Fatima Mata National College(Autonomous)Kollam

Scheme & Syllabus of

Post Graduate Degree in Chemistry2019 Admission Onwards

1

PREAMBLE ThesyllabusofM.ScprogrammeinChemistryofferedunderSemestersystemhasbeenrevisedandtherevisedsyllabusistobeeffectivefrom2019admission.M.Scprogrammeshallextendoveraperiodoftwoacademicyearscomprisingoffoursemesters,eachof450hoursin18weeksduration.Thesyllabusandschemeofexaminationsofthisprogrammesaredetailedbelow.

M.Sc. PROGRAMME IN CHEMISTRY(Revisedsyllabusundersemestersystemwitheffectfrom2019admission)

SYLLABUS AND SCHEME OF EXAMINATION

CourseNoandTitleHoursperweek Duration for

ESA in hoursMarksfor

CAMarksfor

ESA TotalmarksL PSemester I19PCH11InorganicChemistryI 5 3 25 75 10019PCH12OrganicChemistryI 5 3 25 75 10019PCH13PhysicalChemistryI 5 3 25 75 10019PCH14InorganicPracticalsI 3 TobecontinuedinsemesterII19PCH15OrganicPracticalsI 3 TobecontinuedinsemesterII19PCH16PhysicalPracticalsI 4 TobecontinuedinsemesterII TotalmarksforsemesterI 300Distributionofteachinghours/week:Theory-15hours,practicals-10hours

CourseNoandTitleHoursperweek Duration for

ESA in hoursMarksfor

CAMarksfor

ESA TotalmarksL PSemester II19PCH21InorganicChemistryII 5 3 25 75 10019PCH22OrganicChemistryII 5 3 25 75 10019PCH23PhysicalChemistryII 5 3 25 75 10019PCH14InorganicPracticalsI 3 6 25 75 10019PCH15OrganicPracticalsI 3 6 25 75 10019PCH16PhysicalPracticalsI 4 6 25 75 100

TotalmarksforsemesterII 600Distributionofteachinghours/week:Theory-15hours,practicals-10hours

CourseNoandTitleHoursperweek Duration for

ESA in hoursMarksfor

CAMarksfor

ESA TotalmarksL PSemester III19PCH31InorganicChemistryIII 5 3 25 75 10019PCH32OrganicChemistryIII 5 3 25 75 10019PCH33PhysicalChemistryIII 5 3 25 75 10019PCH34InorganicPracticalsII 3 TobecontinuedinsemesterIV19PCH35OrganicPracticalsII 3 TobecontinuedinsemesterIV19PCH36PhysicalPracticalsII 4 TobecontinuedinsemesterIV

TotalmarksforsemesterIII 300Distributionofteachinghours/week:Theory-15hours,practicals-10hours

2

CourseNoandTitleHoursperweek Duration for

ESA in hoursMarksfor

CAMarksfor

ESA TotalmarksL PSemesterIV19PCH41ChemistryofAdvancedMaterials 5 3 25 75 100*19PCH42(a)InorganicChemistryIV 5 3 25 75 100*19PCH42(b)OrganicChemistryIV*19PCH42(c)PhysicalChemistryIV19PCH34InorganicPracticalsII 3 6 25 75 10019PCH35OrganicPracticalsII 3 6 25 75 10019PCH36PhysicalPracticalsII 4 6 25 75 10019PCH43(a)Dissertation 5 70 7019PCH43(b)VisittoR&Dcentre 5 5Internship(2weeksto4weeks)incollaborationwith research institutions

No weightage

19PCH44ComprehensiveViva-Voce 25 25TotalmarksforsemesterIV 600Grandtotal(semesterI+II+III+IV)

1800

Distributionofteachinghours/week:Theory-15hours,Practicals-10hours*Eachstudenthastochooseeither(a),(b)or(c)aselectiveinaccordancewiththedissertationchosen

3

PROGRAMME OUTCOME OF MSc CHEMISTRY

The outcome of the program are as follows.

• TogivestudentsacomprehensiveunderstandingoftheprinciplesofChemistry.

• Togaintheskilltodesignandcarryoutscientificexperimentsandinterpretthedata.

• TounderstandtheinterdisciplinarynatureofChemistryandtobeawareoftheemergingfieldsinChemistry.

• Tobuildascientifictemperandtolearnthenecessaryskillstosucceedinresearchorindustrialfield.

• TobeabletodefineandresolvenewproblemsinChemistryandparticipateinthefuturedevelopmentofchemistry.

4

5

SEMESTER I19PCH11: Inorganic Chemistry-I

Total 90 h

Course Outcome: CO1.Togetaninsightintothevarioustheoriesofmetalcomplexes.CO2.Identifytheprinciples,structureandreactivityofselectedcoordinationcomplexes.CO3.TounderstandtheapplicationsofvarioustechniquestoevaluateanalyticdataandSolveproblemsbasedonvariousanalyticalconcepts.CO4.QuantifyanalyteswithproperdatahandlingandanalysisCO5.Tobeableunderstandthestructureofvariousmetal-metalbondsandmetalclustersCO6.Togainacomprehensiveideaofthepreparation,propertiesanduseofisopoly,heteropolyacids,noblegasesandinterhalogencompoundsCO7.Tounderstandthechemistryofprocessesinatmosphere,andimpactsofvariouspollutantsondestructionofozone,hydrosphere,lithosphere.

Unit I Coordination chemistry-I: Theories of metal complexes 18 hTypes of ligands and complexes. Isomerism: Structural, geometrical and optical isomerism. Crystal fieldtheory:Splittingofdorbitalsinoctahedral,tetragonal,squareplanar,tetrahedral,trigonalbipyramidalandsquarepyramidalfields.Jahn-Tellertheorem,evidenceforJTeffect,staticanddynamicJTeffect.Crystalfieldstabilizationenergy(CFSE)anditscalculations.OctahedralSiteStabilizationEnergy.Factorsaffectingthesplittingparameter.Spectrochemicalseries.EvidenceofcovalencyinMetal-Ligandbond,introductiontoLigandfieldtheory.Molecularorbitaltheory.Sigmaandpibondingsincomplexes.MOdiagramsofoctahedralandtetrahedralcomplexeswithandwithoutpibonds.Experimentalevidenceofpibondonthestabilityofsigmabond.Nephelauxeticeffect.

Unit II Analytical principles 18 hEvaluationofanalyticaldata:Accuracyandprecision.Standarddeviation,varianceandcoefficientofvariation.Student ‘t’ test, ‘Q’ test, and ‘F’ test. Confidence limits. Errors: Classification, distribution, propagation,causesandminimizationoferrors.Significantfiguresandcomputation rules.Correlationanalysis:Scatterdiagram.Correlation coefficient, r. Calculation of r by themethod of least squares.Volumetricmethods:Classificationofreactionsinvolumetry.Theoriesofindicators.Acid-base,redox,adsorption,metallochromicindicators.Complexometrictitrations:TitrationusingEDTA-directandbacktitrationmethods.Precipitationtitrations.Redoxtitrations.Titrationsinnon-aqueoussolvents.Organicreagentsusedingravimetry:Oxine,dimethylglyoximeandcupferron.PrincipleandinstrumentationofTG,DTAandDSC.FactorsaffectingTGandDTAcurves.ApplicationsofTG,DTAandDSCinthestudyofmetalcomplexes.

Unit III Metal-metal bonds and metal clusters 18 hMetal-metalbonds:Factorsaffectingtheformationofmetal-metalbond.DinuclearcompoundsofRe,CuandCr,metal-metalmultiple bonding in (Re2X8)

2- ,Trinuclear clusters, tetranuclear clusters, hexanuclearclusters. Polyatomic zintl anion and cations. Infinitemetal chains.Metal carbonyl clusters. Anionic andhydridoclusters.LNCCsandHNCCs.Isoelectronicandisolobalrelationships.Heteroatomsinmetalclusters:Carbideandnitridecontainingclusters.ElectroncountingschemesforHNCCs.Cappingrule.Chalcogenideclusters.Chevrelphases.

Unit IV Isopoly and heteropoly acids, Noble gases, interhalogens 18 hPreparation,propertiesandstructureofisopolyacidsofMo,WandVandHeteropolyacidsofMoandW.PreparationandpropertiesofXenonfluoridesandKryptoncompounds(KrCl4,KrF4,KrF2,KrBr6,Kr2Cr2O7,KrCrO4 & KrO2), structure of XeF2 (MO theory only) . Preparation, bonding and uses of inter halogencompounds.Propertiesandstructureofaluminosilicatesandzeolites,shapeselectivity.Preparation,propertiesandapplicationsofsilicones.

Unit V Chemistry of Natural Environmental Processes 18 hThechemistryofprocessesinatmosphere;Compositionoftheatmosphere.Automobilepollutantsandthecatalytic converter. Photochemical smog. Chemistry of the stratosphere. Catalytic destruction of ozone.Depletion of the ozone layer.Hazards of common air pollutants on the human health.TheChemistry of

6

processes inhydrosphere;Thehydrologiccycle.Cyclingandpurification.Theuniquepropertiesofwater.Acidbaseproperties.CO2inwater.Alkalinity.O2consumingwaste.DO,BODandCOD.ThechemistryofprocessesinLithosphere;Redoxstatusinsoil.pE,pHpredominancediagramsforredoxsensitiveelements.Acidityinsoilmaterials.Acidneutralizationcapacityandthequantificationofthesoilacidity.Ionspeciationinsoilsolution.Cationexchangecapacityandexchangephasecomposition.

References1. F.A.CottonandG.Wilkinson,AdvancedInorganicChemistry,JohnWileyandSons,6thedition,1999.2. J. E. Huheey, Inorganic Chemistry- Principles of Structure and Reactivity, Harper Collins College

Publishing,4thedition,2011.3. K.F.PurcellandJ.C.Kotz,InorganicChemistry,Philadelphia:Saunders,1977.4. S.F.A.Kettle,PhysicalInorganicChemistry,OxfordUniversityPress,1stedition,1998.5. ShriverandAtkins,InorganicChemistry,OxfordUniversityPress,2010.6. A.I.Vogel,ATextBookofQuantitativeInorganicAnalysis,Longman,5thedition,1989.7. D.A. Skoog, D.M.West and F. J. Holler, Fundamentals ofAnalytical Chemistry, Saunders College

Publishing,7thedition,1996.8. D.A.SkoogandD.M.West,PrinciplesofInstrumentalAnalysis,Saunders College Publishing, 5th

edition,1998.9. F.A.Cotton,ChemicalApplicationsofGroupTheory,WileyEastern,3rdedition,2009.10.A.S.KunjuandG.Krishnan,GroupTheoryanditsApplicationsinChemistry,PHILearning,11.R.L.Carter,MolecularSymmetryandGroupTheory,JohnWiley&Sons,199812.E.JamesGirard,PrinciplesofEnvironmentalChemistry,JonesandBartlettPublishers,3rdEdition,13.H.V.Jadhav,ElementsofEnvironmentalChemistry,HimalyaPublicationHouse,201014.E.MichaelEssington,SoilandWaterChemistry,CRCPress,2ndedition,2015.

19PCH12: ORGANIC CHEMISTRY-I

Total 90 h

Course Outcome:CO1.Tounderstandthebasicconceptsandmechanisminorganicchemistry.CO2.Tobefamiliarizewiththemechanismoforganicreactionsanddifferentfactorswhichaffectthereactionrate. CO3.Tounderstandtheroleofvariousreactionintermediateslikecarbanion,carbocation,carbenes,radicalsetc. inorganicreactions.Comprehendthestructure-reactivitypatternofreactive intermediates involvedinorganic reactions.CO4.Togetinsightintothechemistryofsubstitutionreactions,eliminationandadditionreactions.CO5.Toabletoapplythevariousorganicsyntheticreagentsinthefieldorganicsynthesis.

