Wednesday, February 17, 2010

ALL ABOUT CHEMISTRY AS OPTIONAL


Background

These optional are not so popular, thus very little information available in the market about how to prepare It for UPSC civil service exam & what books to read, hence I'm copy pasting some information that I gathered.

Tips for Chemistry Mains Paper 1

  • Paper-1 has two major branches: Physical Chemistry and Inorganic Chemistry. These two branches are simple as well as scoring. Generally, the main examination question paper Section A contains three questions including compulsory from Physical Chemistry. There is usually one question from Inorganic Chemistry.
  • The first two topics, Atomic Structure and Chemical Bonding, are conceptual and should be prepared from standard sources. Even though these portions can give you direct questions as well, their importance will be felt in many other sections of the course.
  • In Solid State Chemistry, you need to prepare separately for numerical and theoretical problems. Gaseous State is a newly added section in Paper 1 and the best thing about this section is that it has a simple mathematical base. Prepare it adequately and it will fetch you good marks.
  • In Thermodynamics, be careful to maintain an orientation of Chemistry. There is a common tendency among engineers to treat the questions too mathematically. But in Chemistry, you have to treat heat change along with chemical change. For a good score, your derivations must be standard, i.e. as covered in books like S Glasstone's. You can be somewhat selective in Thermodynamics section, based on past trends. Statistical Thermodynamics is a newly-added part, and it is quite scoring. The section
  • on Phase Equilibria needs good writing practice besides command over numerical problems. The emphasis in electrochemistry should be on numerical problems, as they are relatively easy and make the paper scoring.
  • Chemical Kinetics and Photochemistry are, once again, predominantly numerical-based areas. So practice will be the key to handle these sections well. Photochemistry is especially important; it has been giving numerical problems of at least 30 marks every year.
  • Coordination chemistry is a large topic, covering nearly two full-length questions. Students are advised to cover this section thoroughly. The topic of Bio-Inorganic Chemistry requires some good material collection. Bob Buchanan's book on Plant Molecular Biology and Biochemistry will be a useful source.

 

Tips for Paper 2

  • Paper 2 comprises completely of Organic Chemistry. In the new scheme of the syllabus, it's a highly scoring paper due to several factors: mathematical orientation, straight factual queries, objective nature of most of the question, availability of quality material and emphasis on reaction mechanisms.
The student, while preparing for Paper 2, is required to keep the following things in
mind:
  1. Practice the numerical problems rigorously and you must have a clear knowledge of reaction mechanisms, as the questions are increasingly being asked straight and factual.
  2. In Pericyclic Reaction section, a greater emphasis has to be on diagrams rather than on theoretical explanation and practice name reactions thoroughly from standard sources.
  3. The orientation of orbitals and molecular orbital diagrams are necessary.



Suggested Reading:

PHYSICAL CHEMISTRY


  • Gaseous state, Thermodynamics, Phase rule, solutions, Colligative properties,
  • Electro Chemistry, Catalysis, Colloids - Principals of physical chemistry - Puri, Sharma & Pathawa
  • Chemical kinetics - Advance physical chemistry - Gurdeep Raj
  • Photo chemistry - A text book of physical chemistry (Vol. - IV) - K.L. Kapoor
  • Advance physical chemistry - Gurdeep Raj.

ORGANIC CHEMISTRY

  1. Bonding and shape of organic molecules, Stereo chemistry of carbon compound - Reactions and reagents - O.P. Agarwal
  2. A guide to mechanism in organic chemistry - Peter Sykes
  3. Rest of the chapters - A text book of organic chemistry - Bahl & Bahl

INORGANIC CHEMISTRY

  1. Atomic Structure - Principle of physical chemistry - Puri, Sharma & Pathwa
  2. Advance inorganic chemistry - J.D. Lee
  3. Chemical Periodicity, Chemical bonding,Coordination compound - Selected topics in inorganic chemistry - Maden, Malik, Tuli
  4. Theoretical principles of inorganic chemistry - G.S. Manku,
  5. Extradiction of metals, Principle of inorganic chemistry - Puri, Sharma, Jauhar.
  6. Rest all the chapters - An advance inorganic chemistry - J.D. Lee
  7. Pollution and its control - A text book of environmental chemistry and pollution S.S. Dara.


