B. R. A. BIHAR UNIVERSITY MUZAFFARPUR … SYLLABUS...2. Qualitative organic analysis: (a) Detection...

B. R. A. BIHAR UNIVERSITY

MUZAFFARPUR

COURSES OF STUDY FOR

B.Sc. Examination (Chemistry)

B.Sc. (Honours) Part-I

Session: 2006-2007

Time : 3 Hrs F.M. : 75

CHEMISTRY PAPER : I

Nine questions to be set. Five questions to be answered. Short answer type

questions are recommended. There may be several parts in a question and different

units may be mixed in questions. While setting questions the entire syllabus may be

covered as far as practicable. Two questions to be answered from group ‘A’ and

three questions to be answered from group ‘B’

Group : ‘A’ [Physical]

(Four questions) 25 Marks

1. Gaseous State:

Derivation of Van der Waal equation of state, critical phenomenon, critical

constants and their evaluation in terms of van der waals constants.

Determination of van der waals constants, law of corresponding states,

reduced equation of states, Boyle’s temperature.

2. Liquid State:

Free volume of a liquid, vapour pressure, Troutons rule, Surface tension,

viscosity and their measurements, Molar volume, Parachore, Rheocore and

chemical constitution, Kopp’s law, internal pressure, solubility parameters,

liquid crystal.

3. Phase Equilibria:

Phase rule and the definition of terms, involved in it, one component system.

Water and sulphur system, two component system Ag-Pb, KI + water, eutectic

point, Formation of compounds with congruent melting points, Deliquescence,

efflorescence, triple points.

4. Electrical Transport:

Conductance in electrolytic solutions, Equivalent, specific and Molar

conductance, cell constant, effect of dilution on conductance, Ionic mobility,

migration of ions, Kohlrausch’s law, transport number and its determination by

Hittorff’s methods, Applications of conductance measurements.

Group : ‘B’ [Inorganic]

(Five questions) 50 Marks

1. Periodic Properties:

Atomic and ionic radii, ionization potential, electron affinity and electro

negativity, their trends in periodic table and application in explaining and

predicting the chemical behaviours.

2. Chemical Bonding:

Covalent Bond: V.B. theory and its limitations, Directional characteristics of

covalent bond, Hybridisation and shape of inorganic molecules and ions

VSEPR theory with special reference to bond and electronegativity, M.O.

theory. Homonuclear and Heteronuclear diatomic molecules [CO, NO], bond

strength, bond energy. Dipole moment: Percentage ionic character in HX,

Molecular geometry of polyatomic molecules.

Ionic Solids: Lattice energy, Born Haber cycle, solvation energy solubility of

ionic solid, polarizing power and polarizibility of ions, Fajan’s rule. Weak

interactions: H-bonding and van der waals forces.

3. s-Block Elements:

Comparative study, diagonal relationship, hydrides, salvation and complexing

tendencies, an introduction to alkyl and aryl organometallics.

4. p-Block Elements:

comparative study, relationship among metal, nonmetal and metalloids

elements of group 13-17, elementary idea of hydrides, oxides and halides.

Hydrides of boron. Diborane and Higher boranes. Borazine, boro hydrides,

fullerenes.

.



Session: 2006-2007


CHEMISTRY PAPER : II



units may be mixed in questions. While setting questions the entire syllabus may be

covered as far as practicable. Two questions to be answered from group ‘A’ and




1. Atomic Structure:

Black body radiation and planck’s quantum theory, Wave-particle, duality for

electron and de-Broglie equation, experimental verification of de-Broglie

equation by Davission and Germer experiment, de-Broglie wave associated

with Bohr orbit in H-atom, Heisenberg uncertainty principle and its importance.

2. Solid State:

Types of solid, space lattice and unit cell, law of rational indices- Miller and

Weiss indices. Interplaner spacing in cubic system, radius ratio and

coordination number, packing of particles- Octahedral and tetrahedral voids.

3. Thermodynamic:

Objectives of thermodynamics, thermodynamic terms, First law and its

mathematics formulation, Internal energy, enthalpy, Cp and Cv relation, joule

–Thomson effect, Joule Thomson coefficient for ideal an real gases, Inversion

temperature, work done in irreversible expansion, Reversible and irreversible

adiabatic expansion of an ideal gas.

4. Thermo-Chemistry:

Exergonic and endergonic compounds, enthalpy of reaction at constant

volume and constant pressure, enthalpy of combustion, Bomb calorimeter,

enthalpy of neutralization and ionization, Kirchoff’s law, Hess’s law, bond

dissociation energy.

