CHEMISTRY PAPER III (Hons.)- Physical Chemistry
Time: 3 Hours ] Full Marks: 50
In all nine questions are to set. The Q. No. 1 will be objective 10 marks and will Screen the entire paper, Students will be required to answer five questions of which question 1 will be compulsory.
1. THERMODYNAMICS
Definition of thermodynamic terms:
System Surroundings etc. Types of systems, intensive & extensive properties. State & path functions & their differentials, Thermodynamic process, Concept of heat & work.
First Law of Thermodynamics:
Statement, definition of internal energy & enthalpy. Heat capacity, heat capacities at constant volume & pressure & their relationship. Joul's law-Joule-Thomson coefficient & inversion temperature. Calculation of w.q. dU & dH for the expansion of ideal gases under isothermal & adiabatic conditions for reversible process.
Thermochemistry
Standard enthalpy of formation, Hess' Law of heat summation & its
applications. Heat of reaction at constant pressure & at constant volume.
Enthalpy of neutralization, Bond dissociation energy & its calculation from thermo-chemical data, temperature dependence of enthalpy, Kirchoff's equation
2. THERMODYNAMICS
Second Law of thermodynamics need for the law. different statements of the law Carnot cycle & its efficiency. Carnot theorem. Thermodynamic scale of temperature.
Concept entropy. entropy as a state function, entropy as a function of V
&T. entropy as criteria of spontaneity & equilibrium. Entropy change in ideal gases & mixing of gases.
Third law of thermodynamics
Nernst heat theorem, statements & concept of residual entropy. evaluation of absolute entropy from heat capacity data. Gibbs & Helmholtz functions. Gibbs function (G) & Helmholtz function (A) as thermodynamic quantities. A &
G as criteria for thermodynamic equilibrium & spontaneity, their advantage Over entropy change variation of G & A with P. V. & T. equilibrium constant & free energy. Reaction isotherm & reaction isoehore clapeyron equation.
Clausius Clapeyron equation) applications, Thermodynamic derivation of relation between molecular weight & elevation in boiling point & depression in freezing point.
3. LIQUID STATE:
intermolecular forces, structure of liquids (a qualitative description).
Structural differences between solids, liquids & gases.
Liquid crystals Differences between liquid crystal, solid, liquid, Classification, Structure of nematic & phases. Thermography & seven segment cell.
4. PHASE EQUILIBRIUM:
Statements & meaning of the terms Phase, component & degree of
freedom, derivation of Gibbs phase rule, phase equilibria of one component system- water, CO2 & S system.
Phase equilibria of two componant system-Solid-liquid equilibria. simple
eutectic-bi-Cd Pb-Ag systems, desilverisation of lead.
Solid solutions:
Compound formation with congruent melting point (Mgzn) & in-congruent melting point. (Nac-H2o). (Fecl3-H20) system
Liquid Liquid mixtures
Ideal liquid mixtures, Raoults & Henry's law Non-ideal system-azeotropes (enthanol water) system.
Partially miscible liquids - Phenol water, trimethyl amine- water systems, Lower & upper consolute temperature Effect of impurity on Consolute temperature
Immiscible Liquids, steam distillation Nernst distribution Law Thermodynamic derivation, applications.
5. ELECTRO CHEMISTY-
Electrical transport-Conduction in metals & in electrolyte solutions, specific conductance & eguivalent conductance, measurement of equivalent conductance, variation of equivalent & specific conductance with dilution
Migration of ions & kohlrausch law, Arrhecius theory of electrolytic
dis sociation & its limitations, weak & strong electrolytes Qustwalds, dilution law its uses & limitations Debye-Huckle-Onsagers.equn for strong electrolyte &(elementary treatment only). Transport number, definition & determination
by Hittorf method & moving boundary method
Applications of conductinity measurements, determination of degree of dissociation, determination of Ka of acids, determination of solubility. Product of sparingly soluble salt, conductomatic titration.
CHEMISTRY PAPER IV-Inorganic Chemistry
Time: 3 Hours] [Full Marks: 50
In all nine questions are to set. The Q. No. 1 will be objective 10 marks
and will Screen the entire paper, Students will be required to answer five questions of which question 1 will be compulsory.
1. Chemistry of Elements of First Transition Series
Characteristic properties of d-block elements
Properties of the elements of the first transition series their binary compounds and complexes illustrating relative stability of their oxidation states, coordination number and geometry.
2. Chemistry of Elements of Second and Third Transition Series
General Characteristics, comparative treatment with their 3rd-analogues
in respect of ioniC radii, oxidation states, magnetic behaviour, spectral
properties and stereochemistry.
