University of Kashmir Syllabus for M.Sc. Entrance Test in Chemistry
Contents:
Section
A : Inorganic Chemistry
Unit-I
: Atomic Structure, Chemical Bonding
and Periodic Properties (04 Marks)
Unit-II
: S & P - Block Elements (04 Marks)
Unit-III
: Transition & Inner Transition (04 Marks) Elements
Unit-IV
: Coordination & Bioinorganic
Chemistry (04
Marks)
Unit-V
: Qualitative and Quantitative
Analyses (04
Marks)
Section
B : Organic Chemistry
Unit-VI
: Fundamentals of Organic Chemistry (04 Marks)
Unit-VII
: Hydrocarbons and their Halogen
Derivatives (04
Marks)
Unit-VIII
: Nitrogen and Oxygen bearing
Functional Groups (04 Marks)
Unit-IX
: Spectroscopy (04 Marks)
Unit-X
: Biomolecules (04 Marks)
Section
C : Physical Chemistry
Unit-XI
: States of Matter (04 Marks)
Unit-XII
: Chemical Kinetics and
Photochemistry (04
Marks)
Unit-XIII
: Laws of Thermodynamics and Chemical
(04
Marks) Equilibria
Unit-XIV
: Electrochemistry (04 Marks)
Unit-XV
: Quantum Chemistry and Spectroscopy (04 Marks)
Unit- I Atomic Structure
Chemical Bonding and Periodic Properties: (04 Marks)
Wave Mechanical Concept of Atomic
Structure: de- Broglie's wave
equation; derivation; experimental verification.
Heisenberg's Uncertainty principle: Illustration of the principle & significance.
Schrödinger wave equation: significance of Ψ and Ψ2.
Quantum numbers; Radial and
Angular wave functions and Probability distribution curves. Shapes of s, p,
& d orbitals.
Aufbau & Pauli's exclusion principles; Hund's multiplicity rule. Electron Configuration of
Elements. Effective nuclear charge and its determination.
Chemical Bonding : Ionic
Solids: Ionic Structures; Radius
ratio effect, Coordination number and limitations of radius ratio rule. Lattice
defects; Lattice energy and Born Haber Cycle. Solvation energy and solubility
of ionic solids. Polarizing power and polarisibility of ions; Fajan's rules.
Metallic bond: Characteristics;
comparison with ionic and covalent bonds & theories.
Valence bond theory: Directional
Characteristics of Covalent bond; types of Hybridization and Shapes of simple
molecules and ions. Limitations of VB theory.
Molecular Orbital Theory: LCAO,
Energy level diagram of homo- & heteronuclear diatomic molecules like N2, O2 , F2 ,CO, NO and
HCI.
Multicentre bonding in electron deficient molecules; Bond strength and Bond energy. Percent ionic character
from dipole moment and electronegativity difference.
Week
interactions: Hydrogen bonding
(concept, types; effect on properties) and Vander Waal forces.
Periodic properties: Atomic,
Ionic, Metallic and Vander Waal radii. Ionization Potentials, successive
ionization potentials; Electronegativity and Electron affinity: Trends in
Periodic table and Applications in predicting and explaining the Chemical
behaviour.
Unit -II S & P - Block
Elements (04 Marks)
S – Block Elements: General
trends in Physical and Chemical properties of the Elements and their important
classes of Compounds.
Lithium and Beryllium: Anomalous
behaviour and diagonal relationship.
Hydrides: Classification and
general properties.
Noble gases: Isolation and
importance of Noble gases in theoretical Chemistry.
Clathrates: Types,
preparation and stability.
Fluorides and Oxides of Xenon: Preparation,
properties, structure and bonding (VB and MO treatment).
P – Block Elements: Comparative study (including diagonal relationship and anomalous
behaviour) of groups (13 -17). '
Boron
Hydrides: Introduction, Nomenclature,
Preparation, Properties, Structure and bonding in diborane (including higher
boranes) Carboranes (Introductory idea)
Carbides: Classification,
Preparation, Properties and Uses,Intercalation Compounds of graphite.