Group : ‘B’ [Organic]


1. Estimation of nitrogen and sulphur in an organic compounds. Determination of

molecular mass of a caboxylic acid by silver salt method and of an organic

base by chloroplatinate salt method.

2. Structure and bonding:

Hybridization and geometry of hydrocarbons bond lengths, bond angles, bond

dissociation energy, localized and delocalized chemical bond, Vander Waal

interactions and hydrogen bonding resonance,Hyperconjugation, inductive

and electromeric effect, their effects on properties of compounds.

3. Mechanism of Organic Reactions:

Homolysis and heterolysis of covalent bonds. Types of reagents: electrophilic

and nucleophilic. Types of organic reactions, energy consideration with

reference to activation energy and transition state. Reactive intermediates:

carbanions, carbocations and free radicals(generation, structure and stability).

4. Alcohols:

Classification and nomenclature, Monohydric alcohols: Methods of

preparation, physical and properties. Distinction among 1°, 2° and 3° alcohols.

Preparation and properties of (i) Ethylene glycol (ii) Glycerol and (iii) Allyl

alcohol.

5. Organometallic Compounds:

Organomagnesium compounds: The Grignard reagent-formation structure

and application in organic synthesis. Basic idea about organometallics:

Dimethylzing, Dimethylcadmium, Alkylithium and Lithium dialkylencuprate.

6. Organosulphur Compounds:

Preliminary idea of organic sulphomides, sulphonics and sulphonic acids,

methods of formation and chemical reactions of thiols and thioethers.

7. Aldehydes and ketones:

Nomenclature, structure of the carbonyl group, general methods of

preparation, properties of aldehydes and ketones, An introduction to α-β

unsaturated aldehydes and ketones.

8. Carboxylic acids:

General methods of preparations and properties of monocarboxylic acids and

their derivatives such as ester, acid chlorides, amides and anhydrides.

Methods of formation and chemical reactions of (i) unsaturated

monocarboxylic acids and (ii) dicarboxylic acids.

9. Organic compounds of nitrogen

Classification, nomenclature and structure of amines. Preparation and

properties of aliphatic amines. Separation and identification of 1° , 2° and 3°

amines. Preparation, properties and estimation of urea.


Session: 2006-2007


CHEMISTRY PRACTICAL

Following exercise may be performed

1. Qualitative analysis of inorganic salt mixture containing four radicals. 20

2. Qualitative organic analysis:

(a) Detection of elements: N, S and halogens, functional groups. 5

(b) Detection of functional group in simple organic compounds (aldehydes

ketones, carboxylic acid, amides, amine, phenol,nitro group and

sulphonic acid group) preparation of derivatives is not required

15

3. Note book 05

4. Viva-voce 05

B.Sc. Part-I Subsidiary and General Course

Session: 2006-2007


CHEMISTRY PAPER : I

Nine questions to be set and five of them to be answered selecting maximum ot two .

questions from any group A, B and C.


(Three questions) 25 Marks

1. Gaseous State :

Van der Waal’s equation of state for real gases. Principle of conductivity of

states, relationship between critical constants and Van der waal’s constants

law of corresponding states, liquification of gases.

2. Solid State:

Space lattice and unit cell, law of rational indices, distance between crystal

planes, diamond and graphite structures, rutile structure, fluorite structure,

coordination number, radius ratio and geometry, limitations.

3. Conductivity and E.M.F.:

Types of conductivity, effect of dilutions on conductivities, cell-constant,

experimental set up for measurement of conductivity. Electromotive force,

electrode potential, hydrogen electrode, calomel electrode, electromotive

series and its significance.

4. Liquid and Colloidal State:

Structure difference between solid, liquid and gas, molar volume, surface

tension, viscosity, parachore and chemical constitution, intermolecular forces,

classification of colloids, preparation and properties, preparation of colloidal

solutions, electrical and optical properties, coagulation, stability of colloids,

emulsion, gels, soap and surface active agents.

.


(Three` questions)

1. Atomic Structure and Periodicity:

Special features of Bohr model like quantization of energy expression for

radius and energy of orbits, Hydrogen spectrum and its interpretation,

ionization energy, wave particle duality of electron and de-Broglie equation,

quantization of angular momentum as a consequence of de-Broglie relation,

uncertainty principle, variation of atomic and ionic radii, ionization energy,

electron affinity among groups and periods, their application in predicting and

explaining chemical behaviour.