3. Oxidation and Reduction
Use of redox potential data analysis of redox cycle, redox stability in
water-Frost, Latime and Pourbaix diagrams, Principles involved in the
extraction of the elements.
4. Co-ordination Compounds:
Werner's coordination theory and its experimental verification, effective
atomic number concept. chelates nomenclature of coordination compounds. isomerism in coordination compounds, valence bond theory of transition metal complexes
5. Chemistry of Lanthanide Elements:
Electronic structure, oxidation states and ionic radii and lanthanide
contraction, complex formation, occurrence and isolation, lanthanide
compounds.
6. Chemistry of Noble Gases:
Chemical properties of the Noble gases, Chemistry of Xenon, structure
and bonding in xenon compounds.
7. Non-aqueous Solvents
Physical properties of a solvent, types of solvents and their general
characteristics, reactions in non-aqueous solvents with reference to liquid NH3, and liquid SO2
8. Hard and soft acids andrbases (HSAB):
Classification of acids and bases as hard and soft, Pearson's HSAB
Concept, acid base strength and hardness and softness, symbiosis theoretical basis of hardness and softness, electronegativity and hardness and softness.
CHEMISTRY PAPER IV-ORGANIC CHEMISTRY
Time:3 Hours]
In all nine questions are to set. The a. No. 1 will be objective 10 marks
and will screen the entire paper, Students will be required to answer five questions of which question 1 will be compulsory.
1 Electromagnetic spectrum, Absorption Spectrum:
UV absorption spectroscopy absorption laws (Beeriabert law), molar absorptivity. presentation and analysis of UV spectra, types of electronic transitions, effect of conjugation, Concept of chromophore and auxo Chrome. Bathochromic, hypsochremic, hyperchromic and hypochromic shifts. UV spectra of conjugated
enes and enones.
Infrared (R) absorption spectroscopy- molecular vibrations. Hooke's law
selection rules. intensity and position of IR bands, measurement or iR
spectrum, fingerprint region, Characteristic absorption of various functional groups and interpretation of IR spectra of simple organic compounds.
2. Mechanism: Aromatic electrophilic substitution, Directive influence of
group. Mechanism of nitration, Sulphonation and halogenation of benzene. Relative strength of acids and substituted acids. Phenols and substituted phenols, Relative strength of basicity of aliphatic amines, aromatic amines and substituted aromatic amines, Decarboxylation of acids, Synthesis of derivatives of acids, Hydrolysis of esters, Acid & Base, Catalysed opening of epoxide ring.
3. Hydroxy Acids:a, B, &y- Hydroxy acids -preparation and reactions of
lactic acid, tartaric acid and citric acid.
4. organic Synthesis era Enolates-
Acidity of hydrogen atom of a carboxylic group. Active methylene group. Keto Enol tautomerism, Ethyl acetoacetate and Diethl malonate.
5. Carbohydrates: Classification, Monosaccharides Ascending the aldose series, Descending the aldose series, Inter conversions of aldose to Ketose and vice-versa configuration of monosaccharides, mechanism of Osazone formation, Mutarotaton, Epemerisation, Erythro and threo diastereomers Structure of D (+) glucose.
6. Name reactions: Friedel- Craft's reaction Reimer Tiemann reaction,
Reformatsky reaction, Gatermann's Synthesis, Claisen Condensation,
Houben Hoeseh reaction, Kolbe's reaction, Sandmeyer's reaction)
7. Phenols: Isolation from Coal tar, Methods of prepn, Impotant rk, uses
8. Aromatic amines and Diazonium salt
9. Fats, Oils & Detergents
Natural fats, edible and industrial oils of vegetable origin, Common fatty acids, glycerides, hydrogenation of
unsaturated oils, Saponification value, iodine value, acid, value, Soape, Synthetic detergents, alkyl and aryl sulphonates
10. Synthetic Polymers: Addition or chain-growth polymerisation. Free
radical. Vinyl polymerisation. ionic vinyl polymerization, Zieger- Natta
polymorisation and vinyl polymers condensation or step growth
polymerisation. Polyester , Polyamides, Phenols, formaldehyde resins. Urea- formaldehyde resins, Epoxy resins and polyurethanes. Natural & Synthetic rubbers.
PRACTICAL
Time:6 Hours Full Marks: 50
1. Volumetric analysis
(a) Acidimetry and alkalimetry
(b) Use of Potassium Permanganate, Potassium Dichromate and Sodium
Thiosulphate.
2. Detection of Nitrogen, Sulphur and Halogen in Organic Compounds and identification of organic compounds containing one functional group
including monosaccharides.
3. Note Book and Viva-voce.
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