Nitrogen
Compounds: Hydrazine, Hydroxylamine, Oxides and Oxyacids of
nitrogen (Properties, Structure- bonding & Uses).Oxygen fluorides, Oxides and Oxyacids of Sulphur
(Properties, Structure-bonding)
Halogens:General properties, Interhalogens; Polyhalides and
Pseudohalogens, (Structure -bonding),
Unit -III Transition &
Inner Transition Elements (04 Marks) Transition Elements: Definition, Classification, Position in the Periodic
table and the Electronic Configuration.
Physico-chemical properties: Atomic
radii, Ionic radii, Metallic character and related properties. ' Ionization
energies: Relation between the ionization energy and stability of a metal ion
in a given oxidation state.
Variable oxidation states: Ionic! covalent
character and Acidic/ basic character of compounds of a given transition metal
in various oxidation states and stabilization of unusual oxidation states.
Spectral
and Magnetic properties; calculation and uses of magnetic moment value.
Interstitial hydrides, carbides, nitrides and oxides of transition metals:
Preparation, properties and uses ( with respect to first transition series
only).
Inner Transition Elements: Lanthanoids: (At. No.58--); Introduction,
Electronic configuration, Oxidation states, Magnetic properties &
Complexing behaviour.
Ionic radii and
Lanthanide contraction: Cause and
Consequences of lanthanide contraction
Separation
of lanthanoids: Fractional
Crystallization, Ion-exchange and Solvent extraction methods.
Actinoids: (At.
No.90-103); Introduction, Electronic configuration, Oxidation states, Magnetic
properties & Comparison with lanthanoids. . Chemistry of Separation ofNp,
Pu and Am from U.
Unit -IV Coordination
& Bioinorganic Chemistry (04 Marks) Coordination Compounds: Introduction, Werner's Coordination Theory and its
experimental verification.
Effective
atomic number: Concept and its
significance. IUPAC Nomenclature and Stereochemistry of Coordination numbers
(2-6) Isomerism in
Coordination
Compounds : (including geometrical and optical) Valence bond and
Crystal field theories to explain, structure, bonding, magnetic and spectral
properties in transition metal complexes-( tetrahedral; square planar and
octahedral), 10 Dq ; Factors affecting the magnitude of 10 Dq; pairing energy
and CFSE in weak and strong field ligands. Applications of Coordination
Compounds in Analytical Chemistry.
Bioinorganic
Chemistry : The natural selection of
the elements: Abundance in the living systems and the distribution of elements
essential for life in the periodic table. Biochemical role of Li, Na, K, Ca,
Mg, Fe and halogens in living systems. Hannful effects of excess of metals on
human body.
Unit -V Qualitative &
Quantitative Analyses (04 Marks) Qualitative Analysis:
Underlying principles- Common-ion effect, Solubility
product, Relation between Solubility and Solubility product. Types of Qualitative Analysis: - Macro,
Semi micro; Micro; Ultra micro Analyses.
Analysis of Inorganic Mixtures; - Group
reagents, Selective precipitation of captons; Precipitation of Sulphides and
metal hydroxides. Effect of acids, temperature and solvent upon the Solubility
of a precipitate. Salt effect, Reactions involved in Separation and
identification of C!ltions and anions. .
Quantitative
Analysis: Gravimetry: Introduction,
Preparation of Solution and Precipitation methods. Physical properties of
precipitates: Appearance, particle size and purity. Fractional precipitation.
Colloidal State: Supersaturation; Precipitate formation, Co-precipitation and
post - precipitation. Digestion, Washing, Ignition, and Gravimetric
calculations.
Titrimetry: Acid - Base Titrations: Basic principles; preparation
of standard solutions; primary and secondary stapdards, theory of Visual
titration of acids and bases including polybasic acids. .
Indicators:
Types, Selection, and Preparation of indicator solutions. Precipitation
titrations: Basic principles; Detection of Equivalence points, (Mohr, Volhard,
Fajans, and Nephelometric methods). Redox titrations: Basic principles;
Balancing of redox equations, Redox reagents and their Equivalent weights.