2. Structure and Shape of Molecules:

Nature of covalent bond, orbital overlap, directional properties of covalent

bond and hybridization, VSEPR model for geometry of molecules/ions like

ICl3-, H2O, NH3, ClF3, PCl5, polarizing power, polarizibility of ions, Fajan’s

rules, percentage ionic character, dipole moment and electro negativity

difference.

3. Study of s-Block Elements :

Comparative study and diagonal relationship of elements, metal hydrides and

their properties, salvation and complex forming tendencies of ions of the

elements, their importance in two-systems.

4. Study of p-Block Elements:

Comparative study including diagonal relationships of elements from group

13-17, their hydrides oxides, oxy-acids and halides of important members,

preparation properties and structures of diborane, borazine and borohydrides,

structure of silicates, properties of halogens, interhalogens and polyhalides,

preparation, properties and bonding of xenon compounds and their structure.

Group : ‘C’ [Organic]

(Three` questions)

1. Idea of Electron Displacement:

Electrophiles and nucleophiles, inductive, resonance and electronic effects,

strength of acids and bases on the basis of electron displacement.

2. Study of chemistry of alkanes, alkenes, alkynes, alkanols, alkanones, alkanoic

acids and their derivatives, aliphatic amines, emphasis may be given on their

geometrical structures.

3. Simple treatment of geometrical and optical isomerism, E-Z nomenclature of

geometrical isomers, D, L configurations of optical isomers.

4. Properties and synthetic uses of Grignard reagent, reformatsky reaction

5. Estimation of N and S, Determination of molecular weight, organic acid by (a)

AgCl and base by (b) H2PtCl6 methods.

B.Sc. Part-I Subsidiary and General Course

Session: 2006-2007


CHEMISTRY PRACTICAL

1. Analysis of cations and anions in given inorganic salt mixture containing not

more than four radicals. 12

2. Organic preparation:

(i) Acetylation of aniline and paratoluidine 8

(ii) Hydrolysis of methyl salicylate and ethyl benzoate

3. Record and Viva-voce 05


B.Sc. (Honours) Part-II

Session: 2006-2007


CHEMISTRY PAPER : III



units may be mixed in questions. Two questions to be answered from group ‘A’ and




1. Chemical Kinetics and Catalysis:

Rate law for a general reaction. Mathematical derivation of 1st, 2nd and 3rd

order reaction and their life period. Methods of determining order reactions.

Arrhenius equation. Energy of activation. Potential energy diagram and

concept of activated complex. Rate data and mechanism of reactions.

Homogeneous and Heterogeneous catalysis. Effect of catalyst on reaction

rate . Specificity of catalysed reaction.

2. Distribution of velocities of gases:

Maxwell distribution law of velocities and energies of gaseous molecules.

Effect of mass and temperature on molecular velocities. Collision number,

Collision frequency, mean free path, viscosity of gases.

3. Ionic Equilibria:

Ostwald’s dilution law and its verification, pH of buffer solutions. Hydrolysis of

salts. Relation between Kh, Kw, Ka and Kb, Ph of hydrolysed salts solutions,

degree of hydrolysis, Choice of acid base indicator with pH Change, solubility

product , Ionic product and common ion effect.

4. Electrochemical Cell:

Electrochemical cell, reversible and irreversible cells, reversible electrode,

Concept of electrode potential, standard electrode potential, Nernst equation

for electrode potential , Calomel electrode, Quinhydrone electrode,

Applications of emf measurement , determination of pH , ionic product of

water , solubility and solubility product of sparingly soluble salts.



1. Nature of Chemical Bond:

Types of bond : σ, π, Ƭ and δ bonds. Bonding in B2H6 ,copper acetate and

chromous acetate. Concept of resonance and delocalization of orbitals e. g.

NO, NO3, SO2, SO3, SO42- PO4

3- and CO32- ions. Hydrogen bond and related

properties.

2. Chemistry of Elements of First Transition Series:

d-block elements and their characteristic properties, Study of elements of first

transition series and their binary compounds. Complex formation in different

oxidation states and their stabilities. Principle behind volumetric estimation of

Cu2+, Fe2+ and Cr3+ ions, by the use of standard sodium thiosulphate ,

potassium peramagnate and potassium dichromate solution.

3. Chemistry of Elements of Second Transition Series:

General characteristics of heavy elements. comparative study with their 3d

analogous in respect of their ionic radii, stability of oxidation states. Magnetic

behavior of compounds complexes forming tendencies and stereochemistry.