Now the syllabus part (again copypaste job from official UPSC site)

Syllabus for Chemistry Optional in Prelims 2010

Section-A
(Inorganic Chemistry)

  1. Atomic structure : Schrodinger wave equation, significance of y
    and y2
    quantum numbers and their significance, radial and angular probability, shapes of orbitals, relative energies of atomic orbitals as a function of atomic number. Electronic configurations of elements; Aufbau principle, Hund's multiplicity rule, Pauli exclusion principle.
  2. Chemical periodicity : Periodic classification of elements, salient characteristics of s,p,d and f block elements. Periodic trends of atomic radii, ionic radii, ionisation potential, electron affinity and electronegativity in the periodic table.
  3. Chemical bonding: Types of bonding, overlap of atomic orbitals, sigma and pi bonds, hydrogen and metallic bonds. Shapes of molecules, bond order, bond length, V.S.E.P.R. theory and bond angles. The concept of hybridization and shapes of molecules and ions.
  4. Oxidation states and oxidation number : Oxidation and reduction, oxidation numbers, common redox reactions, ionic equations. Balancing of equations for oxidation and reduction reactions.
  5. Acids and bases : Bronsted and Lewis theories of acids and bases. Hard and soft acids and bases. HSAB principle, relative strengths of acids and bases and the effect of substituents and solvents on their strength.


  6. Chemistry of elements:
    1. Hydrogen: Its unique position in the periodic table, isotopes, ortho and para hydrogen, industrial production, heavy water.
    2. Chemistry of s and p block elements : electronic configuration, general characteristics properties, inert pair effect, allotropy and catenation. Special emphasis on solutions of alkali and alkaline earth metals in liquid ammonia. Preparation, properties and structures of boric acid, borates, boron nitrides, borohydride (diborane), carboranes, oxides and oxyacids of nitrogen, phosphorous, sulphur and chlorine; interhalogen compounds, polyhalide ions, pseudohalogens, fluorocarbons and basic properties of halogens. Chemical reactivity of noble gases, preparation, structure and bonding of noble gas compounds.
    3. Chemistry of d block elements: Transition metals including lanthanides, general characteristic properties, oxidation states, magnetic behaviour, colour. First row transition metals and general properties of their compounds (oxides, halides and sulphides); lanthanide contraction.
  7. Extraction of metals: Principles of extraction of metals as illustrated by sodium, magnesium, aluminium, iron, nickel, copper, silver and gold.
  8. Nuclear Chemistry: Nuclear reactions; mass defect and binding energy, nuclear fission and fusion. Nuclear reactors; radioisotopes and their applications.
  9. Coordination compounds: Nomenclature, isomerism and theories of coordination compounds and their role in nature and medicine.
  10. Pollution and its control: Air pollution, types of air pollutants; control of air and water pollution; radioactive pollution.

Section-B
(Organic Chemistry)