Redox potentials and their applications in Volumetric analyses. Redox indicators: Types, selection and analysis of redox
cycle
Unit VI: Fundamentals of
Organic Chemistry & Isomerism (04 Marks)
Hybridization, Inductive, Electrometric, Resonance and hyperconjugative
effects. Requirements of aromaticity, Huckel's rule and its significance.
Carbocations, Carbanions and Free radicals (Structure and stability) Carbenes,
Benzynes and Nitrenes. Methods for determination of reaction mechanism. Concept
of stereo isomerism: elements of symmetry, molecular chirality, enantiomers and
diastereomers, Inversion, retention and racemisation.Sequence rules. R,S-System
of nomenclature. Geometrical isomers, E, Z-system of nomenclature.
Conformations of n-butane, ethylene glycol and 1 ,2-dibromoethane, cyclohexane
and its monosubstituted derivative, Axial and equatorial bonds. Baeyer's strain
theory and its limitations. Ring strain in smaller rings with respect to
cyclopropane ring.
Unit- VII: Hydrocarbons
and their Halogen Derivatives (04 Marks)
Methods of formation of Alkenes , Saytzeff rule, Hoffman rule.
Electrophilic and free radical additions.Marknwnikov's.rule Anti Markownikov's
addition of HBr, hydroboration,ozonolysis.. 1,2 and 1,4 Addition in conjugated
dienes. Diel's Alder reaction. Acidity of alkynes, Mechanism of electrophilic
and nucleophilic addition reactions of Alkynes. Mechanism of nucleophilic
substitution reactions of alkyl and benzyl halides: SN1, SN2 and SNi reactions.
Aromatic Electrophilic substitutions: General pattern of the mechanism of
nitration, halogenation Sulphonation and Friedal Craft's reaction. Activating
and deactivating substituents, orientation and ortho/para ratio. Birch
reduction. Addition - Elimination and Elimination Addition mechanisms of
nucleophilic aromatic substitution reactions.
Unit-VIII Nitrogen and Oxygen
bearing Functional Groups: (04 Marks) Mechanism
of nucleophilic substitution in nitroarenes. Reduction of nitrocompounds.
Preparation, properties and factors affecting basicity of amines. Mechanism of
Electrophilic aromatic substitution in arylamines. Reaction of aryl amines with
nitrous acid and reactions of arenediazonium salts. Azo coupling. Oxidative
cleavage of Alcohols with Pb(OAc)4 and HIO4 and Pinacole- Pinacolone rearrangement Electrophilic
Aromatic substitutions: Mechanism of Fries and Claisen rearrangements,
Gatterman, Huben-Hoesch and Reimer Tieman reactions. Acidic character of
phenols. Methods of formation of ethers and epoxides Acid and base catalysed
ring opening and reactions of Grignard and organolithium reagents with
epoxides. Stereochemistry and mechanism of nucleophilic addition to Carbonyl
group (Cram's rule). Benzoin, Aldol, Perkin, Knoevenagal & Mannich
reactions. Condensation with Ammonia and amines. LiAIH4 and NaBH4 reduction,
Meerwein-pondroff verley reduction. Oppenaner oxidation. Cannizzaro's reaction.
Baeyer-villiger oxidation, Clemmenson reduction, Wolf-Kishner reductions.
Factors affecting acid strength of carboxylic acids. Preparation of carboxylic
acids (using Grignard’s reagent and from nitriles). HVZ reaction, conversion of
acids to acid chlorides, esters,anhydrides and amides, their relative
stabilities and interconversion by nucleophilic acyl substitutions. Reduction
of carboxylic acids.
Unit-IX Spectroscopy: (04
Marks) Types of electronic
excitations, chromophore and auxochrome. Bathochromic and hypsochromic shifts.
UV spectra of conjugated enes and enones. Prediction of λ-max of enes and
enones using Woodward rules.