Unit I Stereochemistry of organic compounds 18hNomenclatureoforganiccompounds-Cyclic,fusedpolycyclicandbridgedpolycyclichydrocarbons,Bridgedandfusedhydrocarbonsystems,Spirocyclichydrocarbonsystems,HeterocyclicsystemscontainingNitrogenandOxygen.Introduction to molecular symmetryand chirality,Axial Chirality, Planar Chirality and Helicity, Relativeconfiguration, Stereochemical nomenclature, R and S, E and Z. Prostereoisomerism, stereotopicityand stereoprojections. Non-carbon chiral centres –Nitrogen, phosphorus and sulfur as chiral centres.Axial stereochemistry:Atropisomerism and its designation, M and P configurations. Stereoselectivity:enatioseelctetivity, diastereeoselectivity and stereoconvergence. Basic introduction to chiral separationmethodsandestimationofenantiomericexcess.Conformationalanalysisofalkanesandcycloalkanes,Biasedsystems.Effectofconformationonreactivityofcyclohexanes–conformationofdecalin.IntroductiontoORD,CD-theirapplicationinassigningconfiguration.Sectorrulessuchasoctantandaxialhaloketonerules.Cottoneffect.Chiral drugs: Ibuprofen,Methyldopa, andThalidomide–Structure, chirality and activity (Basic conceptsonly)

7

Unit II Structure, reactivity and intermediates 18 hReactioncoordinates-differencebetweentransitionstateandintermediates,Homolyticandheterolyticbondfissions. Formation and structure of carbocations, carbanion and free radicals, Stability of intermediates,influence of field effect, inductive, mesomericand steric effects on controlling stability if carbocations,carbanionsandcarbon-centered radicals. Influenceof structural featuresonacidity,basicityand reactivityof organic compounds.Alkyl, aralkyl and allylic cations –influence of substituents. General reactions ofcarbocations, carbanions and free radicals.Introduction to radical ions. Formation, structure, stability andchemicalreactionsofcarbens,nitrenesandarynes.

Unit III Substitution reactions 18 hNucleophilic substitution at sp3carbon - SN1 and SN2 mechanisms.Walden inversion, stereochemistry.Effectofsolvent,leavinggroupandsubstratestructureonratesofSN1andSN2substitutions.Neighbouringgroupparticipation,Non-classicalcarbocations,CompetitionbetweenSN1andSN2reactions.SN1’,SN2’,SNi mechanism.Mechanismofesterificationandesterhydrolysis-acidcatalysedandbasecatalysedreactions.AromaticSubstitutionreactions-Electrophilicsubstitution:mechanismandevidence-Reactionsinvolvingnitrogen,sulphur,carbon,halogenandoxygenelectrophiles.Directiveandratecontrollingfactorsinaromaticswith one or more substituents.AromaticNucleophilicSubstitutionreactions-SN1,SNAr,benzyneandSRN1mechanismandevidencewithexamples.

Unit IV Elimination and addition reactions 18hEliminationreactionsleadingtoC=Cbondformationandtheirmechanisms.E1,E2andE1CBmechanisms.StereoaspectsofC=Cbondformation.Effectofleavinggroupandsubstratestructure.HoffmannandSaytzeffelimination.Ciselimination.StereoaspectsoftheadditionofH2O,X2,HX,andboranestoC=Csystems. Effectofsubstituentsontherateofadditions.Cisandtranshydroxylationofcycloalkenes.NucleophilicadditiontoactivatedC=Csystems.Structureofthetransitionstateintheadditionreactions.Michaeladdition:mechanism.AdditiontoCarbon-Heteroatommultiplebonds:Aldolcondensation(normal,crossedanddirected),Perkin,Stobbe,Knoevenagel,Darzen,Reformatskyandbenzoincondensations.Grignard,Cannizzaro,WittigandWittig-Hornerreactions.ApplicationofCram’srule,Felkin-Annmodel.

Unit V Separation techniques 18 hClassification of chromatographic methods.Theory of chromatography. Applications of chromatographicmethods.Adsorptionandpartitionchromatography.Paper,thinlayerandcolumnchromatographicmethods.CentrifugalTLC,LC,Pressurecolumnchromatography,HPLCandGC.Columnmatrices.Detectors.AffinityandchiralseparationsusingHPLC.Normalandultra-centrifugation.GelandCapillaryelectrophoresisandtheirapplications.Solventextraction.ExtractionusingsupercriticalliquidCO2,Craig’stechniqueofliquid-liquidextraction.

References1. D.Hellwinkel,Systematicnomenclatureoforganicchemistry,Springer,2001.2. D.Nasipuri,“StereochemistryofOrganiccompounds”,2ndEdition,WileyEastern,1994.3. J.Clayden,N.Greeves,andS.Warren,“OrganicChemistry,”2ndEdition,OxfordUniversityPress,2012.4. P. S. Kalsi, “Stereochemistry, conformation and mechanism,” 8th Edition, New Age International

Publishers,2015.5. P.Y.Bruice,“Organicchemistry,”8thEditionPrenticeHall,2016.6. P.Sykes,“Aguidebooktomechanisminorganicchemistry,”6thEdition,PearsonIndia,2003.7. S.N.Issacs,“Physicalorganicchemistry,”PrenticeHall2ndedition,1996.8. M.B.Smith,“March’sadvancedorganicchemistry,”7thEdition,Wiley,2013.9. F.A.CareyandR.S.Sunderg,“Advancedorganicchemistry,PartsAandB,”5thEdition,Springer,2008.10.M.A.FoxandJ.K.Whitesell,“Organicchemistry,”3rdEdition,JonesandBartlett,2004.11.C.J.MoodyandW.H.Whitham,“Reactiveintermediates,”OxfordChemistryPrimers,No.8,Oxford

UniversityPress,1992.12.I.L.Finar,“OrganicchemistryVol2,”3rdEdition,LongmansGreenandCompany,1964.13.F.A.Carey,“Organicchemistry,”5thEdition,McGrawHill,2000.

8

14.M.B.Smith,“Organicsynthesis,”3rdEdition,AcademicPress,2011.15.H.O.House,Modernsyntheticreactions,2ndRevisedEdition,BenjaminCummins,1965.16.R.K.Mackie,D.M.SmithandR.A.Aitken,“Guidebooktoorganicsynthesis,”2ndEdition,Longman

ScientificandTechnical,1990.17.W.Carruthers,“Modernmethodsinorganicsynthesis,”3rdEdition,CambridgeUniversityPress,1987.18.R.O.C.NormanandJ.M.Coxon,“Principlesoforganicsynthesis,”CRCPress,1993.

19PCH13 PHYSICALCHEMISTRY –I

90 h

Course Outcome:CO1.Attheendofthecourse,thelearnersshouldbeableto:Usemathematicaltechniquesinlinearalgebraforeigenvaluesandeigenvectorsandfirstandsecondorderdifferentialequationsnotonlyinquantumchemistrybutinotherareasofphysicalandtheoreticalchemistrythatwillbeofferedduringthewholeprogramme.CO2.Solveallthemodelproblemsinquantummechanicsforwhichexactanalyticalmethodsandsolutionsareavailableandwillapplythemtoanalyzethebasisbehindthepostulatorymethodofquantummechanicsandwhichformsthefoundationsforadvancedstudyofthesubject.CO3.Relateconceptsthatwereoriginallyintroducedpurelyasmodernatomicphysicstomolecularsystemsthroughharmonicoscillator,spinandrigidrotator.CO4.Utilizetheprinciplesofgrouptheorytopredictthehybridizationofmoleculesandfindouttheselectionruleofvariousspectraltechniques.CO5.Understandthevarioustheoriesofreactionrate.CO6. Solve problems on rate/rate constants/efficiency for (i) complex reactions (ii) unimolecular andbimolecularreactions,and(iii)electronicallyexcitedstatedynamicsCO7.Toknowthebasicsprincipleofdifferenttechniquesemployedinmolecularspectroscopy.CO8.Tostudytheorigin,instrumentationandimportantapplicationsofMicrowave,IR,Raman,UVtechniques.

Unit 1- Quantum Chemistry I 18 hClassicalmechanics and its limitations, need of quantummechanics, concept ofmatterwave, deBroglierelationanditsexperimentalproof,uncertaintyprincipleanditsconsequences.Postulates of Quantum MechanicsState function postulate:Born interpretation of the wavefunction, well behaved functions, orthonormalityofwavefunctions.Operatorpostulate:operatoralgebra,linearandnonlinearoperators,Laplacianoperator,commuting and non-commuting operators, Hermitian operators and their properties, eigen functions andeigen values of an operator. Eigen value postulate: eigen value equation, eigen functions of commutingoperators.Expectationvaluepostulate.Postulateof time-dependentSchrödingerequation,Quantizationofangularmomentum,quantummechanicaloperatorscorrespondingtoangularmomenta(Lx,Ly,LzandL2)-commutation relations between these operators.Application of Quantum mechanics to Exactly Solvable Model ProblemsTranslationalmotion: free particle in one-dimension, particle in a boxwith infinite potential barrier- onedimensionalbox,threedimensionalboxandcubicalbox-degeneracy-particlewithfinitepotentialbarriers-onepotentialbarrier,twofinitebarriers,potentialbarriersofdefinitethickness-Quantummechanicaltunneling(Qualitativeconceptonly)Vibrationalmotion: one-dimensional harmonic oscillator (complete treatment),Hermite equation (solvingbymethodofpowerseries),Hermitepolynomials,recursionrelation,wavefunctionsandenergies-importantfeatures,Harmonicoscillatormodelandmolecularvibrations.Symmetricandantisymmetricwavefunctions,Pauli’santisymmetryprinciple,thepostulateofspin.Spinorbitals.Spin-orbitcoupling.Vectoratommodel-Termsymbols,explanationofspectrallines(forsandpblocksonly)

Unit II Molecular symmetry and Applications of Group Theory 18 hSymmetry and Character table: Symmetry elements and symmetry operation. Matrix representation ofsymmetryoperations.Characterofamatrix.Conditionsforasetofelementstoformagroup.Pointgroups.Multiplication of operations. Group multiplication table. Similaritytransformation and classification of

9

symmetryoperation,Matrix representationofpointgroup.Reducibleand Irreducible representations.TheGreatOrthogonalitytheorem.RulesderivedfromGOT(proofnotrequired).SettingupofcharactertableofC2v,C3vandC2hgroups.Directproductrepresentations.Reductionformula,reductionofreduciblerepresentationtoIRs.Transformationpropertiesofatomicorbitals.Hybridisation: identificationofatomicorbitals takingpartinhybridisationoftriangularplanar,squareplanar,trigonalbipyramidal,squarepyramidalandtetrahedralmolecules. Spectroscopicapplications:Transitionmomentintegraltransitionmomentoperator.Vanishingmatrixelement.SymmetryselectionruleforIR,Ramanandelectronicspectra.

Unit III Spectroscopy –I 18 hMicrowave spectroscopy:Rotationalspectrum,intensityofspectrallines,calculationofinternucleardistance.Non-rigidrotorsandcentrifugaldistortion.Rotationalspectraofpolyatomicmolecules-linearandsymmetrictopmolecules.Introductiontoinstrumentation.Vibrational Spectroscopy:Vibrationalspectraofharmonicandanharmonicoscillator.Selectionrules.Morsecurve,fundamentalsandovertones.Determinationofforceconstant.Rotationalfinestructure,P,Q,Rbranchesofspectra.Vibrationalspectraofpolyatomicmolecules:Normalmodes,classificationofvibrationalmodesintostretching(asymmetric,symmetric),bending,parallelandperpendicularvibrations.Fingerprintregionandgroupfrequencies.IntroductiontoFTIRandinstrumentation.Raman spectroscopy:Ramanscattering,polarisabilityandclassicaltheoryofRamanspectrum.Rotationaland vibrationalRaman spectrum.Raman spectra of poly atomicmolecules.Complementarity of IR andRamanspectra.Mutualexclusionprinciple.Introductiontoinstrumentation.LaserRamanspectrum.Electronic spectra.Electronicspectraofdiatomicmolecules.Vibrationalcoarsestructureandrotationalfinestructureofelectronicspectrum.Franck-Condonprinciple.Typesofelectronic transitions.Fotratdiagram.Predissociation.Calculationofheatofdissociation.Electronicspectraofpolyatomicmolecules:Electronictransition among molecular orbitals and absorption frequencies. Effect of conjugation. Introduction toinstrumentation.Simultaneousdeterminationoftwocomponents.

Unit IV Chemical kinetics 18 hTheories of reaction rates: Collision theory and its failure,. Transition state theory-Eyring equation.Comparisonofthetwotheories.Thermodynamicformulationofthereactionrates.potentialenergysurfacesTheoriesofunimolecularreactions-Lindemanntheory,Lindemann-Hinshelwoodmechanism,qualitativeideaofRRKMtheory,Kinetics of complex reactions-parallelreactions,opposingreactions,consecutivereactionsandchainreactions,steadystatetreatment,kineticsofH2-Cl2andH2-Br2reactions,decompositionsofethane,acetaldehydeandN2O5.Rice-Herzfieldmechanism,branchingchainreactionsHinshelwoodmechanismofchainreactionsandexplosion.Fast reactions:Relaxationmethod,relaxationspectrometry,flowmethod,shockmethod,fastmixingmethod,fieldjumpmethod,pulsemethod,FlashphotolysisandNMRmethod.Reactions in solution:Factors affecting reaction rates in solutions, effect of dielectric constant and ionicstrength,cageeffect,Bronsted-Bjerrumequation,primaryandsecondarykineticsalteffect,influenceofsolventonreactionrates,significanceofvolumeofactivation,linearfreeenergyrelationship.HammetequationandTaftequation.