  • 2.1 Bonding and shapes of organic molecules : Electronegativity, electron displacements-inductive, mesomeric and hyperconjugative effects; bond polarity and bond polarizability, dipole moments of organic molecules; hydrogen bond; effects of solvent and structure on dissociation constants of acids and bases; bond formation, fission of covalent bonds : homolysis and heterolysis; reaction intermediates-carbocations, carbanions, free radicals and carbenes; generation, geometry and stability; nucleophiles and electrophiles.
  • 2.2 Chemistry of aliphatic compounds: Nomenclature; alkenes-synthesis, reactions (free radical halogenation) -- reactivity and selectivity, sulphonation-detergents; cycloalkanes-Baeyer's strain theory; alkenes and alkynes-synthesis, electrohilic addition reactions, Markownikov's rule, peroxide effects, 1- 3-dipolar addtion; nucleophilic addition to electron-deficient alkenes; polymerisation; relative acidity; synthesis and reactions of alkyl halides, alkanols, alkanals, alkanones, alkanoic acids, esters, amides, nitriles, amines, acid anhydrides, a, ß-unsaturated ketones, ethers and nitro compounds.
  • 2.3 Stereochemistry of carbon compounds : Elements of symmetry, chiral and achiral compounds. Fischer projection formulae; optical isomerism of lactic and tartaric acids, enantiomerism and diastereoisomerism; configuration (relative and absolute); conformations of alkanes upto four carbons, cyclohexane and dimethylcyclo-hexanes-their potential energy. D, L-and R, S-notations of compounds containing chiral centres; projection formulae-Fischer, Newman and sawhorse-of compounds containing two adjacent chiral centres; meso and dl-isomers, erythro and threo isomers; racemization and resolution; examples of homotopic, enantiotopic and diasteretopic atoms and groups in organic compounds, geometrical isomers; Eand Znotations. Stereochemistry of SN1, SN2, E1 and E2 reactions.
  • 2.4 Organometallic compounds : Preparation and synthetic uses of Grignard reagents, alkyl lithium compounds.
  • 2.5 Active methylene compounds : Diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate-applications in organic synthesis; tautomerism (keto-enol).
  • 2.6 Chemistry of aromatic compounds : Aromaticity; Huckel's rule; electrophilic aromatic substitution-nitration, sulphonation, halogenation (nuclear and side chain), Friedel-Crafts alkylation and acylation, substituents effect; chemistry and reactivity of aromatic halides, phenols, nitro-, diazo, diazonium and sulphonic acid derivatives, benzyne reactions.
  • 2.7 Chemistry of biomolecules : (i) Carobhydrates : Classification, reactions, structure of glucose, D, L-configuration, osazone formation; fructose and sucrose; step-up step-down of aldoses and ketoses, and ther interconversions, (ii) Amino acdis : Essential amino acids; zwitterions, isoelectric point, polypeptides; proteins; methods of synthesis of a-amino acids. (iii) Elementary idea of oils, fats, soaps and detergents.
  • 2.8 Basic principles and applications of UV, visible, IR and NMR spectroscopy of simple organic molecules.

Section-C
(Physical Chemistry)

  • Gaseous state : Deviation of real gases from the equation of state for an ideal gas, van der Waals and Virial equation of state, critical phenomena, principle of corresponding states, equation for reduced state. Liquification of gases, distribution of molecular speed, collisions between molecules in a gas; mean free path, speicific heat of gases
  • Thermodynamics : (i) First law and its applications: Thermodynamic systems, states and processes, work, heat and internal energy, zeroth law of thermodynamics, various types of work done on a system in reversible and irreversible processes. Calorimetry and thermochemistry, enthalpy and enthalpy changes in various physical and chemical processes, Joule-Thomson effect, inversion temperautre. Heat capacities and temperature dependence of enthalpy and energy changes.
  • (ii) Second law and its applications : Spontaneity of a process, entropy and entropy changes in various processes, free energy functions, criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities.
  • Phase rule and its applications : Equilibrium bewteen liquid, solid and vapours of a pure substance, Clausius-Clapeyron equation and its applications. Number of components, phases and degrees of freedom; phase rule and its applications; simple systems with one (water and sulphur) and two components (lead-silver, salt hydrates). Distribution law, its modifications, limitations and applications.
  • Solutions : Solubility and its temperature dependence, partially miscible liquids, upper and lower critical solution temperatres, vapour pressures of liquids over their mixtures, Raoult's and Henry's laws, fractional and steam distillations.
  • Colligative Properties : Dilute solutions and colligative properties, determination of molecular weights using colligative properties.
  • Electrochemistry : Ions in solutions, ionic equilibria, dissociation constants of acids and bases, hydrolysis, pH and buffers, theory of indicators and acid-base titrations. Conductivity of ionic solutions, its variation with concentration, Ostwald's dilution law, Kohlrausch law and its application. Transport number and its determination. Faraday's laws of electrolysis, galvanic cells and measurements of their e.m.f., cell reactions, standard cell, standard reduction potential, Nernst equation, relation between thermodynamic quantities and cell e.m.f., fuel cells, potentiometric titrations.
  • Chemical kinetics : Rate of chemical reaction and its dependence on concentrations of the reactants, rate constant and order of reaction and their experimental determination; differential and integral rate equations for first and second order reaction, half-life periods; temperature dependence of rate constant and Arrhenius parameters; elementary ideas regarding collision and transition state theory.
  • Photochemistry : Absorption of light, laws of photochemistry, quantum yield, the excited state and its decay by radiative, nonradiative and chemical pathways; simple photochemical reactions.
  • Catalysis : Homogeneous and heterogeneous catalysis and their characteristics, mechanism of heterogeneous catalysis; enzyme catalysed reactions (Michaelis-Menten mechanism).
  • Colloids : The colloidal state, preparation and purification of colloids and their characteristics properties; lyophilic and lyophobic colloids and coagulation; protection of colloids; gels, emulsions, surfactants and micelles.