4. Non-aqueous Solvents :

Physical properties of solvents. Types of solvents and their general

characteristics, reactions in nonaqueous solvents such as liquid ammonia and

liquid sulphur dioxide.

5. Coordination compounds:

Werner’s coordination theory and its justification from physical data,

Isomerism in complexes. Sidwick theory of effective atomic number.

Chelates. Nomenclature of coordination compounds , valence bond theory of

metal-ligand bonding with respect to coordination number 4 and 6 Inner and

outer orbital complexes inner complexes metal ions with organic reagents

such as 8-hydroxyquinoline cupferron and dimethyl glyoxime.


Session: 2006-2007


CHEMISTRY PAPER : IV



units may be mixed in questions. Two questions to be answered from group ‘A’ and




1. Thermodynamics :

Spontaneous and non-spontaneous process, necessity of second law of

thermodynamics, Carnot cycle and its efficiency, Clausius inequality, entropy,

entropy change of an ideal gas. Entropy of mixing, Helmholtz energy and

Gibb’s energy, their variation with pressure and temperature, Gibbs Helmoltz

equation, Clausius-Clapeyron equation and its application in colligative

properties.

2. Solutions:

Types of solution, solutions of gases in liquids, Henry’s law, solutions of

liquids in liquid. Raoult’s law, vapour pressure of ideal solution, free energy,

volume and enthalpy, change for an ideal and non-ideal solution, Duhem

Margules equation, variation of total vapour pressure with variation of

composition of the liquid phase, azeotropic mixture, Principle of steam

distillation and fractional distillation.

3. Surface Chemistry:

Types of adsorption, Langmuir’s adsorption isotherm and Adsorption and

Catalysis, Effect of temperature and pressure on surface reaction with

reference to heterogeneous catalysis, classification, preparation and

purification of colloidal sols., their optical and electrical properties, hardy-

Schultze law, Gel, Synthesis, thixotropy, Association of colloidal electrolytes,

soap, micelles, emulsions.

4. Distribution law:

Nernst distribution law, its thermodynamic derivation and limitations factors

affecting partition coefficient, essential conditions for validity of distribution

law, Modification of distribution law for association, dissociation and solvent

participation, Applications: Complex formation between KI and I2, CuSO4 and

NH3, solvent extraction process.

.

Group : ‘B’ [Organic]


1. Stereochemistry of organic compounds:

Optical Isomerism:

Element of symmetry, molecular chirality, Stereogenic centre, optical activity,

Enantiomers and their properties, Chiral and achiral molecules with two

stereogenic centres. Diastereomers and meso compounds. Resolutions of

racemic mixture. Relative and absolute configurations. Representation of

configurations by Fischer and Flying Wedge formulae. Threo and erythro

nomenclature of diastereomers having two chiral centres. Sequence rules, D,

L, and R,S systems of nomenclature.

Geometrical Isomerism:

Restricted rotation about double bonds, Geometrical isomerism about C=C

and C=N, specification of configuration by Cis/Trans and E-Z system. Basis

idea about geometrical isomerism in alicyclic compounds.

Conformational Isomerism:

Conformational analysis of ethane, propane and n-butane, Representation of

conformations by Newmann and Sawhorse projection formulae. Difference

between configuration and conformation, conformations of cyclohexane and

its monosubstituted derivatives.

2. Active Methylene Compounds:

Acidity of α-hydrogens. Preparation of ethyl acetacetate and diethyl malonate

and their applications to organic synthesis, Keto enol tautomerism of ethyl

acetacetate and β-dicarboxyl compounds.

3. Hydroxy Acids:

General methods of preparation and properties of α, β and γ hydroxyl acids

with special reference to lactic , tartaric and citric acids structure of tartaric

and citric acids.

4. Carbohydrates :

Classification and nomenclature. Glucose open chain structure. Mechanism of

osazone formation . Conversion of glucose into fructose and vice-versa.

Chain lengthening and chain shortening of aldoses. Configuration of D & L-

Glucose. Determination of ring size of glucose & fructose, Cyclic structures of

D glucose: α and β- D- glucose granoses & furanases. Mutarotation,

Metarotation of Glucose

5. Aromatic Chemistry:

Aromaticity: the Huckel rule, Aromatic, nonaromatic and antiaromatic structure

of benzene, resonance and resonance energy of benzene. Electrophilic

aromatic substitution: general pattern of the mechanism, role of σ and π-

complexes, Mechanism of nitration, halogenations, sulphonation and Friedel-

Craft reactions. Directing influence of substituents in aromatic substitution and

their activating and deactivating effect, ortho-para ratio in substitution

reaction.

