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Chemistry paper 2

OBJECTIVE: Paper II deals with a practical approach to the principles of semi micro
techniques. The students get acquainted with various oxidation and reductions reactions.
The student is well versed with organic basics, reaction mechanisms. The organic
chemistry enlightens with structural and spatial chemistry. The student also deals with
important applications of phase rule, Electro chemistry where power has got huge
demands nowadays.

SYLLABUS

UNIT I. INORGANIC CHEMISTRY

I. 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 covalent 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
staes.colour –d-d transition, colour and spectral behaviour of transition metal ions with
respect to d1-d9 configuration. Magnetic behaviour- determination of magnetic moment,
Gouy’s balance, paramagnetism, diamagnetism.complexation behaviour, stability of
complexes-oxidation states, I 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 behaviour, 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 +I,+II and +III states.

II. 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. Magnetic 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 color and complex formation. Comparision with lanthanides.
III. 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 floatation, calcinations
and roasting. Acid and alkali digestion. Reduction of oxides, carbonates, halides,
sulfides, sulphates – smelting, flux auto reduction, Alumino-Thermic reduction,
Hydrometallurgy, Electrolytic reduction. Purification of impure metals- liquation,
fractional distillation, zone refining, oxidative processes – cupellation,
bessimerisation, puddling, poling, thermal decomposition, amalgamation, electrolysis.
Alloys – classification, substitutional solid solutions, interstitial solid solutions, inter
metallic compounds, Hume-Rothery rules. Preparation of alloys- fusion electro
deposition, reduction and compression. Uses – ferrous and non-ferrous alloys.

IV. Non aqueous solvents

Classification and characteristics of a solvent. Reactions in liquid ammonia – physical


properties, auto ionization, examples of ammono acids and ammono base. Reactions
taking place in liquid ammonia – precipitation, neutralization, solvolysis, solvation-
solutions of metals in ammonia, complex formation, redox reactions. Reactions in
HF- auto ionization, reactions taking place in HF – precipitation, acid base reactions,
protonation.

UNIT II (ORGANIC CHEMISTRY)

I. Halogen compounds

Nomenclature and classification of alkyl (into primary, secondary, tertiary), aryl,


aralkyl, allyl, vinyl, benzyl). Chemical reactivity – reduction, formation of RMgX,
Nucleophilic substitution reaction – classification into SN1 and SN2.Mechanism of
energy profile diagrams of SN1 and SN2 reactions. Stereochemistry of SN2 (Walden
Inversion), SN1 (Racemisation) explanation of both by taking the example of
optically active alkyl halide -2-bromo butane. Structure and reactivity – Ease of
hydrolysis – comparision of allyl, benzyl, alkyl, vinyl and aryl halides.

II. 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 (intra and intra molecular) effect of hydrogen bonding
on boiling point and water solubility. Chemical properties (a) acidic nature of Phenols
(b) Formation of alkoxide/phenoxides and their reaction with RX. (c) Replacement of
OH by X using PCl5, PBr3, SOCl2 and with HX/ZnCl2.Esterification by (a) acid
halides, anhydrides and acids (mechanism) (b) Esters of inorganic acids (c)
dehydration of alcohols. Oxidation of alcohols by CrO3, 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 FeCl3, and by the solubility in
NaOH.Polyhydroxyl compounds – pinacol-pinacolone rearrangements, oxidative
cleavage (Pb(OAc)4 and HIO4).

III.Ethers and epoxides

Nomenclature, preparation by (a) Williamson’s synthesis (b) from alkenes by the


action of conc.H2SO4.Physical properties – Absence of Hydrogen bonding, insoluble
in water, low boiling point. Chemical properties - inert nature, action of conc.
H2SO4 and HI. Acid and base catalysed ring opening of epoxides – orientation.