Unit V Gaseous and liquid state 18 hMaxwell’s distribution ofmolecular velocities, influence of temperature onmolecular velocities, types ofmolecular velocities-average velocity and most probable velocity and its determination fromMaxwell’sequationTransportphenomenaingases-viscosityofgases,Chapmanequation,determinationofviscosityofgases,calculationofmeanfreepath,Thermalconductivity,diffusion,DegreesoffreedomofgaseousmoleculesTranslational, Rotational and vibrational. Equation of state of real gases-van derWaal’s equation, Otherequationofstates—Radlich-Kwongequation,Clausiusequation,Virialequation,secondvirialcoefficientanddeterminationofdiameterofamolecule.Inter molecular forces—dipole-dipole interaction, induceddipole- dipole, induceddipole-induceddipoleinteractionsLiquid state Liquidvapourequilibria,vapourpressure-methodsofmeasuringvapourpressure-barometricmethodanddynamicmethod-equationofstateforliquids,structureofliquids,X-raydiffractionofliquids-

10

vacancymodelforaliquid,paircorrelationfunction,surfacetension,determinationofsurfacetension,dropweightmethodanddropnumbermethod,viscosity,determinationofcoefficientofviscosityusingOstwaldviscometer.

References1. I.N.Levin,“QuantumChemistry”,PrenticeHall,NewJersey,Vthedn.,2000.2. D.A.McQuarrie,“QuantumChemistry”,VivaPublishers,NewDelhi,2003.3. M.W.Hanna,“QuantumMechanicsinChemistry”,Benjamin,NewYork-Amsterdam,1965.4. R.K.Prasad, “QuantumChemistry”,NewAge International (p)Limited-Publishers,NewDelhi, IVth

edn.,2009.5. T.Angel,“QuantumChemistryandSpectroscopy”,PearsonEducationIIIrdedn.6. P.W.Atkins,R.S.Friedman,“MolecularQuantumMechanics”,OxfordUniversityPress,Oxford, IVth

edn.,2005.7. J.PLowe,K.Peterson,“QuantumChemistry”,AcademicPress,IIIrdedn.,2006.8. S.Glasstone,“ThermodynamicsforChemists”,ReadBooks,2007.9. G.W.Castellan,“PhysicalChemistry”,Addison-LesleyPublishing.10.P.W.Atkins,”Physicalchemistry’,OxfordUniversityPress.11.D.A.McQuarrie,J.D.Simon,“PhysicalChemistry-AMolecularApproach”,VivaPublishers,1997.12.K.JLaidler,“ChemicalKinetics”,McGrawHill,1965.13.J.E.House,“PrinciplesofChemicalKinetics”,Elsevier,2007.14.J.Rajaram,J.C.Kuriakose,”KineticsandMechanismsofChemicalTransformations”,McMillan.15.C.Kalidas,“ChemicalKineticMethods:PrinciplesofFastreactionTechniquesandApplications,New

AgeInternational,2ndedn.,2005.16.K.KRohatgi-Mukherjee,“FundamentalsofPhotochemistry”,NewageInternational,3rdedn.,2014.17.A.W.Adamson,“PhysicalChemistryofSurfaces”,5theditionWileyIndia,1990.18.D.K.ChakrabartyandB.Viswanathan,Heterogeneouscatalysis,NewAgePublications,2009.19.G.A.Somorjai,Y.Li,IntroductiontoSurfaceChemistryandCatalysis.International,2ndedn.,2010.20.Puri,Sharma,Pathania,“PrinciplesofphysicalChemistry”Vishalpublishingcompany,2013.21.GurdeepRaj“AdvancedPhysicalChemistry”GOELPublishingHouse,Meerut,2004.

19PCH14: INORGANIC CHEMISTRY PRACTICALS -I

Total 125 h

Course Outcome:CO1.Tobeabletoidentifyandseparaterare/lessfamiliarionssuchasTi,W,Se,Mo,Ce,Th,Li,Zr,V,Uetc.CO2.toestimatecolorimetricallyionssuchasFe,Cu,Ni,Mn,CrandMnetc.CO3.Developingtheskilltopreparevariousmetalcomplexestherebydevelopingresearchaptitude.

1. Separationandidentificationofrare/lessfamiliarcationssuchasTi,W,Mo,Th,Zr,V,UandLi2. VolumetricestimationusingEDTA,ammoniumvanadate,cericsulphateetc.3. ColorimetricestimationofCr,Fe,Mn,Ni,Cuetc.4. Preparationofmetalcomplexes:selectioncanbemadefromthefollowingoranyotherfromtheexisting

literature.[Co(NH3)6]Cl3[Cu(NH3)4]SO4K3[Cr(C2O4)3]K3[Fe(C2O4)3]Cisandtransisomersof[Co(en)2Cl2]Cl[Cr(en)3]Cl3

References1. A.I.Vogel,ATextBookofQuantitativeInorganicAnalysis,Longman,4thedition,1978.2. A.I.Vogel,ATextBookofQualitativeInorganicAnalysis,Longman5thedition,1979.

11

3. D.A.SkoogandD.M.West,AnalyticalChemistry:AnIntroduction,SaundersCollegePublishing,4thedition,1986.

4. W.G.Palmer,ExperimentalInorganicChemistry,CambridgeUniversity,1959.

19PCH15: ORGANIC PRACTICALS-I

Total 125 h

Course Outcome:CO1.Tolearntheseparationandpurificationofanorganicmixturebychemical/solventseparationmethods.CO2.TogaintheskilltoseparatethemixtureoforganiccompoundusingTLCplate.CO3.ToidentifytheorganiccompoundsbasedontheirRfvalues.CO4.Tobeabletoconducttwostageorganicpreparations.CO5.TotodrawthestructureofcompoundsusingChemdrawsoftware

A. Separation and identification of organic compounds1. Quantitativewetchemistryseparationofamixtureoftwocomponentsbysolventextraction2. TLCof thepurifiedsamplesalongwiththemixture insameTLCplates (component 1 with mixture

and component 2 with mixture on separate TLC plate ) and calculation of Rfvalues-ReportingandrecordingTLCinstandardformats-preparationofsamplesolution,adsorbent,dimensionsoftheplate,saturationtime,developingtime,visualizationanddetection,RfValue,Drawing-intheformofatable.

B. Separation of a mixture of by column chromatography (not for End semester evaluation)1)Malachitegreenandmethyleneblue2)o-nitroanilineandp-nitroaniline.C. Preparation of compounds by two stages.Recording/downloadingUV,IR,1HNMRand13CNMRandEImassspectraofsynthesizedcompounds.TLCanalysis-(stage1reactantsandproductsonTLCplate1andstage2reactantsandproductsonplate2)-RecordTLCinstandardformatasinseparationAll preparations must be restricted to 1 g level Nitration1)Acetanilide-→p-nitroacetanilide→p-nitroaniline2)Methylbenzoate→methylm-nitrobenzoate→m-nitrobenzoicacidBromination3)Acetanilide→p-bromoacetanilide→p-bromoanilineAldol condensation- Synthesis of heterocycles4)benzaldehyde→Dibenzylideneacetone→1,5-Diphenyl-3-styryl-2-pyrazolineDiazocoupling5)Aniline→Diazoaminobenzene→p-aminoazobenzeneRerrangement6)Pthalicanhydride→Pthalimide→anthranilicacidSynthesis of Dyes7)N,N-Dimethylaniline→N,N-dimethyl-4-nitrosoaniline→methyleneblueTheboardofexaminershavetoselecteitherTLCofseparatedcomponentsOR TLC of preparation for an examination.ButbothTLCexaminationsaretobepracticedandenteredintherecordofexperiments

References1. B.S.Furniss,“Vogel’stextbookofpracticalorganicchemistry,”5thEdition,Longman,1989.2. D.L.Pavia,G.M.Lampman,G.S.KrizandR.G.Engel,“Amicroscaleapproachtoorganiclaboratory

techniques,”WadsworthPublishing,5thEdition,2012.3. R.K.Bansal,“LaboratorymanualoforganicChemistry,”WileyEastern,19944. N.K.Vishnoi,“AdvancedPracticalOrganicChemistry,”3rdEdition,Vikas5. F.G.MannandB.C.Saunders,“PracticalOrganicChemistry,”PearsonEducation,20096. J.B.Cohen,“Practicalorganicchemistry,”ForgottenBooks,20157. P.FShalz,Journal of Chemical Education, 1996,173:267.8. Monographongreenlaboratoryexperiments,DST,GovernmentofIndia,pp1-79.9. Forspectraldataoforganiccompounds,see:http://sdbs.riodb.aist.go.jp/sdbs/cgi-bin/direct frame top.

cgi.

12

19PCH16 PHYSICAL PRACTICALS –I

125 h

Course Outcome:CO1. To verify the some important principles in physical chemistry and to determine various physicalproperties.CO2.Tolearntocarryoutsomesimplecomputationalchemistrycalculations

AdsorptionFreundlichandLangmuirisothermsforadsorptionofacetic/oxalicacidonactivecharcoal.Determinationofconcentrationofacetic/oxalicacid.KineticsDeterminationofrateconstantofacidhydrolysisofmethylacetate.Determination of Arrhenius parameters.Determinationofconcentrationofgivenacid.DeterminationofrateconstantofthesaponificationofethylacetateandevaluationofArrheniusparameters.DeterminationofrateconstantofreactionbetweenK2S2O8andKI.Studythekineticsofiodinationofacetoneinacidmedium.Phase ruleSolid-liquid equilibriaConstruction of phase diagram and determination of the composition of unknownmixture (naphthalene/biphenyl,naphthalene/benzophenone,naphthalene/diphenylamine)Constructionofphasediagramwithcongruentmeltingpoint-naphthalene/metadinitrobenzenePartially miscible liquid pairs-CSTofphenol-watersystem.Effectof impurities(KCl/NaCl/succinicacid)onthemiscibility temperatureofphenol-watersystemandhencethedeterminationofconcentrationofgivenunknownsolution.Threecomponentsystem-Constructionofternaryphasediagramofaceticacidchloroform-watersystemandhencethecompositionofgivenhomogeneousmixture.Constructionoftie-line.Distribution lawDistributioncoefficientofammoniabetweenchloroformandwater.Determinationofequilibriumconstantofcopper-ammoniacomplexbypartitionmethodorcoordinationnumberofCu2+incopper-ammoniacomplex.Distributioncoefficientofbenzoicacidbetweentolueneandwater.Distributioncoefficientofiodinebetweenhexaneandwater/CHCl3andwater/CCl4andwaterDeterminationoftheequilibriumconstantofthereactionKI+I2 KI3 andhencetheconcentrationofgivenKIinhexaneandwater/CHCl3andwater/CCl4andwater.Determinationofhydrolysisconstantofaniliniumhydrochloride.Dilute SolutionsDeterminationofKfofsolidsolvent,molarmassofnon-volatilesolute,massofsolventandcompositionofgivensolution(Solvent-Naphthalene/Biphenyl/Benzophenoneetc.Solute-Naphthalene/Biphenyl/Diphenylanmineetc)DeterminationofvantHoff’sfactorforbenzoicacidinNaphthalene.Determinationofatomicityofsulphur.Transition temperatureDeterminationofKTofsalthydrate,molarmassofsolute,massofsalthydrateandcompositionofgivensolution(Solvent-Na2S2O3.5H2O/CH3COONa.3H2O,Solutesglucose,sucrose,urea)ThermochemistryDeterminationoftheconcentrationofgivenstrongacid/alkali.ThermometrictitrationofNaOHVsstandardHCl.HeatofdisplacementofCu2+byZn.Determinationoftheheatofionisationofaceticacid.

References1. V.D.Athawal,“ExperimentalPhysicalChemistry”,NewAgeInternational,1stedn.,2001.2. B. P. Levitt and J.A. Kitchener,”Findlay’s Practical Physical Chemistry”, Longmans, London, 9th

edn.,1973.