General methods of preparation and reactions of arenens and monofuctional

benzene derivative like amines, phenols, aldehydes, ketones, carboxylic and

sulphonicacid. Synthesis of organic compounds via diazonium salts.

6. Name Reactions and their Mechanism:

(i) Cannizaro (ii) Aldol condensation (iii) Reimer-Tiemann (iv) Sandmayer (v)

Perkin reaction (vi) Reformatsky reaction (vii) Wurtz-Fittig reaction (vii) Wolff-

Kishner (ix) Knoevengel reaction (x) Williamson ether synthesis.


Session: 2006-2007


CHEMISTRY PRACTICAL

One exercise with be performed in the examination out of items 1 or 2. Item 3 is

compulsory.

1. Volumetric Analysis :

(i) Preparation and standardization of potassium permagnates and

sodium thiosulphate solution

(ii) Estimation of Fe2+ using dichromate

(iii) Estimation of Cu2+ ion using thiosulphate

2. Gravimetric Analysis:

(c) Estimation of Ba2+ as barium sulphate

(d) Estimation of Ni2+ as nickel dimethyl glyoximate 20

3. Organic Qualitative Analysis:

Identification of monofuntional compounds Determination of melting point and

preparation of suitable derivatives. 20

4. Note book 05

5. Viva-voce 05

B.Sc. Part-II Subsidiary and General Course

Session: 2006-2007


CHEMISTRY PAPER : II

Nine questions to be set and five of them to be answered selecting maximum ot two .

questions from any group A, B and C.


(Three questions) 25 Marks

1. Thermodynamics :

Thermodynamic terms, statement and mathematical formulation of first law of

thermodynamics, enthalpy and heat capacities at constant pressure and

volume, relationship between Cp and Cv, work done in adiabatic and

isothermal changes. Joule-Thomson effect and μπ for ideal and real gases.

Thermochemistry-standard state, enthalpy of formation, Hess’s law, heat of

reaction at constant pressure and constant volume, enthalpy of neutralization,

Kirchoff’s equations, necessity of second law, second law-its statement.

Entropy, Carnot cycle, efficiency, entropy changes for an ideal gas at constant

pressure, constant volumre and constant temperature.

2. Phase Rule:

Phase rule and meaning of phase component and degree of freedom, one

component system-water, triple point, two component system- Zn-Cu system

FeCl3+H2O, freezing mixtures, azotropes-HCl+H2O, ethanol+H2O, principle of

steam distillation, efflorescence and deliquescence.

3. Electrochemistry:

Migration of ions, Kohlrausch’s law, Ostwald’s dilution law, and its verification,

transport number and its measurement, abnormal transport number, Buffer

solution and its pH, hydrolysis of salts and calculation of hydrolysis constant

along with Ka, Kb and Kw, theory of indicators, pH diagram and indicator

range, chemical cells and concentration cells with and without transference,

reversible and irreversible electrodes, hydrogen and calomel electrode, e.m.f.

of a cell.

4. Kinetics and Catalysis:

Order of general reactions, rate law and reaction mechanism, Expression for

rate constant for first and second order reactions, their half-life period

determination of order of reactions, temperature dependence of order of

reaction, Arrhenius equation, activation energy, catalysis, homogeneous and

heterogeneous catalytic reactions, effect of catalyst on reaction rate, auto

catalyst, industrial catalysts, promoter, inhibitor.

.


(Three` questions)

1. Chemistry of Elements of First Transition Series:

Characteristics of d-block elements, comparative study of ionic radii, oxidation

states, oxidizing and reducing properties, magnetic behaviour and complex

forming tendency of ions with respect to coordination numbers (4 and 6) and

their stereochemistry.

2. Oxidation Potential Diagram and Oxidising and Reducing Properties:

Oxidation state diagrams for oxidized and reduced systems for hydrogen

sulphur, nitrogen, manganese and chromium systems along with their redox

potentials and their stability in water, in acid and alkaline media. Application of

oxidation potential diagrams

3. Coordination Compounds :

Double salts and coordination compounds, Werner’s theory-primary and

secondary valency, experimental verification including isomerism,

nomenclature of complex compounds, EAN rule, chelates and inner

complexes, valence bond theory of M-L bonding and its limitations, spin-only

magnetic moments and stereochemistry, study of complex formation for

solubility of compounds and inner complex salts with DMG and 8-hydroxy

quinoline, EDTA.