Syllabus for Mains Chemistry Optional

PAPER - I



  1. Atomic Structure:


    1. Heisenberg's uncertainty principle, Schrodinger wave equation (time independent); Interpretation of wave function, particle in one-dimensional box, quantum numbers, hydrogen atom wave functions; Shapes of s, p and d orbitals.


  2. Chemical Bonding:


    1. Ionic bond, characteristics of ionic compounds, lattice energy, Born-Haber cycle; covalent bond and its general characteristics, polarities of bonds in molecules and their dipole moments; Valence bond theory, concept of resonance and resonance energy; Molecular orbital theory (LCAO method); bonding in H2+, H2, He2+ to Ne2, NO, CO, HF, and CN–; Comparison of valence bond and molecular orbital theories, bond order, bond strength and bond length.


  3. Solid State:


    1. Crystal systems; Designation of crystal faces, lattice structures and unit cell; Bragg's law; X-ray diffraction by crystals; Close packing, radius ratio rules, calculation of some limiting radius ratio values; Structures of NaCl, ZnS, CsCl and CaF2; Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors.


  4. The Gaseous State and Transport Phenomenon:


    1. Equation of state for real gases, intermolecular interactions and critical phenomena and liquefaction of gases, Maxwell's distribution of speeds, intermolecular collisions, collisions on the wall and effusion; Thermal conductivity and viscosity of ideal gases. 


  5. Liquid State:


    1. Kelvin equation; Surface tension and surface energy, wetting and contact angle, interfacial tension and capillary action.


  6. Thermodynamics:


    1. Work, heat and internal energy; first law of thermodynamics.


    2. Second law of thermodynamics; entropy as a state function, entropy changes in various processes, entropy–reversibility and irreversibility, Free energy functions; Thermodynamic equation of state; Maxwell relations; Temperature, volume and pressure dependence of U, H, A, G, Cp and Cv, α and β; J-T effect and inversion temperature; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem, introductory idea of third law of thermodynamics.


  7. Phase Equilibria and Solutions:


    1. Clausius-Clapeyron equation; phase diagram for a pure substance; phase equilibria in binary systems, partially miscible liquids–upper and lower critical solution temperatures; partial molar quantities, their significance and determination; excess thermodynamic functions and their determination.


  8. Electrochemistry:


    1. Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law for various equilibrium and transport properties.


    2. Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. of cells and its applications fuel cells and batteries.


    3. Processes at electrodes; double layer at the interface; rate of charge transfer, current density; overpotential; electroanalytical techniques: Polarography, amperometry, ion selective electrodes and their uses.