Infrared spectroscopy: Infrared region,
Molecular vibrations, Hooks law (No derivation), selection rules, the infrared
spectrum, Finger Print region, effect of resonance, Inductive effect, H-bonding
electronegativity on IR spectra. Characteristic absorption of the following
functional groups- Alkanes, Alkenes, Alkynes, Alcohols, ethers, carbonyl
compounds, amines and carboxylic acids. Interpretation of IR spectra of simple
molecules.
Nuclear Magnetic resonance (NMR) spectroscopy: Basic
principles, Proton magnetic resonance (1H NMR). Shielding and deshilding of - protons,
chemical shift and equivalent and nonequivalent protons, spin-spin splitting
and coupling constants for vicinal, geminal and long range coupling. Areas of
signals. Interpretation of NMR spectra of simple organic molecules such as
ethyl bromide, ethanol, acetaldehyde, ethyl acetate and acetophenone.
Unit-X Biomolecules: (04 Marks) Carbohydrates:
Introduction,
classification Determination of ring size. Mechanism of osazone formation,
glycoside formation, acetylation and methylation, chain lengthening and chain
shortening of aldoses. Interconversion of glucose and fructose and conversion
of glucose into Mannose, Mechanism of mutarotation.
Proteins: Introduction,
classification, structure and stereochemistry of amino acids. Acid base
behaviour and isoelectric points, the peptide bond, primary secondary and
tertiary structure of proteins.
Lipids: Definition, natural fats and
oils, structural features of triglycerides, common fatty acids. Hydrogenation
of oils. Saponification, iodine and acid values. Introduction to steroidal
compounds (Cholesterol, sex harmones and cortisone). Introduction,
classification and importance of terpenoids and Alkaloids. Structural features
of their representative examples.
Unit XI: States of Matter
(04 marks) Gaseous State:
Deviation of gases from ideal behavior, PV isotherms
of real gases, continuity of states, the isotherms of vander Waal's equation,
relationship between critical constants and vander Waal's constants, the law of
corresponding states, reduced equation of state. Root mean square, average and
most probable velocities. Maxwell's distribution of molecular velocities,
collision number, mean free path and collision diameter, Liquefaction of gases
(based on Joule-Thomson effect).
Liquid
State: Intermolecular forces,
structure of liquids (a qualitative description). Dipole moment, induced dipole
moment, Measurement of dipole moment (temperature method and refractivity
method), Dipole moment and structure of molecules.
Liquid crystals: Classification &
structure of nematic, smectic and cholesteric phases. Liquid crystal displays
and Thermography.
Solid State: Definition of space lattice, unit cell and it's
dimensions, crystal systems. Laws of crystallograhy:- (i) Law of constancy of
interfacial angles (ii) Law of rational indices (iii) Law of symmetry. Symmetry
elements in crystals, Lattice planes and Miller indices. X-ray diffraction by
crystals.
Unit XII: Chemical
Kinetics & Photochemistry (04 marks)
Determination of order of reaction by differential, integration, half
life period and isolation methods. Techniques for kinetic investigation:
Conductometry, Potentiometry, Polarimetry and Spectrophotometry. Effect of
temperature on rate of reaction, Arrhenius equation, concept of activation
energy. Theories of chemical kinetics: Simple Collision theory – Basic
approximations, evaluation of rate constant for atomic reactions, extension to
molecular reactions and limitations. Photochemical decomposition of hydrogen
iodide. Photochemical combination of Hydrogen-chlorine and hydrogen-bromine
reactions. Photochemistry: Interaction of radiation with matter, difference
between thermal and photochemical processes. Laws of photochemistry.
Lambert-Beer law, Grothus-Drapper law, Stark-Einstein law, Jablonski diagram -
fluorescence, phosphorescence, non-radiative processes (internal conversion,
intersystem crossing) quantum yield, photosensitized reactions.