4. Radioactivity:

Nuclear transformation, binding forces at the nucleus, nuclear stability,

radioactive equilibrium, nuclear isomerism, radio active series, artificial

radioactivity, isotopes effect and isotope exchange reaction, nuclear fission

and fussion reactions, moderators

Group : ‘C’ [Organic]

(Three` questions)

1. Reaction Mechanism:

Types of organic reactions, types of reagents, reactive intermediates-

carbocations, carbanions and free radicals

2. Hydroxy Acids:

Isolation, Synthesis and properties of lactic, tartaric and citric acids, optical

isomerism in lactic and tartaric acids.

3. Carbohydrates :

Open chain and ring structures of glucose and fructose, methods of their

interconversion, chain lengthening and chain shortening of aldoses, osazone

formation.

4. Active Methylene Compounds:

Active methylene group, keto-enol tautomerism, preparation and synthetic

applications of ethyl acetoacetate and diethyl malonate.

5. Aromatic Chemistry:

Aromaticity, the Huckel rule, aromatic ions, structure of benzene including

valence bond and m.o. pictures, aromatic electrophilic substitution – general

pattern of the mechanism, mechanism of nitration, halogenations,

sulphonation and Friedel-Craft reaction, directive influence of functional

groups orientation, study of nitrobenzene, aniline, phenol, benzenediazonium

chloride, benzaldehyde, acetophenone, benzoic acid, benzene sulphoric acid

B.Sc. Part-II Subsidiary and General Course

Session: 2006-2007


CHEMISTRY PRACTICAL

1. Volumetric Analysis :

(iv) Acidmetry alkalimetry: Estimation of mixture of sodium carbonate and

bicarbonate

(v) Oxidation and reduction titration using oxalic acid and potassium

permanganate, mixture of sulphuric acid and oxalic acid estimation of

Ca in calcium carbonate 10

2. Determination of functional group in a given organic compounds: aldehyde,

ketone, carboxylic acids and amines. 10

3. Record and Viva-voce 05

B.Sc. (Honours) Part-III

Session: 2006-2007

Time : 3 Hrs F.M. : 100

CHEMISTRY PAPER : V


questions are recommended. There may be several parts in a question and

different units may be mixed in questions. While setting questions the entire

syllabus may be covered as far as practicable.

1. Electrochemistry:

Galvanic cells, thermodynamics of Galvanic cells, chemical cells with and

without transference, liquid junction potential, Glass electrode for the

measurement of Ph, Storage batteries, Lead accumulator, PPolarisation,

Hydrogen and oxygen overvoltage, Decomposition voltage in aqueous

solution, Electrical double layer, corrosion of metals and its prevention.

2. Wave Mechanics:

Inadequacy of classical mechanics.Wave, quanta and motion of vibrating

string, basic concept of quantum mechanics, postulates, eigen function and

eigen value, physical properties of wave function, orthogonality and

normalization of wave functions, Schrodinger wave equation and its

importance, Treatment of free particle and particle in one , two and three

dimensional boxes, rigid rotator-expression for energy rotational quantum

number and degeneracy of states.

Elementary idea of H atoms, radial and angular parts of wave functions R, ɵ

and ɸ, concept of quantum numbers and their significance, radial distribution

functions, radial factors, Rnl-r, R2nl-r and 4πr2R2nl-r plots. Angular dependence

of orbitals –shape of s,p and d orbitals, concept of electronic spin.

3. Spectroscopy:

Component of molecular energy and their quatization, different parts of

electromagnetic radiation and theircharacterization, energy level spacings and

relative population among levels, types of molecular spectra , band

width,band intensity and position of spectral bands.

UV-visible spectra:

Frank-condon principle, selection rules, λ and ε max values, Qualitative

description of σ, π and n molecular orbitals, transitions in H2, ethylene,

butadiene, formaldehydes, α, β, unsaturated carbonyl compounds. Red and

blue Shifts, calculation of λmax, Woodward rules.

Infrared-spectra:

Energy levels of simple harmonic oscillator, selection rule, Hooke’s law and

force constant, qualitative relationship between force constant, bond length,

bond angle, bond order, bond energy, and stretching frequency of molecules,

vibrational spectra of H2O, NO2 and CO2, concept of group frequency.

4. Magnetic Resonance Spectra:

N.M.R. spectra, nuclear spin system, nuclear spin quantum number, nuclear

spin angular momentum, nuclear magnetic moment, nuclear magneton, effect

of magnetic field on system with nuclear spin, nuclear energy levels, magnetic

quantum number for nuclear spin, energy level separation and resonance

condition in a magnetic field N.M.R., chemical shift, factor affecting chemical

shift, shielding and deshielding mechanisms, nuclear spin-, spin coupling,

coupling constant and contributing factors to it, first order rules.