IV.Carbonyl compounds

Nomenclature 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. Special methods of preparing aromatic aldehydes and
ketones by (a) Oxidation of arenes (b) Hydrolysis of benzal halides. Physical
properties – absence of Hydrogen bonding. Keto-enol tautomerism, polarisability of
carbonyl groups, reactivity of the carbonyl groups in aldehydes and ketones.
Chemical reactivity – i) Addition of (a) NaHSO3 (b) HCN (c) RMgX (d) NH3 (e)
RNH2 (f) NH2OH (g) PhNHNH2 (h) 2,4DNP,Schiff bases, Addition of H2O to Form
hydrate (unstable), comparision with chloral hydrate (stable), addition of alcohols –
hemi acetal and acetal formation, Halogenation using PCl5 with mechanism. Base
catalysed reactions – with particular emphasis on Aldol, Cannizaro reaction, Perkin
reaction, Benzoin condensation, haloform reaction, 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, Fehlings test,
Schiff’s test, haloform test (with equations). Introduction to alpha, beta unsaturated
carbonyl compounds.

V. Carboxylic acids and derivatives

Nomenclature, classification and methods of preparation (a) hydrolysis of Nitrites,


amides and esters. (b) Carbonation of grignard reagents. Special methods of
preparation of aromatic acids. Oxidation of side chain. Hydrolysis of
benzotrichlorides. Kolbe reaction. Physical properties –hydrogen bonding; dimeric
association, acidity-strength of acids with the examples of trimethyl acetic acid and
trichloro acetic acid, Relative differences in the acidity of aromatic and aliphatic
acids. Chemicals properties-Reactions involving H,OH and COOH groups-salt
formation, anhydride formation,acidhalide formation, Esterification (mechanism)
&Amide formation. Reduction of acid to corresponding primary alcohol-via ester or
acid chloride. Degradation of carboxylic acids by Huns Diecker reaction, Schmidt
reaction (Decarboxylation). Arndt-Eistert synthesis, Halogenation by Hell-Volhard-
Zelensky reaction. Carboxylic acid derivatives – Reactions of acid halides, acid
anhydrides, acid amides and ester (mechanism of ester hydrolysis by base and acid).

VI. Synthesis based on Carbanions

Acidity of alpha hydrogen, structure of carbanion. Preparation of Acetoacetic ester


by Claisen condensation and synthetic application of Aceto acetic ester. (a) Acid
hydrolysis and ketonic hydrolysis. Preparation of i) monocarboxylic acids ii)
dicarboxylic acids (b) malonic ester – synthetic applications. Preparation of i)
substituted mono carboxylic acids ii) substituted dicarboxylic acids iii) trialkyl acetic
acid.

UNIT III (PHYSICAL CHEMISTRY)

I. Phase rule

Statement and meaning of the terms – phase, component and degrees of freedom,
Gibb’s phase rule, phase equilibria of one component system – water system. Phase
equilibria of two-component system – solid-liquid equilibria, simple eutectic –Pb-Ag
system, desilverization of lead. Solid solutions – compound with congruent melting
point –(Mg-Zn) system and incongruent melting point –(NaCl-H2O) system. Freezing
mixtures.

II. Solutions

Liquid –liquid mixtures-ideal liquid mixtures, Raoult’s and Henry’s law. Non-ideal
systems. Azeotropes – HCl-H2O, ethanol-water systems. Fractional distillation.
Partially miscible liquids –phenol-water, trimethylamine-water, nicotine-water
systems, Lower and upper consolute temperature. Effect of impurity on consolute
temperature. Immiscible liquids and steam distillation.

III. Electrochemistry

Electrical transport- conduction in metals and in electrolyte solutions, specific


conductance and equivalent conductance, measurement of equivalent conductance,
Variation of specific and equivalent conductance with dilution. Migration of ions and
Kholrausch’s law, Arrhenius theory of electrolyte dissociation and its limitations, Weak
and strong electrolytes, Oswald’s dilution law, its uses and limitations. Debyle-Huckel –
Onsagar’s equation for strong electrolytes (elementary treatment only). Transport
number, definition and determinations by Hittorf method for attackable electrodes.
Applications of conductivity measurements. Determinations of degree of dissociation
determination of Ka of acids, Determination of solubility products of sparingly soluble
salt, conductometric titrations. Types of reversible electrodes- gas-metal ion, metal-metal
ion, metal-insoluble salt-anion and redox electrodes. Electrodes reactions, Nernst
equation, cell EMF and single electrode potential and standard hydrogen electrode-
reference electrodes- standard electrodes potential, sign conventions, electrochemical
series and its significance.