13

3. J.M. Newcombe, R. J. Denaro,A. R.Rickett, R.M.WWilson, “Experiments in Physical Chemistry”Pergamon,1962.

4. A.M.James,andF.E.Pichard,“PracticalPhysicalChemistry”,Longman.5. R.C.DasandBehera,“ExperimentalPhysicalChemistry”,TataMcGrawHill,1983.6. B.Viswanathan,“PracticalPhysicalChemistry”,VivaPublications,2012.7. P.S.Sindhu,“PracticalsinPhysicalChemistry-AModernApproach”,McMillanIndia,2005.8. D.P.Shoemaker,C.W.Garland&J.W.Nibler.“ExperimentsinPhysicalChemistry

MODEL QUESTION PAPER19PCH11: INORGANIC CHEMISTRY- I

Time : 3 Hrs Max. Marks: 75

S ECTION AAnswer two among (a), (b) and(c) from each questioncarries2 marks

1. a)WhatismeantbyNephelauxeticeffect?b)Explainlinkageisomerismwithsuitableexample.c)Whatismeantbycrystalfieldstabilizationenergy?

2. a)Whatdoyoumeanbysignificantfigure?Howmanysignificantfiguresareinthefollowing?i)0.0026i)6.023x1023b)Whataremetallochromicindicators?Giveanexample.c) In a volumetric experiment the volumes of the titrant used are 9.98, 9.99, 9.98, 9.95, 10.00 and 1 0.02mL.Calculatethestandarddeviation.

3. a)Theelectronicspectrumof[Ti(H2O)6]3+exhibitsadoublehumpedcurve.Why?

b)WhatarePascalsconstant?Wherearetheyused?c)Chromiumacetatedihydratecrystalsarediamagneticatroomtemperature.Why?

4. a)Explaintheterm‘shapeselectivity’.b)GivethepreparationofKrCl4andKrO2.c)Whatarezeolite?Explaintheiruseaswatersofteners.

5. a)Brieftheroleofcatalyticconvertersinautomobiles.b)Explaintheformationofphotochemicalsmog.c)Mentionthedifferentregionsofatmosphere.

(2x10= 20 marks)SECTION B

Answer either among (a) or (b) from each questioncarries5 marks6. a)StateandillustrateJahnTellereffect.

b)Explainthecrystalfieldtheoryofoctahedralcomplexes.7. a)Giveabriefnoteonscatterdiagramanditssignificance.

b)Explainthetitrationsinnon-aqueoussolvents.8. a)Two complexes (A andB) ofNi (II) are believed to be octahedral and tetrahedral. Each has three

absorptionbands,but‘A’has =10and‘B’has =150.Whichoneofthemisprobablyatetrahedralcomplex? Explain measurement of which physical property would exclude the probability of eithercomplexbeingsquareplanar.Explain.b)Comparetheelectronicspectraoflanthanideswiththatofthefirstrowtransitionmetals.Whydothelanthanidesionsgiverisetoverysharpbandsintheirelectronicspectra?

9. a)Giveanaccountofinterhalogencompounds.b)Writeashortnoteonsilicones.

10.a)Listoutthemajorpollutants.Outlinehowtheyaffecthumanhealth?b)Describehowwecanquantifysoilacidity.

(5x5= 25 marks)

14

SECTION CAnswer any three questions.Each questioncarries10 marks

11.ExplainthebondinginoctahedralcomplexeswithandwithoutpibondsusingMOTheory.12.Brieflyexplaintheprinciple,instrumentationandapplicationsofTGandDTA.13.Explain,whatismeantbyspin-onlymagneticmoment.Illustratewithsuitableexamplestheapplication

ofthevaluesofspin-onlymagneticmomentsinthestructuralelucidationoftransitionmetalcomplexes.14.WriteashortnoteonthepreparationandpropertiesofheteropolyacidsofMoandW.15.WhatarePourbaiuxdiagrams?Outlineitsroleinexplainingthechemistryofprocessesinlithosphere.

(10x3= 30 marks)

MODEL QUESTION PAPER19PCH12: Organic Chemistry-I

Time: 3 hours Maximum marks:75

Section AAnswer any two among (a), (b) and (c) from each question. Each sub question carries 2 marks

1. a)WriteIUPACnamesofthefollowing.

b)Indicatetheelementofsymmetrypresentineachofthefollowingmolecules.i)trans-1,4-dichlorocyclohexane-

i)c)Whatisatropisomerism?

2. a)Howarynesareformed?b)p-Nitroanilineislessbasicthanm-nitroanile,explain.c)Arrangethefollowingcarbocationsinorderofincreasingstabilityandgivereasons.

3. a)WhatisSNireaction?

b)AlkalinehydrolysisofEt2NCH(Cl)CH2CH3producesEt2NCH(Et)CH2OH.Accountforthisobservationc)Writetwoexamplesofnonclassicalcarbocations.

4. a)Howwouldyoupreparetrans-1,2-dihydroxycyclohexanefromcyclohexene?b)Writethemechanismofbenzoincondensation.c)HowcantheE1CBpathwaybedistinguishedfromthekineticallyindistinguishableE2pathway?

5. a)Whatistheprincipleofchromatographyb)Whatispaperchromatography?Howisithelpfulinidentifyingvariousalphaaminoacids?c)OutlinetheapplicationsofGelelectrophoresis.

(2x10= 20 marks)Section B

Answer either (a) or (b) from each question. Each sub question carries 5 marks6. a)CompareORDandCDandexplaintheirrelationship

b)Writeanoteonstereochemistryofnitrogencompounds7. a)ExplaintheFelkin-Annmodelwithanexample

b)Howcarbenesaregenerated?Explainitsstructureandproperties

15

8. a)ExplainwhyantiMarkonikoff’sadditionisnotexhibitedbyHClorHIwhenreactedwith1-butene?b)AfterstandinginaqueousacidR-2-butanolisfoundtohavelostitsopticalactivity.Accountforthisobservation.

9. a)Writeanoteoncisandtranshydroxylationofalkenesb)StateCramsrule.Explainitwithsuitableexample

10.a)Explaintheprincipleofgaschromatographyandionexchangechromatography.Whattypeofsubstancesareanalysedusingtheabove?b)DescribetheprincipleandinstrumentationofHPLC

(5x5= 25 marks)Section C

Answer any three questions.Each questioncarries10 marks11.Giveabriefaccountonstereoselectivity,enantiomericexcessandchiralseparation.12.Explainthefollowing

a)SNArmechanism,b)Orientationeffectinaromaticelectrophilicsubstitution13.Discuss the following

a)competitionbetweenSN1andSN2b)Stereochemistryofnucleophilicsubstitution14.Describe the following

a)Mechanismwithevidencesofaldolcondensationb)Wittigreactionsandapplications

15.Withaschematicdiagramexplaintheprinciple,instrumentation,andapplicationsofGC(10x3= 30 marks)

MODEL QUESTION PAPER19PCH13: Physical Chemistry- I

Time: 3 h Max.Marks:75Section A

Answer any two from a,b,c,ofeachquestion.Eachsubquestioncarries2 marks.1. (a)CalculatedeBrogliewavelengthofmass1mgmovingwithavelocityof10ms-1

(b)Whatisanoperator?Giveexample.(c)WritespectroscopictermsymbolforthegroundstateofOatom

2. (a)Identifythesymmetryelementspresentinthefollowingandassignthepointgroupi)H2Oii)HCl(b)Explainimproperaxisofsymmetry.(c)Whatismeantbycharactertable.

3. (a)Whatareovertones?Whyaretheyweak?(b)Stateandexplaintheruleofmutualexclusionwithoneexample.(c)StateFranck-Condonprinciple.

4. (a)Howisnmrspectroscopymadeuseofinthestudyoffastreactions?(b)Whatissteadystateapproximation?(c)Definequantumyield

5. (a)Whatistheeffectoftemperatureonthedistributionofmolecularvelocitiesofagas?Explain.(b)Calculatetherootmeansquarevelocityofnitrogenat27oC(c)Writethevirialequationofstate.Explaintheterms.

(10x2=20marks)Section B

Answer either a or b ofeachquestion.Eachquestioncarries5 marks.6. (a)ExplainQuntaummechanicalTunneling

(b)Writekineticenergyoperator.ShowthatitisaHermitionoperator7. (a)ConstructthemultiplicationtableforthesymmetryoperationsofNH3 molecule.

(b)Stateandexplainorthogonalitytheorem.8. (a)ExplaintheprincipleandapplicationofLaserRamanSpectrum.

(b)ExplaintheoriginofPandRbranchesinrotational-vibrationalspectrum.

16

9. (a)ExplainJabalonskidiagram(b)DerivetheratelawforthedecompositionofN2O5

10.(a)CalculatetheviscosityofO2at25oC.Themoleculardiameteris3.6Å

(b)Writeanyonemethodforthedeterminationofsurfacetensionofliquid(5x5=25marks)

Section CAnswer any three questions.Eachquestioncarries10 marks.

11.ApplySchrodingerWaveequationforasimpleharmonicoscillator.Findeigenvaluesandeigenfunctions12.Construct the character table for C2vandexplain.13.(i)Giveanaccountofrotationspectraofdiatomicmolecules.Explaintheeffectofnonrigidityofthebond

on the spectra.(ii)Howistherotationalspectrumofadiatomicmoleculeaffectedbyisotopicsubstitution?

14.Explainchainreactions.DiscussSeminoffHenshelwoodtheoryofbranchingchainreactions15.DiscussviscosityofagasandChapmanequation.Howcanwecalculatemeanfreepathandcollision

diameterfromviscositydetermination(3x10=30marks)

17

SEMESTER II19PCH21: INORGANIC CHEMISTRY –II

Total 90 h

Course Outcome:CO1. To get an insight into the preparation and properties of sulphur, nitrogen, phosphorus and boroncompounds.CO2.Toknowthestructureandbondingofimportantcoordinationcompounds.CO3. To understand themagnetic properties of complexes and to know howmagnetic moments can beemployedfortheinterpretationoftheirstructure.CO4.Tolearntheextractionandseparationoflanthanidesandactinides.CO5.TobeabletoapplytheextractiontechniquestoexplorethemineralwealthofbeachsandsofKerala.CO6.Arriveatthechemicalcompositionsbasedonunitcellcontentsandfractionalcoordinates.CO8.Identifyandapplyasuitablestrategiesforsynthesizinginorganiccrystallinesolidsinpolycrystallineandsinglecrystalforms.CO9.CorrelateandPredictstructure-composition-properties(magnetic,electricalandoptical) in inorganiccrystallinesolids.

Unit I Sulphur, nitrogen, phosphorus and boron compounds 18 hSulphur-nitrogencompounds:Tetrasulphurtetranitride,disulphurdinitrideandpolythiazylSXNYcompounds.S-Ncationsandanions.Sulphur-phosphoruscompounds:MolecularsulphidessuchasP4S3,P4S7,P4S9andP4S10. Phosphorous-nitrogen compounds: Phosphazines. Cyclo and linear phosphazines. Boron-nitrogencompounds: Borazine, substituted borazines and boron nitride. Boron hydrides: Reactions of diborane.Structureandbonding.Polyhedralboranes:Preparation,properties,structureandbonding.Thetopologicalapproachtoboronhydridestructure.Styx numbers.Importanceoficosahedralframeworkofboronatomsinboronchemistry.Closo,nidoandarachnostructures.Wade’srules.Carboranesandmetallocarboranes.

Unit II Coordination chemistry-II: Spectral and magnetic properties of transition metal complexes 18 hElectronicspectraofmetalcomplexes-Termsymbolsofdn system,Racahparameters,splittingoftermsinweakandstrongoctahedralandtetrahedralfields.Correlationdiagramsfordn andd10-n ionsinoctahedralandtetrahedralfields(qualitativeapproach),d-d transition,selectionrulesforelectronictransition-effectofspinorbitcouplingandvibroniccouplingInterpretationofelectronicspectraofcomplexes-Orgeldiagrams,Tanabe-Suganodiagrams,CalculationofDq , B andâ(Nephelauxeticratio)values,chargetransferspectra.Magneticpropertiesofcomplexes-paramagneticanddiamagneticcomplexes,molarsusceptibility,Gouy’smethodforthedeterminationofmagneticmomentofcomplexes,spinonlymagneticmoment.Temperaturedependenceofmagnetism.Temperature Independent Paramagnetism (TIP). Spin state crossover,Antiferromagnetism-interandintramolecularinteraction.Applicationofmagneticmeasurementsinthedeterminationofstructureoftransitionmetalcomplexes.