E.S.R. spectra: Electronic spin system, electronic spin quantum number,

electron spin angular momentum, electron spin magnetic moment,Bohr

magneton, effect of magnetic field on electronic spin system, electron spin

energy levels, magnetic quantum number for electronic spin states,

separation between energy levels caused by the presence of magnetic field,

condition for electron spin resonance, selection rule, derivative curve,

hyperfine coupling, hyperfine coupling constant, spectra of H. CH3. CH2OH.

NO. C6H6.

5. Equilibrium Thermodynamics:

Maxwell relations, thermodynamic equation of state, free energy change in a

chemical reactionand equilibrium constants, thermodynamic derivation of law

of mass action, Denuder’s concept of chemical equilibria and reaction

potential, pressure and temperature dependence of equilibrium constant, van’t

Hoff equation. Nerst heat theorem, third law of thermodynamics and its

experimental verification, entropy and probability.

6. Theories of Rate Process:

Derivation of Maxwell law of distribution of velocities of gaseous molecules.

Average R.M.S. and most probable velocity, Collision theory of bimolecular

reaction and its validity, Lindemann theory of unimolecular reaction.

Hinselwood theory, Transition state theory-thermodynamic-traetment

activation parameters viz volume of activation, free enegy of activation and

Entropy of activation.

Steady state approximation and rate law for thermal decomposition of Ozone,

N2O5 and non[photo chemical combinations of

H2+Cl2…………………2HCl

7. Photochemistry:

Primary and secondary photochemical processes, laws of photochemistry,

Jablonski diagram, radiative and non-radiative transitions, quantum efficiency

and its variation.

Photochemical reactions:

H2 + Cl2 ………….2HCl,

H2 + Br2…………..2HBr,

Decompositionof HI, fluorescence and phosphorescence, photosensitization.


Session: 2006-2007

Time : 3 Hrs F.M. : 100

CHEMISTRY PAPER : VI





1. Molecular orbital and valence bond methods:

Principles of linear combination, criteria of maximum overlapping for effective

combination, Energy and probability plots of bonding and anti bonding

molecular orbitals in H2+, energy versus internuclear separation in H2 both for

attractive and repulsive states, non-bonding M.O. and three centre bonding,

valence bond wave functions of H2 molecule, quantitative description of sp,

sp2 and sp3 hybrid orbitals and inter orbital, comparison between V.B. and

M.O. methods.

2. Magnetic Properties:

Diamagnetic, paramagnetic, ferromagnetic and antiferro-magnetic behaviour.

Paramagnetic susceptibility and method of its determination, Variation of

magnetic susceptibility with temperature, Curie and Neel temperature, Ground

Term Symbols and Hund’s rule, dependence of magnetic moment value on

L.S. and J quantum numbers, spin only magnetic moment, quenching of

orbital angular momentum, magnetic moment data in case of transition metal

complexes.

3. Metal Ligand Bonding in Transition Metal Complexes:

V.B. model of M-L bonding and its limitations, crystal field model d-orbital

splitting in oh and Td environments, crystal field splitting parameter (10Dq)

and factors affecting it, crystal field stabilization energy, magnetic properties

and colour of complexes, variation of ionic radii of M2+ ions in 3d series.

Thermodynamic stability constants and factors affecting stability of

complexes, chelate effect, entropy effect..

4. Nuclear Chemistry:

Nuclear stability and binding, artificial radioactivity, position emission and β-

decay process, Nuclear fission, Liquid drop model, nuclear chain reaction,

moderator, nuclear fusion reactions, neutron activation analysis, isotope

dilution method, isotope effect and isotope exchange reactions.

5. Electronic Spectra of Transition Metal Cmplexes:

Types of electronic transition, selection rules for electronic transition,

spectrochemical series, Free ion ground terms and Orgel diagram for d1 to

d9.systems in octahedral and tetrahedral fields, Visible spectra of [Ti(H2O)6]3+

ions.

6. Hard and Soft Acid and Bases:

Classification of metals into A and B, acid-base behaviour of hard and soft

acids and bases, classification, their acid-base strength, hardness-softness,

symbiosis, theory of hardness and softness, electronegativity and hardness

and softness.

7. Inorganic Polymers:

Classification of polymers, chemistry of inorganic ring and chain compounds

containing boron, nitrogen, phosphorous and silicon atoms.