Electrolytic and Galvanic cells-reversible and irreversible cells, conventional


representation of electrochemical cells. EMF of a cell and its measurement. Computation
of EMF. Calculation of thermodynamic quantities of cell reactions -^G, ^H and K.

UNIT-IV (GENERAL CHEMISTRY II) 30h (1 h/w)

I. Molecular Symmetry 3h

Symmetry elements and symmetry operations in molecules. Definition of plane of


symmetry, centre of symmetry and Axis of symmetry (simple axis (Cn) and
alternating axis (Sn). Examples.

II. Physical properties and molecular structure 3h

Orientation of dipoles in an electric field, dipole moment, induced dipole moment,


dipole moment ands structure of molecules, magnetic properties – paramagnetism,
diamagnetism and ferromagnetism.

III. Molecular Spectroscopy 12 h

Electromagnetic radiation = different regions = wavelength, wave number, frequency,


and energy. Interaction with molecules and types of molecular spectra. Concept of
potential energy curves for bonding and anti bonding molecular orbitals. Qualitative
description of sigma, pi and n M.O., their energy levels and the respective transitions.

Ultra violet- visible absorption spectroscopy – presentation and analysis of spectra,


types of electronic transitions, effect of conjugation, concept of chromophore and
auxochrome. Batho chromic, hypsochromic, hyper chromic and hypo chromic shifts.
Examples.

Infra red absorption spectroscopy – energy levels of simple harmonic oscillator.


Molecular vibrations, Hooke’s law, intensity, determination of force constant and
qualitative relation of force constant and bond energies, effect of an harmonic motion
and isotope on the spectrum, modes of vibrations in polyatomic molecules, intensity
and position of IR bands. Instrumentation. Characteristic absorption bands of various
functional groups. Interpretation of IR spectra of simple organic molecules.
IV. Stereochemistry of carbon compounds 9h

Molecular representations: Wedge, Fischer, Newmann, and Saw-horse formulae.


Isomerism: Definition of homomers and isomers. Classification of isomers:
Constitutional and Stereoisomers. Definition and examples. Constitutional isomers:
Chain, fuctional, positional isomers and metamerism. Stereoisomers: Enantiomers
and diastereomers- Definitions and examples. Conformational and configurational
isomerism- definition.

Enantiomers: Optical activity: wave nature of light; plane polarized light, interaction
with molecules, optical rotation and specific rotation. Chiral molecules: Definition
and criteria – absence of plane, center and Sn axis of symmetry – asymmetric and
dissymmetric molecules. Examples of asymmetric molecules (Glyceraldehyde, Lactic
acid, Alanine) and dissymmetric molecules (trans – 1,2- dichlorocyclopropane).
Chiral centers: definition- molecules with similar chiral carbons (Tartaric acid) –
definition of mesomers. Molecules with dissimilar chiral carbons (2,3-
dibromopentane). Number of enantiomers and mesomers – calculation. D, L & R, S
configuration for asymmetric and dissymmetric molecules. Cohn- Ingold- Prelog
rules. Racemic mixture, Racemisation and resolution techniques.

Diastereomers: Definition- Geometrical isomerism with reference to alkenes – cis,


trans and E, Z configuration.

V. Theory of Semi micro qualitative analysis 3h

Principles involved – solubility product, common ion effect, classification and


reactions of anions. Classification, separation and reactions of cations into groups –
Group reagents.

LABORATORY COURSE - Paper II 90 h (3 h/ w)

I. Semi – micro qualitative analysis of mixtures containing two cations and two
anions.

II. Preparations:

o Ammonium chloride
o Potash alum
o Copper – ammonia complex
o Nickel – DMG complex