  1. Chemical Kinetics:


    1. Differential and integral rate equations for zeroth, first, second and fractional order reactions; Rate equations involving reverse, parallel, consecutive and chain reactions; branching chain and explosions; effect of temperature and pressure on rate constant; Study of fast reactions by stop-flow and relaxation methods; Collisions and transition state theories.


  2. Photochemistry:


    1. Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.


  3. Surface Phenomena and Catalysis:


    1. Absorption from gases and solutions on solid adsorbents, Langmuir and B.E.T. adsorption isotherms; determination of surface area, characteristics and mechanism of reaction on heterogeneous catalysts.


  4. Bio-inorganic Chemistry:


    1. Metal ions in biological systems and their role in ion transport across the membranes (molecular mechanism), oxygen-uptake proteins, cytochromes and ferredoxins.


  5. Coordination Compounds:


    1. Bonding theories of metal complexes; Valence bond theory, crystal field theory and its modifications; applications of theories in the explanation of magnetism and electronic spectra of metal complexes.


    2. Isomerism in coordination compounds; IUPAC nomenclature of coordination compounds; stereochemistry of complexes with 4 and 6 coordination numbers; chelate effect and polynuclear complexes; trans effect and its theories; kinetics of substitution reactions in square-planer complexes; thermodynamic and kinetic stability of complexes.


    3. EAN rule, Synthesis structure and reactivity  of metal carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl compounds.


    4. Complexes with aromatic systems, synthesis, structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadienyl complexes; coordinative unsaturation, oxidative addition reactions, insertion reactions, fluxional molecules and their characterization; Compounds with metal-metal bonds and metal atom clusters.


  6. Main Group Chemistry:


    1. Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds; Sulphur – nitrogen compounds, noble gas compounds.


  7. General Chemistry of 'f' Block Elements:


    1. Lanthanides and actinides; separation, oxidation states, magnetic and spectral properties; lanthanide contraction.

PAPER - II



  1. Delocalised Covalent Bonding:


    1. Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.


  1. (i) Reaction Mechanisms: General methods (both kinetic and non-kinetic) of study of mechanism of organic reactions: isotopic method, cross-over experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions.


    1. Reactive Intermediates: Generation, geometry, stability and reactions of carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.


    2. Substitution Reactions: SN1, SN2 and SNi mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds–pyrrole, furan, thiophene and indole.


    3. Elimination Reactions: E1, E2 and E1cb mechanisms; orientation in E2 reactions–Saytzeff and Hoffmann; pyrolytic syn elimination – Chugaev and Cope eliminations.


    4. Addition Reactions: Electrophilic addition to C=C and C≡C; nucleophilic
      addition to C=0, C≡N, conjugated olefins and carbonyls.


    5. Reactions and Rearrangements: (a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer–Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.


    1. (b) Aldol condensation, Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin condensations; Fischer indole synthesis, Skraup synthesis, Bischler-Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactions.


  2. Pericyclic Reactions:


    1. Classification and examples; Woodward-Hoffmann rules – electrocyclic reactions, cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO approach.


  3. (i) Preparation and Properties of Polymers: Organic polymers–polyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.


    1. (ii) Biopolymers: Structure of proteins, DNA and RNA.


  4. Synthetic Uses of Reagents:


    1. OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, NaBH4,  n-BuLi and  MCPBA.


  5. Photochemistry:


    1. Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.


  6. Spectroscopy:


    1. Principle and applications in structure elucidation:


      1. Rotational: Diatomic molecules; isotopic substitution and rotational constants.


      2. Vibrational: Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.


    2. (iii) Electronic: Singlet and triplet states; n       * and       * transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules; Charge transfer spectra.


      1. Nuclear Magnetic Resonance (1H NMR):  Basic principle; chemical shift and spin-spin interaction and coupling constants.


      2. Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.

      3.  

Mains

Question Paper of 2005



[PDF File]

Prelims

Question Paper of 2009[PDF File]



Question Paper of year 2008[New]

Question Paper of 2005



[PDF File]

Chemistry 2004 Prelims



(Solved)[PDF File]



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