Unit III Crystalline state 18 hCrystalsystemsandlatticetypes.Bravaislattices.Crystalsymmetry-Introductiontopointgroupsandspacegroups.Miller indices. Reciprocal lattice concept. Close packed structures: BCC, FCC and HCP.Voids.Coordinationnumber.Crystalbinding:Molecular,covalent,metallicandhydrogenbondedcrystals.X-Raydiffractionbycrystals:Functionof crystals.Transmissiongratingand reflectiongrating.Braggs equation.Diffractionmethods:Powderand rotatingcrystal. Indexinganddeterminationof lattice typeandunit celldimensionsofcubiccrystals.Crystaldefects:Perfectandimperfectcrystals.Point, lineandplanedefects.ThermodynamicsofSchottkyandFrenkeldefects.Colourcentersinalkalihalidecrystals.Defectclusters.Extended defects: Crystallographic shear structure and stacking faults.Dislocations and crystal structure.Structure of compounds ofAX (Zinc blende,Wurtzite),AX2 (Rutile, fluorite, antifluorite),AmX2 (Nickelarsenide),ABX3(Perovskite,Ilmenite).Spinels.Inversespinelstructures.

Unit IV Lanthanides and actinides 18 hLanthanides:Characteristicproperties.Electronicconfigurationsandtermsymbols.Occurrenceandextraction.Separationtechniques.Oxidationstates.Spectralandmagneticproperties.Shapesofforbitalandtheirsplittingincubicligandfield.Lanthanidecomplexesasshiftreagents.Actinides:Occurrenceandgeneralproperties.

18

Extractionofthoriumanduranium.Electronicconfigurationandtermsymbol.Oxidationstates.Spectralandmagneticproperties.Comparativepropertiesoflanthanidesandactinides.Trans-uraniumelementsandtheirstabilities.Applicationsoflanthanideandactinidecompounds.ComprehensivestudyofthebeachsandsofKeralaandtheirimportantcomponentssuchasmonazite,ilmenite,zirconandsillimanite.

Unit V Solid state chemistry 18 hKronig-Penneymodel,Freeelectrontheory,ZonetheoryandMOtheoryofsolids.Energybands-conductorsandnon-conductors,intrinsicandextrinsicsemiconductors.Electronsandholes.Mobilityofchargecarriers.HallEffect.Pyroelectricity,piezoelectricityandferroelectricity.Conductivityofpuremetals.Solidstatereactions-diffusioncoefficient,mechanisms,vacancydiffusion, thermaldecompositionofsolid-TypeIreactions,TypeIIreactions.Phasetransitioninsolids:classificationofphasetransitions-firstandsecondorderphasetransitions,Martensitictransformations,order-disordertransitionsandspinodaldecomposition.Kineticsofphasetransitions,sintering.Growingsinglecrystals-crystalgrowthfromsolution,growthfrommeltandvapordepositiontechnique.

References1. F.A.CottonandG.Wilkinson,AdvancedInorganicChemistry,JohnWileyandSons,6thedition,1999.2. J. E. Huheey, Inorganic Chemistry- Principles of Structure and Reactivity, Harper Collins College

Publishing,4thedition,2011.3. S.F.A.Kettle,PhysicalInorganicChemistry,OxfordUniversityPress,1stedition,1998.4. A.R.West,SolidStateChemistryanditsApplications,WileyEastern,1990.5. H.J.EmeleusandA.G.Sharp,ModernAspectsofInorganicChemistry,VanNostrand,4thedition,1973.6. L.V.Azaroff,IntroductiontoSolids,McGraw-Hill,1960.7. S.Cotton,LanthanidesandActinides,Macmillan,1991.8. B.N.FigginsandM.A.Hitchman,LigandFieldTheoryanditsApplications,Wiley-VCH,2000.9. A.SyamalandR.L.Datta,ElementsofMagnetochemistry,AffiliatedEast-WestPress,1980.10.C.Kittel,IntroductiontoSolidStatePhysics,WileyandSons,8thedition,2004.11.N.N.GreenwoodandA.Earnshaw,ChemistryofElements,REPPLtd,2ndedition,2005.12.A.Earnshaw,IntroductiontoMagnetochemistry,AcademicPress,1968.

19PCH22: ORGANIC CHEMISTRY- II

Total 90 h

Course Outcome:CO1.ComprehendandPredicttheroleoftemperature,solvents,andcatalystsinorganicreactions.CO2.Elucidatereactionmechanismsusingisotopeeffects.CO3.Comprehendtheorbitalinteractionsandorbitalsymmetrycorrelationsofvariouspericyclicreactions.CO4.WritemechanismoforganicreactionsinvolvingreactiveintermediatesandconcertedprocessesCO5.Applythesereactionsinorganicsynthesis.CO6.TofamiliarizewiththeimportantphotochemicalreactionsinOrganicChemistry.CO7.Understandthebiomoleculesandtheirroleinmetabolicactivities.

Unit I Physical organic chemistry 18 hReactivityinrelationtomolecularstructureandconformation.Stericeffects.F strain.Orthoeffect,Bondanglestrain.Linear free energy relationships.TheHammett equationand its applications.Taft equation.Solventpolarityandparameters.Y,ZandEparametersandtheirapplications.Primaryandsecondarykineticisotopeeffects.SalteffectsandspecialsalteffectsinSNreactions.Kineticandthermodynamiccontrolofreactions.Energy profiles, Hammond postulate. Principle of microscopic reversibility. Marcus theory. Methods ofdeterminingreactionmechanisms.Phasetransfercatalysisanditsapplications.

Unit II Molecular rearrangement and transformation reactions 18hTypes of organic rearrangements: Anionic, cationotropic, prototropic, free radical, carbene and nitreneintermediates. Mechanism with evidence of Wagner-Meerwein, Pinacol, Demjanov, Hofmann, Curtius,Schmidt,Lossen,Beckmann,Wolf,Fries,Fischer-Hepp,Hofmann-Martius,von-Richter,Orton,Bamberger,

19

Smiles, Dienone-phenol, Benzilic acid, Benzidine, Favorskii, Stevens, Wittig, Sommelet-Hauser, Bayer-Villigerrearrangements.

Unit III Aromaticity and symmetry controlled reactions 18 hAromaticityandantiaromaticity.Homo,heteroandnon-benzenoidaromaticsystems.Aromaticityofannulenes,mesoioniccompounds,metallocenes,cycliccarbocations,carbanions.Symmetry properties of MOs. Classification of pericyclic reactions. Mechanism and stereochemistry ofelectrocyclic, cycloaddition and sigmatropic reactions.Woodward-Hoffmann rules. FO,CD andHuckel-Mobiusanalysisofelectrocyclic,cycloadditionandsigmatropic reactions.FOanalysisof [1, j]and[3,3]migrations. 1,3-dipolar cycloaddition. Stereo aspects of Diels-Alder reaction and Cope re arrangement.Intramolecular Diels-Alder, Retro Diels-Alder, Alder-ene, retro-ene and cheletropic reactions. SyntheticapplicationsofDiels-Alderreactions.Fluxionalmolecules.

Unit IV Organic photochemistry 18 hPhotochemical processes.Energy transfer, sensitization and quenching.Singlet and triplet states and theirreactivity.Photoreactionsofcarbonylcompounds,enes,dienesandarenes.NorrishTypeIandTypeIIreactionsofacyclicketones.Freeradicalreactions:Patterno-BuchiandBartonreactions,photo-FriesandDi-ðmethanerearrangements. Photoreactions of Vitamin D. Photosynthesis, photochemistry of vision. Singlet oxygengenerationandtheirreactions.Introductiontochemiluminescence.Applicationsofphotochemistry.

Unit V Chemistry of natural products and biomolecules 18 hIntroductiontoprimaryandsecondarymetabolitesinplants.Extractionmethodsofchemicalconstituentsfromplants,suchasfractionationusingsolvents,specificextractionofalkaloidsandsupercriticalfluidextraction.Characterizations of isolated compounds (terpenes, sterols, alkaloids, carbohydrates, flavonoids and polyphenols)bycolourreactionsandsprayreagents.Biosynthesisofterpenesfrommevalonicacidandsterolsfromsqualene.Structureelucidationofocimene,classificationofpigments,structureelucidationofβ-carotene.Structural differences between a triterpene and a sterol. Synthesis of quercetin, synthesis of testosterone,androsterone,estroneandprogesterone.Determinationofcarbonskeletonofalkaloids(Hofmann,EmdeandVonBraundegradationmethods).Structuralelucidationofephedrine,nicotine,atropine.

References1. L.M.Harwood,“Polarrearrangements,”OxfordUniversityPress1995.2. M.B.Smith,“March’sadvancedorganicchemistry,”7thEdition,Wiley,2013.3. J.Clayden,N.Greeves,andS.Warren,“OrganicChemistry,”2ndEdition,OxfordUniversityPress,2012.4. S.N.Issacs,“Physicalorganicchemistry,”PrenticeHall2ndedition,1996.5. P.Y.Bruice,“Organicchemistry,”8thEditionPrenticeHall,2016.6. C.H.DupuoyandO.L.Chapman,“Molecularreactionsandphotochemistry,”2ndEdition,PrenticeHall,

1988.7. VonJ.Kagan,“Organicphotochemistry.PrinciplesandApplications,”AcademicPress,1993.8. J.M.CoxonandB.Holton,“Organicphotochemistry,”CambridgeUniversityPress,1987.9. S.H.Pine,“Organicchemistry,5thEdition,Mc-GrawHill,1987.10.I.L.Finar,“Organicchemistry”Vol2(3rdEdition),LongmansGreenandCompany,1964.11.R.J.Simmonds,“Chemistryofbiomolecules:Anintroduction,”RoyalSocietyofChemistry,1992.12.J.Mann,J.HarborneandR.S.Davidson,“Naturalproducts:Theirchemistryandbiologicalsignificance,”

Longman,199413.G.R.Chatwal,Organicchemistryofnaturalproducts,Vol1and2,HimalayaPublishingHouse,2011.14.A.Kar,“Medicinalchemistry,”NewAgeInternational,2005.15.N.R.Krishnaswamy,“Chemistryofnaturalproducts:Aunifiedapproach,”UniversitiesPress,1999.16.N.R.Krishnaswamy,“Chemistryofnaturalproducts:Alaboratoryhandbook,”CRCPress,2012.17.K.G.Krebs,D.HeusserandH.Wimmer,“Sprayreagents”(availableonline).18.J.B.Harborne,“Phytochemicalmethods,”SpringerScience,1998.

20

19PCH23: PHYSICAL CHEMISTRY –II

Total 90 h

Course Outcome: CO1.UnderstandthetheoryandinstrumentationofNMR,ESR,NQR,PESspectroscopictechniques.CO2.Interprettheabovespectroscopicdataofunknowncompounds.Usethesespectroscopictechniquesintheir research. CO3.Toknowthebasicconcepts inclassical thermodynamicsandto learn the thermodynamicaspectsofvariousprocessesandreactions.CO4.Tounderstandthedifferentaspectsofstatisticalthermodynamicsanditsapplications.CO5.Writeequations representingelectrochemicalcell, explainvariousoverpotential involvedduring theoperation of the cell. CO6.Calculateelectrochemicalcellparameters,electrochemicalactivesurfacearea,currentandoverpotentialundergivencondition,amountofcorrosionanditsrate.CO7.SolveproblemsbasedonDebye-Huckellimitinglaw.

Unit IQuantum Chemistry II 18 hRotationalmotion:Cartesianandsphericalpolarcoordinates.Thewaveequationinsphericalpolarcoordinates-particleonaring,thephiequationanditssolution,wavefunctionsintherealform.Non-planarrigidrotor(orparticleonasphere)-separationofvariables,thephiandthethetaequationsandtheirsolutions,Legendreand associated Legendre equations, Legendre and associated Legendre polynomials. Spherical harmonics(imaginaryandrealforms)-polardiagramsofsphericalharmonics.Quantum Mechanics of Hydrogen-like systems-Potential energy of hydrogen-like systems. The waveequationinsphericalpolarcoordinates:separationofvariables-R,thetaandphiequationsandtheirsolutions,wavefunctionsandenergiesofhydrogen-likesystems.Orbitals-radialfunctions,radialdistributionfunctions,angularfunctionsandtheirplots.

Unit II: Classical Thermodynamics 18 hEntropy-dependenceofentropyonvariablesofasystem(S,TandV;S,TandP).Thermodynamicequationsofstate.Criteriaforequilibriumandspontaneity,Euler’srelation,GibbsandHelmholtzfreeenergy,Maxwellrelations and significance, temperature dependence of free energy, Gibbs Helmholtz equation and itsapplications.Partial molar quantities: chemical potential, Gibbs-Duhem equations, determination of partial molarproperties–partialmolarvolumeandpartialmolarenthalpy.Fugacity-relationbetweenfugacityandpressure,determinationoffugacityofarealgas,variationoffugacitywithtemperatureandpressure.Fugacityofliquidmixtures,fugacityofmixtureofgases,LewisRandallrule.Activity,activitycoefficients,dependenceofactivityontemperatureandpressure.DeterminationofactivityandactivitycoefficientsofelectrolytesandnonelectrolytesThermodynamicsofmixing,Duhem-Margulesequation,Konowaloff’srule,Henry’slaw,excessthermodynamicfunctions-Determinationofexcessenthalpyandvolume.Chemicalaffinityandthermodynamicfunctions,effectoftemperatureandpressureonchemicalequilibrium-van’tHoffreactionisochoreandisotherm.