8. Methods of Analysis:

(a) Complexometric titration using EDTA, estimation of Mg2+ ion and Ca2+.

(b) Chromatographic technique: Principles of TLC and gas chromatography,

determination of Rf value.

(c) Introduction of Colourimetry coulometry and flame photometry.


Session: 2006-2007

Time : 3 Hrs F.M. : 100

CHEMISTRY PAPER : VII





1. Reaction Mechanism:

Methods of determination of reaction mechanism (product analysis,

intermediates, use of isotopes, Cross over experiment, kinetic and stereo-

chemical studies).Mechanism of nucleophilic substitution reactions at

saturated carbon atom SN1, SN2 and SNi. Relative reactivities of alkyl halides,

allyl, vinyl and aryl halides, α- and β- Elimination reaction. E1 and E2

mechanism and their region and stereo selectivities. Electrophilic additions to

carbobn-carbon multiple bonds, Regio and stereo selectivities, Nucleophilic

additions to carbon-oxygen double bond..

2. Reagents use in organic synthesis:

Diazomethane, Lithium aluminium hydride, Sodium borohydride, Diborane, N-

bromo succinimide, Raney Nickel, Aluminium isoproxide, Periodic acid, Lead

tetraacetate, Lithium dialkylcuprate and Osmium tetroxide. Discussion on

specificity of the reagents and mechanism involved

3. Organic Reactions and Molecular Rearrangements:

i) Mannich reaction

ii) Michael addition reaction

iii) Hofmann exhaustive Methylation and elimination

iv) Wagner-Meerwein rearrangement

v) Wolf rearrangement

vi) Hofmann rearrangement

vii) Beckmann rearrangement

viii) Curtius rearrangement

ix) Schmidt rearrangement

x) Pinacol-Pinacolon rearrangement

4. Polynuclear Hydrocarbons:

Preparation, properties and structure determination of naphthalene,

anthracene and phenanthrene..

5. Heterocyclic compounds:

(a) Five membered, heterocyclics: Preparation, properties and aromatic

character of pyrrole, furan and thiophene.

(b) Six membered heterocyclics: Preparation, properties and aromatic

character of pyridine.

(c) Condensed heterocyclics: Preparation, properties of quinoline and

isoquinoline.

6. Dyes:

Classification, correlation of colour with constitution. Chemistry of the

following dyes: methyl orange, Congo-red, Malachite green, Crystal violet,

Phenolphthalein, Fluorescein, Alizarin and Indigo..

7. Ureides:

Purines, Islation, structure and synthesis of Uric acid..

8. (a) Amino Acids and Proteins::

(i) Classification, structure and stereo chemistry of amino acids, Acid-

base behaviour, isoelectric point and electro-phoresis, preparation and

reactions of α-amino acids.

(ii) Peptide linkage, Basic idea about primary and secondary structure of

proteins.

(b) Nucleic Acids

(i) Brief knowledge of purine and pyridine bases.

(ii) D-Ribose and de-ribose.

(iii) Constitution of nucleic acid and basic idea of double helix structure of

DNA.


Session: 2006-2007

Time : 6 Hrs F.M. : 100

CHEMISTRY PRACTICAL

The following exercises are to be performed:

Physical (1 to 7):

1. To determine the specific reaction rate of hydrolysis of methyl acetate

catalyzed by H+ ion at room temperature.

2. To compare strength of HCl andH2SO4 by studying the kinetics of hydrolysis

of ethyl acetate.

3. To determine the distribution coefficient of iodine between waterand CCl4.

4. To determine the surface tension of a liquid.

5. To determine the heat of neutralization of NaOH with HCl.

6. To determine enthalpy of neutralization of acetic acid using NaOH solution

and determine enthalpy of ionization.

7. To determine the viscosity of a liquid.

8. Synthesis of organic compounds:

(i) Acetylation of salicylic acid

(ii) Benzoylation of aniline

(iii) Nitration of monobenzene to m-dinitrobenzene.

(iv) Selective reduction of m-dinitrobenzene to m-nitroaniline.

Distribution:

One experiment from physical 60

One experiment from organic out of exercise in item 8 20

Noote Book 05

Viva-Voce 15

B. R. A. BIHAR UNIVERSITY MUZAFFARPUR … SYLLABUS...2. Qualitative organic analysis: (a) Detection...

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Transcript of B. R. A. BIHAR UNIVERSITY MUZAFFARPUR … SYLLABUS...2. Qualitative organic analysis: (a) Detection...