 5. Reaction with Nitrous acid of 1°, 2°, 3° (Aliphatic and aromatic amines). Electophilic substitutions of Aromatic amines - Bromination and Nitration, oxidation of aryl and 3° Amines, diazotization. 6. Diazonium salts: Preparation with mechanism. Synthetic importance - (a) Replacement of diazonium group by - OH, X (Cl) - Sandmeyer and Gatterman reaction, by fluorine (Schiemann's reaction), by iodine, CN, NO2, H and aryl groups. Coupling Reraction of diazonium. (i) with phenols (ii) with anilines. Reduction to phenyl hydrazines.

14. Heterocyclic Compounds

Introduction and definition: Simple 5 membered ring Compounds with one hetero atom Ex. Furan, Thiophene and pyrrole. Importance of ring systems - presence in important Natural products like hemoglobin and chlorophyll. Numbering the ring systems as per Greek letters and Numbers. Aromatic character - 6- electron system (Four - electrons from two double bonds and a pair of non bonded electrons from the hetero-atom). Tendency to undergo substitution reactions.

15. Carbohydrates

Introduction: Classification and nomenclature - classification into mono, oligo and polysacchrides into pentoses, hexoses etc. into aldoeses 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, reducation 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-glyceraldehydes 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 (methylaltion, hydrolysis 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 and Haworth formula). Inter Conversion of Monosaccharides: Aldopentose to aldo hexose - eg: Arabinose to D-glucose, D-mannose (kiliani - Fischer method). Epimers, Epimerisation. Lobry debruyn van Ekenstein rearrangement. Aldohexose - Aldopentose eg: D-g!ucose to D-arabinose by Ruff's degradation. Aldohexose (+) (glucose) to ketohexose (-) (fructose) and Ketochexose (Fructose) to aldohexose (Glucose).

16. 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 syntheis of alpha amino acids (specific examples - Glycine, Alanine, valine and Leucene) by following methods: (a) From halogenated Carboxylic acid (b) Malonic ester syntheis (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 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.

Physical Chemistry

17. Gaseous state

Deviation of real gases from ideal behavior, Vanderwaal's equation of state. Critical Prenomena: PV - isotherms of real gases, continuity of state, Andhrew's isolthems of carbon dioxide. The vander waals equation and the critical state, Derivation of relationship between critical constants and Vander waal's constants. Experimental determination critical constants. The law of corresponding states, reduced education of state. Joule-Thomson effect and inversion temperature of a gas. Liquid action of gases: i) Linde's method bases on Joule-Thomson effect, ii) Claude's method based on Adiabatic expansion of a gas.

18. Liquid state

Intermoie alar forces, structure of liquids (qualitative description). Structural different between solids, liquids and gases. Liquid crystals, the mesomorphic state: classification of liquid crystals into Semectic and Nematic, differences between liquid crystal and solid/liquid. Application of liquid crystals as LCD devices, lubricants and in digestion/assimilation of food.

19. Solid state:

Laws of Crystallography - (i) Law of Constancy of interfacial angles (ii) Law of Symmetry, symmentry elements in crystals (iii) Law of rationality of indices. Definition of space lattice, unit cell. Bravais Lattices and Seven crystal systems. Structure of NaCI (Bragg's method and Powder method). Defects in crystals: Stoichiometric and Non-stoichiometric defects. Band theory of Semiconductors: Extrinsic and Intrinsic semi conductors, n-type and p-type and their applications in photo electro chemical cells

20. Dilute Solutions and Colligative properties

Dilute solutions, colligative properties, ideal and non-ideal solution. Raoult's law, relative lowering of vapor pressure, molecular weight determination. Osmosis laws of somotic pressure, its measurement, determination of molecular weight from osmotic pressure. Elevation of boiling point and depression of freezing point. Derivation of relation between molecular weight and elevation in boiling point and depression in freezing point. Experimental methods for determing various colligative properties. Abnormal molar mass, Van't Hoff factor, degree of dissociation and association of solutes.

21. Colloids and Surface Chemistry

Definition of colloids, classification of colloids. Solids in liquids (sols): Preparation and properties - kinetic, optical and electrical: stability of colloids, protective action, Hardy-Schultz law, gold number. Liquids in liquids (emulsions): types of emulsions, preparation and emulsifier. Liquids in solids (gels) classification, preparation and properties, inhibition, general applications of colloids.

22. Solutions

Liquid - liquid mixtures - ideal liquid mixtures, Raoult's and Henry's law. Nonideal systems. Axeotropes - HCI-H2O, ethanol-water systems. Fractional distillation. Partially miscible liquids - phenol-water, trimethyl amine-water,nicotine-water systems, Lower and upper consolute temperature. Effect of impurity on consolute temperature. Immiscible liquids and steam distillation.

23. Chemical Kinetics
Rate of a reaction, factors influencing the rate of a reaction - concentration, temperature, pressure, solvent, light and catalyst. Concentration dependence of rates, mathematical characteristics of simple chemical reactions - Zero order, first order, second order, pseudo first order, half-life and mean life. Determination of order of a reaction - differential method, method of integration, half-life method and isolation method. Radioactive decay as first order phenomenon. Arrhenius equation, and concept of activation energy. Theories of chemical kinetics: effect of temperature on rate of a reaction Simple collision theory based on hard sphere model.

24. Thermodynamics

Definition of thermodynamic terms: System, surroundings, types of systems, and intensive and extensive properties. State and path functions and their differentials. Thermodynamic process. Concept of heat and work. First law of Thermodynamics: Statement, definition of internal energy and enthalpy. Heat capacity, heat capacities at constant volume and pressure and their relationship. Joule's law - Joule. Thomson coefficient and inversion temperature. Calculation of w,q, dU and dH for the expansion of ideal gases under isothermal and adiabatic conditions for reversible process. Temperature dependence of enthalpy - Kirchoff s equation. Second law of Thermodynamic: need for the law, different statements of the law. Carnot cycle and its efficiency, Carnot Theorem. Thermodynamic scale of temperature. Concept of entropy, entropy as a state function, entropy as a function of V & T, entropy as a function of P & T, entropy change in physical processes. Gibbs and Helmholtz functions: Gibbs function (G) and Helmholtz function (A) as thermodynamic quantities. A & G as criteria for thermodynamic equilibrium and spontaneity, their advantage over entropy change. Variation of G with P,V and T.

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