Unit III Spectroscopy II 18 hResonance spectroscopy: Nuclear Magnetic resonance Spectroscopy, Nuclear spin.Interaction betweennuclearspinandappliedmagneticfield.ProtonNMR.Populationofenergylevels.Nuclearresonance.Chemicalshift.Relaxationmethods.Spin-spincoupling.Finestructure.Elementaryideaof2Dand3DNMR.Introductiontoinstrumentation.ESR spectroscopy:Electronspin.Interactionwithmagneticfield.Kramer’srule.Thegfactor.Determinationofgvalues.Finestructureandhyperfinestructure.ElementaryideaofENDORandELDOR.Mossbauer spectroscopy:Basicprinciples.Dopplereffect,chemicalshift,recordingofspectrum,application.Quadrupoleeffect.NQR spectroscopy -PrincipleandapplicationPhotoelectron spectroscopy.IntroductiontoUVphotoelectronandX-rayphotoelectronspectroscopy.

21

Unit IV Statistical Mechanics –I 18 hMicrostates. Concept of ensembles Canonical and Grand canonical ensemble. Classical distribution ofparticles-MaxwellBoltzmanndistribution.Bose-Einsteinstatistics,Bose-Einsteindistribution.Thermodynamicprobability,BoseEinsteindistributionfunction. Examples of particles.Theory of Paramagnetism.Bose Einstein condensation, LiquidHelium.Supercooledliquid.Fermi-DiracStatistics.Fermi-Diracdistribution,examplesofparticlesFermi-Diracdistributionfunction.Thermionicemission.RelationbetweenMaxwellBoltzmann,BoseEinsteinandFermi-DiracStatistics.

Unit V Electrochemistry I 18 hIonics-Ionsinsolution.Deviationfromidealbehaviour.Ionicactivity.Ion-solventinteraction.Bornequation.Ion-ion interaction. Strong electrolytes Debye-Huckel theory of strong electrolytes,Onsager equation.LimitationofthemodelConductanceathighfrequenciesandhighpotentials–Weineffect—Activitycoefficientanditsdetermination.Ionic strength, Debye-Huckel limiting law. Equation for appreciable concentration. Osmotic coefficient.Activitiesinconcentratedsolutions.Ionassociations.Iontransport.Electrodics:Differenttypeofelectrodes.Originofelectrodepotential,Electrochemicalcells,Concentrationcellsandactivitycoefficientdetermination.Liquidjunctionpotential.evaluationofthermodynamicproperties,the electrode double layer, Electrode-electrodeinterface. Theory of multilayer capacity. Electrocapillarity.Lippmannpotentialandmembranepotential.Electro kinetic phenomena.Mechanismofchargetransferatelectrode-electrolyteinterface.Electrolysis.Current-potential curve.Dissolution,depositionanddecompositionpotentials.Energybarriers atmetal–electrolyte interface.Different typesofoverpotentials.Butler-Volmerequation.TafelandNernstequation.Ratedeterminingstepinelectrodekinetics.Thehydrogenandoxygenovervoltage.Theoriesofovervoltage.

References1. I.N.Levin,“QuantumChemistry”,PrenticeHall,NewJersey,Vthedn.,2000.2. D.A.McQuarrie,“QuantumChemistry”,VivaPublishers,NewDelhi,2003.3. M.W.Hanna,“QuantumMechanicsinChemistry”,Benjamin,NewYork-Amsterdam,1965.4. R.K.Prasad, “QuantumChemistry”,NewAge International (p)Limited-Publishers,NewDelhi, IVth

edn.,2009.5. C.N.Banwell,E.M.McCash,“FundamentalsofMolecular6. Spectroscopy”,TataMcGrawHill,NewDelhi,1994.7. G.Aruldhas,“MolecularStructureandSpectroscopy”,PrenticeHallofIndia,2ndedn.,2007.8. R.S.Drago,“PhysicalMethodsinChemistry”,SaundersCollege,2ndedn.,1992.9. P.S.Sindhu,”FundamentalsofMolecularSpectroscopy”,NewAgeInternational,2006.10.R.P.Rastogi,R.R.Misra,“AnIntroductiontoChemicalThermodynamics”,VikasPublishingHouse,6th

edn.,1995.11.J.Rajaram,J.C.Kuriakose,“Thermodynamics”,S.ChandandCo.12.I.Pregogine,“IntroductiontoThermodynamicsofIrreversibleProcess”,InterScience,3rdedn,.196713.M.C.Gupta,”ElementsofStatisticalthermodynamics”,NewAgeInternational.14.F.W.SearsandG.L.Salinger,“AnIntroductiontoThermodynamics,KineticTheoryofGasesandStatistical

Mechanics”,Addison-LesleyPublishing.15.C.Kalidas,M.V.Sangaranarayanan,“Non-equilibriumThermodynamics”,MacmillianIndia2012.16.McQuarrie,“StatisticalMechanics”,OrientLongman,2000.17.D.R.Crow,“PrinciplesandApplicationsofElectrochemistry”,BlackleAcademicandProfessional,4th

edn.,1994.18.J.O.M.BokrisandA.K.N.Reddy,“ModernElectrochemistry”,PlenumPress,1973.19.S.Glasstone,“IntroductiontoElectrochemistry”,D.VanNostrandCompany,1942.20.G.WCastellan,“PhysicalChemistry”,Addison-LesleyPublishing.21.P.W.Atkins,“PhysicalChemistry”,OxfordUniversityPress,1978.22.Puri,Sharma,Pathania,“PrinciplesofphysicalChemistry”Vishalpublishingcompany,2013.23.GurdeepRaj“AdvancedPhysicalChemistry”GOELPublishingHouse,Meerut,2004.

22

MODEL QUESTION PAPER19PCH21: INORGANIC CHEMISTRY-II

Time:3 h Max marks:75

SECTION-AAnsweranytwoamong(a),(b),and(c)fromeachquestion.Eachsub-questioncarries2marks.

1. a)Classifythefollowingascloso,nido,arachnoorhypho.1)B5H9 2)B5H11 3)B6H12 4)B9H15.b)Whichsulphur–nitrogencompoundisknownas‘one-dimensional’metal?Whyisitcalledso?c)WhyareP4N4Cl8puckeredandP4N4F8planar?

2. a)Howwouldyoudistinguishbetweenferromagneticandantiferromagneticmaterial?b)Explainnon-crossingrule.c)Theeffectivemagneticmomentofacomplexis4.90BM.Calculatetheno:ofunpairedelectronperunitcomplex.

3. a)WhatisthetypeofdefectobservedinAgBrcrystals?Why?b)Giveoneexampleeachformolecular,covalent,metallicandH-bondedcrystals.c)DifferentiatebetweenH-centreandV-centreinNaClcrystals.

4. a)Writeanytwodifferencesbetween4fand5forbitals.b)GivethetermsymbolsforEu3+andLu3+.c)ExplainwhyActinideshavegreatertendencyforcomplexformationthanlanthanides?

5. a)Whatisbandgap?b)Whatismeantbyorder-disordertransitions?c)Writeashortnoteonsintering.

[2x10=20marks]SECTION-B

Answereither(a)or(b)ofeachquestioncarries5marks.6. a)Howisdiboraneprepared?Discussthestructureandbondingindiborane.

b)Writeanoteonmetallocarboranes.7. a)DescribetheGuoy’smethodtodeterminemagneticsusceptibility.Howarethesemeasurementsused

tocalculateeffectivemagneticmoments?b) Even though d-d transitions are forbidden, why such transitions occur in many transition metalcomplexes?Illustratewithexamples.

8. a)Distinguishbetweenspinelsandinversespinelswithsuitableexamples.b)Writebrieflyonlineandplanedefectsinsolids.

9. a)Brieflydiscussthebasisoftheion-exchangemethodfortheseparationofLanthanides.b)ComparethespectralandmagneticpropertiesofLanthanidesandActinides.

10.a)Withsuitableexamplesexplainthephenomenonofmetalconductivity.b)Writeashortnoteontheapplicationsofferro,piezoandpyroelectrics.

[5x5=25marks]SECTION-C

Answeranythreequestionsandeachquestioncarries10marks.11.HowisBorazineprepared?Discussitsstructureandcomparethebondingwithphosphazenemolecule.12.Write an account on the selection rules and characteristics of d-d transition and application of each

electronicspectrainelucidatingthestructureofmetalcomplexes.13.Discussbrieflyonthepackingofatomsandionsinsolids.14.a)Correlatetheoxidationstatesandionicradiiwithelectronicconfigurationoflanthanides.

b)Writeashortnoteonthebeachsandsofkerala.15.Discussthesalientfeaturesofbandtheoryofsolidsandcompareitwiththefreeelectrontheoryofsolids.

[10x3=30marks]

23

MODEL QUESTION PAPER19PCH22: Organic Chemistry-II

Time-3 hours Maximum marks :75

Section AAnswer any two among a), b) and c) from each question.Eachsub-questioncarries,2marks.

1. a)Givethemechanismofrearrangementofarylhydroxylaminestoaminophenols.b)DescribeStevensrearrangement.c)Showthemechanisminvolvedintherearrangementofanunsubstitutedamidetoaprimaryamine.

2. a)Explainwhycyclodecapentaenewith10πelectronsisnotaromatic.b)WritebrieflyonHomoaromaticity.c)StateWoodwardHoffmannrules.

3. a)ExplainPhosphorescence.b)WriteashortnoteonNorrishtypeIreaction.c)Describeanyonemethodofgenerationofsingletoxygen.

4. a)ExplainvonBraunreaction.b)ShowtheproductsformedwhenQuercetinistreatedwithdimethylsulphatefollowedbyboilingwithethanolicKOH.c)DrawthestructureofCholesterol.

5. a)ExplainTaftequationb)Describesalteffectinsubstitutionreactionc)StateMarcustheory

[2x10=20 marks]Section B

Answer either a) or b) of each question, and each question carries 5 marks.6. a)DiscussthemechanismandapplicationsofBaeyerVilligerreaction.

b)DiscussthemechanismofBenzidinerearrangement.Alsowriteprooftosupportthemechanism.7. a)ExplaintheacidityofCyclopentadieneandCycloheptatriene.

b)ExplainbrieflyClaisenrearrangement.8. a)BrieflyexplainBartonreaction.

b)Explainthephotochemistryofolefins.9. a)DiscusthestructureelucidationofCarotene.

b)Brieflydescribethebiosynthesisofterpenes.10.a)Explainkineticandthermodynamiccontrolinreactionsinvolvingketones.

b)Explainthereasonforthedifficultyinthehydrolysisof2,6-disubstitutedbenzoicacidesters.[5x5=25 marks]

Section CAnswer any three questionsandeach questioncarries10marks.

11.i)DiscussthemechanismandapplicationsofBeckmannrearrangement.ii)DiscussthesimilarityintheintermediatesofCurtius,SchmidtandLossenrearrangements.

12.Explainbrieflyoni)Sigmatropicreactionsii)1,3-DipolarandEnereactions.

13.Discussthefollowing:i)Photochemistryofvisionii)PhotoreactionofVitaminD.

14.Explainthefollowing:i)StructureofEstrone.ii)Chemical,spectroscopicandchiropticalmethodsforestablishingcarbonskeleton. .

15.Discussthefollowing:i)Principlesandapplicationsofphasetransfercatalysis.ii)Methodsofdeterminationofreactionmechanism.

[10x3=30 marks]

24

MODEL QUESTION PAPER19PCH23: Physical Chemistry- II

Time : 3 Hours Max mark : 75

Section AAnswer any two among (a),(b) and(c) fromeachquestion.Each sub-divisioncarries2 marks.

1. a)SetuptheSchrodingerequationforarigidrotator.b)Giveplotsof(a)radialprobabilitydistributionfunctionsof2Sorbitaland(b)angularplotof2Px orbital.c)WritetheexpressionforFockoperatorandexplaintheterms

2. a)Definechemicalpotentialb)StateLewis–Randallruleoffugacityc)WriteKonowaloff’srule

3. a)WritetheexpressionforchemicalshiftinMossbauerspectroscopyandexplaintheterms.b)Calculate theESRfrequencyofanunpairedelectron inamagneticfield0.33Tesla.Given for freeelectrong=2,β=9.273×10-27J/Tc)ExplainthebasicprincipleofX-rayphotoelectronspectroscopy.