Unit XIII: Laws of
Thermodynamics and Chemical Equilibria (04 marks)
First Law of thermodynamics: Heat capacity, heat capacities at constant volume and
constant pressure and their relationship. Joule's law, Joule-thomson
coefficient and inversion temperature. Calculation of w, q, dU & dH for the
expansion of ideal and non-ideal (van der Waals) gases under isothermal and
adiabatic conditions for reversible. Bond dissociation energy and its
calculation from thermo-chemical data. Kirchhoff s equation. Second law of thermodynamics: Different statements of the law. Carnot cycle and its
efficiency, carnot theorem. Concept of entropy, entropy as a state function,
entropy as a function of V&T and P&T, entropy change in physical
processes. Clausius inequality, entropy as a criteria of spontaneity and
equilibrium. Entropy change in ideal gas expansion and entropy of mixing of
ideal gases.
Third law of thermodynamics:
Nernst heat theorem, statement of
third law, concept of residual entropy, evaluation of absolute entropy from
heat capacity data. Gibbs function (G) and Helmholtz function (A) as criteria
for thermodynamic equilibrium and spontaneity.
Variation of G and A with P, V and T. Equilibrium constant and free energy
change. Reaction isotherm and reaction isochore, Clapeyron equation and
Clausius-Clapeyron equation, applications. Thermodynamics of elevation in
.boiling point and depression in freezing point. Activity and activity
coefficient. Thermodynamic mixing functions of ideal and nonideal solutions,
Excess thermodynamic functions of non-ideal solutions. Statement and meaning of
the terms: phase, component and degree of freedom. Gibbs phase rule, phase
equilibria of one component svstem - water. CO2 and S systems. Phase equilibria
of two component system: solid liquid equilibria, simple eutectic(Pb-Ag)
system, Solid solutions-compound formation with congruent melting point (Mg-Zn)
and incongruent melting point (FeCl3-H2O systems). Partially miscible liquids: Lower and
upper consolute temperature, (examples of Phenol-water, trimethylamine-water,
nicotine-water systems). Nernst distribution law- applications.
Unit-XIV: Electrochemistry
(04 marks)
Migration of ions and
Kohlrausch law, Debye-Huckel-Onsager's equation for strong electrolytes
(elementary treatment only). Transport number, definition and determination by
Hittorf’s method and moving boundary method. Application of conductivity
measurements: determination of degree of dissociation and dissociation
constants of acids; determination of solubility product of a sparingly soluble
salt, conductometric titrations. Types of reversible electrodes: gas-metal-ion,
metal-metal ion, metal-insoluble salt- anion and redox electrodes. Electrode
potential, standard electrode potential, standard hydrogen electrode, reference
electrodes, sign conventions. Electrode reactions, Nernst equation,
determination of cell E.M.F, electrochemical series and its significance.
Electrolytic and Galvanic cells reversible and irreversible cells, conventional
representation of an electrochemical cell. Measurement of EMF of a cell.
Calculation of thermodynamic functions of cell reactions (G, H and K.).
Concentration cells, valency of ions, solubility product and activity
coefficient. Potentiometric titrations.
Unit XV: Quantum Chemistry & Spectroscopy
(04 marks)
Limitation
of Classical mechanics: Black-body radiation, Planck's radiation law,
photoelectric effect, heat capacity of solids and atomic spectra. De Broglie
hypothesis, the Heisenberg's uncertainty principle. Introduction to operators
and operator algebra. Hermitian operator, Hamiltonian operator, Schrodinger
wave equation and its importance, physical interpretation of the wave function,
postulates of quantum mechanics, Quantum mechanical treatment of particle in a
one dimensional box. Quantum numbers and their importance, hydrogen like wave
functions, radial wave functions, angular wave functions. Spectroscopy: Electromagnetic
radiation, regions of the spectrum and associated spectroscopies. Rotational
spectroscopy: Moment of inertia, classification of molecules on the basis
of moment of inertia, classical treatment of rotation of rigid diatomic
molecules, quantization of angular momentum, quantization of energy levels of
rigid diatomic molecules, selection rules for transitions and associated
spectrum, intensity of spectral lines, determination of bond length. Vibrational
Spectroscopy: Classical and quantum (qualitative) treatments of harmonic
vibrations of diatomic molecules. Pure vibrational spectrum of diatomic
molecules, selection rules, determination of force constant. vibrational
degrees of freedom, idea of vibrational frequencies of different functional
groups.