4. a)Deriveidealgaslawfromtranslationalpartitionfunction.b)Explainthetermcanonicalensemble.c)ElectronwouldneverfollowMaxwellBoltzmannstatistics.Why?

5. a)WhatisLippmannpotential?Howdoesitarise?b)Calculatethemeanactivitycoefficientof0.01MBaCl2inwaterat25

oC.c)Explaintheoriginofconcentrationoverpotential.

(10X2=20Marks)Section- B

Answer either (a) or (b) ofeachquestionandeachquestioncarries5 marks6. a)Explainself-consistentfieldmethodtosolvemanyelectronsystems.

b)WritetheSchrodingerequationforhydrogenatominpolarcoordinatesandseparatethevariables.7. a)Definefugacity.Writethemethodforthedeterminationoffugacityofagas

b)DeriveGibbsDuhemequation8. a)Writeabriefaccountof2D-NMRspectroscopy.

b)WhatisKramer’sdegeneracy?Discuss.9. a)ApplyFermi-Diracstatisticstounderstandparamagnetisminsolids.

b)Derivetheexpressionforpartitionfunctionforparticleexecuting(i)freelinearmotionand(ii)freelinearharmonicvibration.

10.a)DeriveDebye-Huckellimitinglaw.b)Discussthevariousmodelsforelectricaldoublelayer.

(5X5=25Marks)Section-C

Answer any three questionsandeach questioncarries10 marks11.(i)ApplySchrodingerequationforparticleinaring.Findeigenvaluesandeigenfunctions.

(ii)ShowthatanytwoassociatedLegendrefunctionssatisfyorthonormalitycondition.12.Writeabriefaccountofthemethodsforthedeterminationofactivitycoefficientofelectrolytesandnon

electrolytes13.ExplaintheprincipleandapplicationsofNQRspectroscopy.14.DerivetheexpressionforthedistributionfunctionofaBosonandBose-Einsteincondensation.15.(i)DeriveButler-Volmerequation.Deducetheexpressionforthelowandhighfieldlimitsofthisequation.

(ii)DiscusstheapplicationofDebye-HuckelOnsagarequationasappliedtostrongelectrolytesandpointout its limitations.

(10x3=30Marks)

25

SEMESTER III19PCH31: INORGANIC CHEMISTRY- III

Total 90 h

Course Outcome:CO1.Identifythestructureandbondingaspectsofsimpleorganometalliccompounds.CO2.Applydifferentelectroncountingrulestopredicttheshape/geometryoflowandhighnuclearitymetalcarbonyl clusters.CO3.Identifythedifferenttypesoforganometallicreactionsandapplytheaboveconceptstoexplaindifferentcatalytic reactions.CO4.Toknowtheimportantreactionsofcoordinationcompounds.CO5.Togetaninsightintotheroleofessentialandtraceelementsinbiologicalsystemsandunderstandthemechanismofphotosynthesis,respirationetc.CO6.Usevariousspectroscopicprinciplestocharacterizeinorganicandorganometalliccompounds.CO7.Toimpartessentialtheoreticalknowledgeonnuclearchemistry.

Unit I Organometallic compounds 18hNomenclatureoforganometalliccompounds.Haptonomenclature.18and16electronrule,isoelectronicandisolobalanalogy.Typesofmetalcomplexes.Metalcarbonyls,bondinginmetalcarbonyls.Bondinginmetalnitrosylsandcyanides.Synthesis,structureandbondingofpolynuclearcarbonylswithandwithoutbridging.Complexeswithlinearπdonorligands:Olefins,acetylenes,dienesandallylcomplexes.Complexeswithcyclicπdonors:Cyclopentadiene,benzenecomplexes,structureandbondingofferroceneanddibenzenechromiumcomplexes(MOtreatment).Oxidativeadditionandreductiveelimination,insertionandeliminationreactionsCatalysisbyorganometalliccompounds:Alkene hydrogenation usingWilkinson’s catalyst, hydroformylation of olefins using cobalt catalyst andpolymerizationreactionbyZiegler-Nattacatalyst.Fluxionalmolecules.

Unit II Coordination chemistry-III: Reactions of metal complexes 18 hEnergy profile of a reaction -Thermodynamic and kinetic stability, Stability of complex ions in aqueoussolutions: Formation constants. Stepwise and overall formation constants. Factors affecting stability ofcomplexes. Determination of stability constants: spectrophotometric, polarographic and potentiometricmethods. Stability of chelates.Thermodynamic explanation,macrocyclic effects.Classification of ligandsubstitutionreactions-kineticsandmechanismofligandsubstitutionreactionsinsquareplanarcomplexes,transeffect-theoryandsyntheticapplications.Kineticsandmechanismofoctahedralsubstitution-waterexchange,dissociative mechanism, associative mechanism- Eigen-Wilkins mechanism, Eigen-Fuoss equation, basehydrolysis,racemisationandisomerisationreactions.Electrontransferreactions:Outerspheremechanism-Marcustheory,innerspheremechanism-Taubemechanism.Photochemicalreactions-substitutionandredoxreactionsofCr(III),Ru(II),andRu(III)complexes.Photo-isomerisationandphoto-aquationreactionsofmetalcomplexes.

Unit III Bioinorganic chemistry 18 hEssential and trace elements in biological systems, structure and functions of biological membranes,mechanism of ion transport across membranes, sodium-potassium pump. Photosynthesis, porphyrin ringsystem,chlorophyll,PSIandPSII.Syntheticmodelforphotosynthesis.Roleofcalciuminbiologicalsystems.Oxygencarriersandoxygentransportproteins-haemoglobinandmyoglobin.Non-haemeiron-sulphurproteinsinvolved in electron transfer-ferredoxin and rubredoxin. Iron storage and transport in biological systems-ferritin and transferrin. Redox metalloenzymes-cytochromes, peroxidases and superoxide dismutase andcatalases.Nonredoxmetalloenzymes-CarboxypeptidaseA-structureandfunctions.Nitrogenases,biologicalnitrogenfixation.VitaminB12andcoenzymes.Toxiceffectsofmetals(Cd,Hg,CrandPb).

Unit IV Spectroscopic Methods in Inorganic Chemistry 18 hInfraredspectraofcoordinationcompounds.Structuralelucidationofcoordinationcompoundscontainingthefollowingmolecules/ionsasligands-NH3,H2O,CO,NO,OH

-,SO42-,CN-,SCN-,NO3

-,NO2-,CH3COO

-andX-(X=halogen).Changesinligandvibrationoncoordinationwithmetalions. Vibrational spectra of metal carbonyls- CD and ORD spectra of metal complexes.

26

ESRspectra:ApplicationtoCu(II)complexesandinorganicfreeradicalssuchasPH4,F-and[BH3]

-. Nuclear Magnetic Resonance Spectroscopy: The contact and pseudocontact shifts, some applications includingbiologicalsystems,anoverviewofNMRofmetalnuclideswithemphasisonP-31andF-19NMR.MossbauerSpectroscopy:Applicationofthetechniquetothestudiesofironandtincomplexes.

Unit IV Nuclear chemistry 18 hFissionproductsandfissionyield.Neutroncapturecrosssectionandcriticalsize.Nuclearfusionreactionsandtheirapplications.Chemicaleffectsofnucleartransformations.Positronannihilationandautoradiography.PrinciplesofcountingtechniquesuchasG.M.counter,proportional,ionizationandscintillationcounters.Cloudchamber.SynthesisoftransuranicelementssuchasNeptunium,Plutonium,Curium,Berkelium,Einsteinium,Mendelevium,Nobelium,Lawrenciumandelementswithatomicnumbers104to109.Analyticalapplicationsof radioisotopes-radiometric titrations, kinetics of exchange reactions,measurement of physical constantsincludingdiffusionconstants,Radioanalysis,NeutronActivationAnalysis,PromptGamaNeutronActivationAnalysisandNeutronAbsorptiometry.Applicationsofradioisotopesinindustry,medicine,autoradiography,radiopharmacology, radiation safety precaution, nuclearwaste disposal.Radiation chemistry ofwater andaqueous solutions.Measurement of radiation doses.Relevance of radiation chemistry in biology, organiccompoundsandradiationpolymerization.

References1. F.A.CottonandG.Wilkinson,AdvancedInorganicChemistry,JohnWileyandSons,6thedition,1999.2. J.E.Huheey,InorganicChemistry-PrinciplesofStructureandReactivity,HarperandCollins,4thedition,

2011.3. E.A.V.Ebsworth,D.W.H.RankinandS.Cradock,StructuralmethodsinInorganicChemistry,Blackwell,

Oxford,1987.4. K.Nakamoto,InfraredandRamanSpectraofInorganicandCoordinationCompounds,JohnWiley,3rd

edition,1978.5. R.V. Parish, NMR,NQR, EPR andMossbauer Spectroscopy in Inorganic Chemistry, Ellis Harwood,

Chichester,UK1999.6. G.FriedlanderandJ.W.Kennady,IntroductiontoRadiochemistry,JohnWileyandSonsNewYork,1949.7. H.J.Arnikar,EssentialsofNuclearChemistry,NewAgeInternational,NewDelhi,4thedition,1995.8. F.BasaloandR.G.Pearson,MechanismofInorganicReactions,JohnWileyandSons,NewYork,1967.9. R.W.Hay,BioinorganicChemistry,EllisHorwood,Chichester,1987.10.P.Powell,PrinciplesofOrganometallicChemistry,ChapmanandHall,2ndEdition,NewYork,1988.11.S.J.LippardandJ.M.Berg,PrinciplesofBioinorganicChemistry,UniversityScienceBooks,MillValley,

California,1994.12.D.E.Fenton,BiocoordinationChemistry,OxfordUniversityPress,Oxford,1995.13.R.C.MehrothraandA.Singh,OrganometallicChemistry:AUnifiedApproach,Wileyeastern,1991.14.D.F.Shriver,P.W.AtkinsandC.H.Langford, InorganicChemistry,ELBS,OxfordUniversityPress,

1990.15.L.Bertin,H.B.Gray,S.J.lippardandJ.S.Valentine,BioinorganicChemistry,VivaBooksPvt.Ltd,New

Delhi,1998.16.S.N.Goshal,NuclearPhysics,S.ChandandCompany,2006.

19PCH32: ORGANIC CHEMISTRY-III

Total 90 h

Course Outcome:CO1.ApplyNMR,IR,MS,UV-Visspectroscopictechniquesinsolvingstructureoforganicmoleculesandindeterminationoftheirstereochemistry.CO2.Interprettheabovespectroscopicdataofunknowncompounds.CO3.Usethesespectroscopictechniquesintheirresearch.CO4.Tounderstandtheconceptofvariousorganicsyntheticreactionsanddifferentseparationtechniquesandits use in research.

27

Unit I UV-Vis and IR Spectroscopy and Mass spectrometry 18hElectronictransitionsandanalysisofUVspectraofenes,enonesandarenes.Woodward-Fieserrules.Effectof solvent polarity onUV absorption. Principle of characteristic group frequency in IR. Identification offunctionalgroupsandotherstructuralfeaturesbyIR,HydrogenbondingandIRbands.Samplingtechniques.Massspectrometry-EI,CI,FAB,ElectrosprayandMALDIionsources.Magnetic,Highresolution(Doublefocusing), TOF and quadrupole mass analysers. Characteristic EIMS fragmentation modes and MSrearrangements.Massspectralfragmentationpatternsoflongchainalkanes,alkenes,alkynes,alcohols,ethers,thiols,aromaticcompounds,aldehydes,ketones,acids,amides,nitro,aminoandhalocompounds.

Unit II NMR spectroscopy and structural elucidation 18hTheoryofNMRspectroscopy,chemicalshifts,anisotropiceffectsandcouplingconstant.Spin-spininteractionsintypicalsystems.Firstorderandhigherorderspectra.SimplificationmethodsofcomplexspectrabyhighfieldNMR,shiftreagents,chemicalexchangeanddoubleresonance.13C NMR chemical shifts. Applications ofNOE,DEPT,and2DtechniquessuchasCOSY,HSQC,HMQCandHMBC.Spectralinterpretationandstructuralelucidation.Solvingofstructuralproblemsonthebasisofnumericalandspectrumbaseddata.

Unit III Organic synthesis 18 hC-CandC=Cbondformingreactions.Mannich,Reimer-Tiemann,Synthesisofsmallrings.Simmons-Smith,Vilsmeier-Haack,UllmannandChichibabinreactions.RingformationbyDieckmann,Kostanecki,Thorpe,Pschorr and acyloin condensations. Stork enamine, Shapiro, Peterson,Heck, Stille, Ritter and Prilezhaevreactions. Reduction and oxidation in synthesis. Catalytic hydrogenation. Alkali metal reduction, Birchreduction,ClemmensenreductionandWolff-Kishnerreduction,Huang-Minlonmodification.Boranes,LAHandsodiumborohydrideasreductants.Hydrogenation,Oppenaueroxidation,Jonesoxidation.ApplicationsofHIO4,OsO4andmCPBA.Organopalladiumcatalysts-Heck,Negishi,SonagashiraandSuzukicoupling

Unit IV Methods in organic synthesis 18 hRetrosynthetic analysis and disconnection approach. Synthetic strategy and synthons. Regioselectivity inenolandenaminealkylation.Stereospecificandsteroselectivesynthesis,Sharplessasymmetricepoxidation,Chiralpool,chiralauxiliary,Chiral reagents,BINAP,Mitsunobureaction.1,3-dipolarcycloaddition in theconstructionofrings.Olefinsynthesisbyextrusionreactions.Olefinmetathesis–firstandsecondgenerationGrubbs’catalysts.Umpolungconcept,functionalgroupequivalents.Reductivecouplingreactions.Epoxideto alkene.Introduction to combinatorial synthesis. Electrochemical reduction of organohalogen, nitro andcarbonylcompounds.ElectrochemicalKolbeoxidation.Protectinggroupstrategy:Tetrahydropyranyl,silyl,t-butyl, trichloroethyl,acetaland thioacetalashydroxyl, thiol,carboxylandcarbonylprotectinggroups insynthesis.

Unit V Reagents in organic synthesis 18hApplications of hydrogenation catalysts, hindered boranes, bulky metal hydrides. NaCNBH3 DIBAL, Litrialkylborohydrides,tri-n-butyltinhydride,diimide,Lindlarcatalystsandaluminiumalkoxide.RosenmundreductionandMcFadeyan-Stevensreaction.OxidationusingSeO2,leadtetraacetate,ozone,peracids,DDQ,manganese(IV)oxide,silvercarbonateandCr(VI)reagents.Swernoxidation,Moffattoxidation,allylicandbenzylicoxidation.Sommeletreaction.Elbsreaction.Oxidativecouplingofphenols.Chemoandregioselectivityinreductionsandoxidations.

References1. D.H.WilliamsandI.Fleming,“Spectroscopicmethodsinorganicchemistry,”6thEdition,TataMcGraw

Hill,20112. W.Kemp,“Organicspectroscopy,”3rdEdition,PalgraveMacmillan,19913. D.L.Pavia,G.M.Lampman,G.S.KrizandJ.A.Vyvyan,“IntroductiontoSpectroscopy,”4thEdition,

BrooksCole,2008.4. S.N.Issacs,“Physicalorganicchemistry,”PrenticeHall2ndedition,1996.5. R.A.Y.Jones,“Physicalandmechanisticorganicchemistry,”CambridgeUniversityPress,1979.6. J.Hine,“Physicalorganicchemistry,”2ndEdition,McGraw-Hill,19627. M.B.Smith,“March’sadvancedorganicchemistry,”7thEdition,Wiley,2013.8. H.O.House,“Modernsyntheticreactions,”2ndRevisedEdition,BenjaminCummins,1965.

28

9. R.K.Mackie,D.M.AmithandR.A.Aitken,“Guidebooktoorganicsynthesis,”2ndEdition,LongmanScientificandTechnical,1990.

10.W.Carruthers,“Modernmethodsinorganicsynthesis,”3rdEdition,CambridgeUniversityPress,1987.11.J.SinghandL.D.S.Yadav,“OrganicSynthesis,”PragatiPrakashan,2010.12.J.Clayden,N.Greeves,andS.Warren,“OrganicChemistry,”2ndEdition,OxfordUniversityPress,2012.13.D.A.Skoog,D.M.WestandF.J.Holler,“Fundamentalsofanalyticalchemistry,”9thEdition,Brooks

Cole,2013.14.D.J.HolmeandH.Perk,“AnalyticalBiochemistry,”3rdEdition,PrenticeHall,1998.

19PCH33: Physical Chemistry -III

90 h

Course Outcome:CO1.Tounderstandtherequirementofapproximationmethodsinquantummechanics.CO2.Togaintheknowledgetoapplyimportantapproximationmethodstoproblemsinquantummechanics.CO3.TogaininsightintovalancebondtheorymolecularorbitaltheoryandtheconceptofhybridisationCO4.TogetanexposuretotheemergingworldofcomputationalchemistryCO5.Tohaveabasicideaaboutcomputationalchemistrycalculations.CO6.Calculatechangeinthermodynamicproperties,equilibriumconstants,partialmolarquantities,chemicalpotential. CO7.Identifyfactorsaffectingequilibriumconstant.CO8.Applyphaseruleand,drawphasediagramsforone,andtwocomponentsystems,identifythedependencyoftemperatureandpressureonphasetransitions,andidentifyfirst/secondorderphasetransitions.CO9.Solveproblemsbasedonpartitionfunctions.CO10.Calculateexcessthermodynamicproperties.CO11.Tounderstandtheprincipleandapplicationsvariouselectroanalyticalandspectrophotometricmethods.

Unit I Chemical Bonding 18 hApproximatemethods:method ofVariation -Variation theorem and its proof.Linear variation functions.Secular equations and secular determinants.Perturbation method-Successive correction to an unperturbedproblem.Detailedtreatmentoffirstordernon-degeneratecaseonly.Waveequationformultielectronsystems. Hartree-Fock Self- Consistent Field (HF-SCF)method for atoms,Hartree-Fock equations (derivation notrequired)&theFockoperator.Treatment of molecules-TheBorn-Oppenheimer approximation-LCAO-MOTheory-MO theoryofH2andH2

+.MOtreatmentofotherhomodiatomicmoleculesLi2,Be2,B2¸ C2,O2andF2. MO treatment of hetero diatomicmoleculesLiH,CO,NOandHF.Spectroscopictermsymbolsforhomodiatomicmolecules.Valance bond theory ofdiatomicmoleculesH2,O2andF2.ComparisonofMOandVBtheories,Quantummechanicaltreatmentofsp,sp2andsp3 Hybridisation.HMOtheoryofconjugatedsystems.Bondorderandchargedensitycalculations,Freevalance.ApplicationofHMOmethodtoethylene,allylsystem,butadieneandbenzene.

Unit II Computational Chemistry 18 hIntroductiontocomputationalchemistry:asatoolanditsscope.Potentialenergysurface-stationarypoint,saddle point or transition state, local and globalminima.Slater andGuassian functions and its properties.Basis sets :minimal,doublezeta, triple zetabasis sets, contractedbasis sets,Pople’s stylebasis sets andtheirnomenclature.Basisfunctions-Roothan’sconcept,Slatertypeorbitals(STO)andGaussiantypeorbitals(GTO).SlaterdeterminantsQuantum mechanical computational methods-Abinitiomethods:IntroductiontoSCF.Wavefunctionsforopenshellstate,RHF,ROHFandURHF.(nocalculation).ElectroncorrelationandintroductiontopostHFmethods.Semiempiricalmethods.HuckelsandextendedHuckelmethods.Strengthsandweaknesses.PPP,ZDOandCNDOapproach.(Mentioningonly).Density functional theory-Hohenberg-Kohn theorems,Exchange correlational functional. (Only thebasicprinciplesandtermstobeintroduced).

29

Non-quantum mechanical computational methods-Molecularmechanics: Force fields, bond stretching,angle bending, torsional terms, non-bonded interactions, electrostatic interactions and the correspondingmathematicalexpressions.Namesofsomecommonlyusedforcefields.Construction of Z-matrix for simple molecules. H2O,H2O2,H2CO,CH3CHO,NH3andCO2.

Unit III Applications of Thermodynamics 18 hThermodynamics of irreversible processes:Simpleexamplesofirreversibleprocesses.GeneraltheoryofnonequilibriumprocessesThephenomenologicalrelations.Onsagerreciprocalrelation.Generalizedequationfor entropy production, Entropy production from heat flow,matter flow and current flow.Application ofirreversiblethermodynamicstodiffusion.Thermaldiffusion,Thermoosmosisandthermomolecularpressuredifference.Electrokineticeffects,theGlansdorf-Pregogineequation.Farfromequilibriumregion.Principleofminimumentropyproduction,Le-ChatelierBra(u)wnPrinciple.Three component systems: Graphical representation. Three component liquid systems with one pair ofpartiallymiscibleliquids.Influenceoftemperature.Systemswithtwopairsandthreepairsofpartiallymiscibleliquids.Solid- Liquid systems:Twosaltsandwatersystems-nochemicalcombination,doublesaltformation,onesaltformsahydrate,doublesaltformshydrate,Isothermalevaporation.

Unit IV Statistical Mechanics II 18 hMolecularpartitionfunctions.Translational(1D,2Dand3D),vibrational,rotationalandelectronicpartitionfunctions.TotalpartitionfunctionsLangevinfunctionanditsuseforthedeterminationofdipolemomentandmolecular energiesRelationshipbetweenPartitionfunctionsand thermodynamicproperties,Theprincipleofequipartitionofenergy.Chemicalequilibrium.Lawofmassaction.Transformationoftheequilibriumexpressions.Statisticalderivation.Thermodynamicprobabilityandentropy.EquipartitionprincipleQuantumtheoryofheatcapacity.Calculationofheatcapacityofgases,limitationofthemethod.Heatcapacityofsolids.DulongandPetit’slaw,Kopp’slaw,Classicaltheoryanditslimitation.Thevibrationalpropertiesofsolids.Einsteintheoryofheatcapacity.Thespectrumofnormalmodes.LimitationsofEinstein’stheory.TheDebyetheory,theelectronicspecificheat.

Unit V Electro Analytical and Spectrophotometric methods. 18 hPotentiometric methods:Reference electrodes and indicator electrodes.Thehydrogen,calomel,Ag-AgClelectrode.Theglasselectrode-itsstructure,performanceandlimitations.MeasurementofpH.Potentiometrictitrations-redoxandprecipitationtitrations.Electrogravimetry:Principleandmethod.DeterminationofCopper.Separationofmetalions.Conductometry:Principleandmethod.Conductometrictitrations.Coulometry: Principleandmethod.Coulometrictitrations.Voltametry: principle and method of polarography, cyclicvoltammetry, stripping voltammetryandamperometry.Flame emission and atomic absorption spectrometry. InstrumentationforAAS.Theflamecharacteristics.Atomiserusedinspectroscopy.Hollowcathodelamp.InterferenceinAAS.ApplicationofAAS.

References1. I.N.Levin,“QuantumChemistry”,PrenticeHall,NewJersey,5thedn.,2000.2. D.A.McQuarrie,“QuantumChemistry”,VivaPublishers,NewDelhi,2003.3. M.W.Hanna,“QuantumMechanicsinChemistry”,Benjamin,NewYork-Amsterdam,1965.4. R.K.Prasad, “QuantumChemistry”,NewAge International (p)Limited-Publishers,NewDelhi, IVth

edn.,2009.5. T.Engel,“QuantumChemistryandSpectroscopy”,PearsonEducationIIIrdedn,2012.6. P.W.Atkins, R.S.Friedman, “Molecular QuantumMechanics”, Oxford UniversityPress, Oxford, IVth

edn.,2005.7. J.PLowe,K.Peterson,“QuantumChemistry”,AcademicPress,IIIrdedn.,2006.8. E.Lewars, “ComputationalChemistry- Introduction to theTheory andApplicationsofMolecular and

QuantumMechanics”,KluwerAcademicPublishers,NewYork,2004.9. D.Young,”Computational Chemistry”, A Practical Guide for Applying Techniques to Real-World

Problems”,JohnWiley&Sons.Inc.,Publication,NewYork,2001.

30

10.C.N.Banwell,E.M.McCash,“FundamentalsofMolecularSpectroscopy”,TataMcGrawHill,NewDelhi,1994

11.G.Aruldhas,“MolecularStructureandSpectroscopy”,PrenticeHallofIndia,2ndedn.,2007.12.R.S.Drago,“PhysicalMethodsinChemistry”,SaundersCollege.2ndedn.,1992.13.W.Kemp,“NMRinChemistry”,McMillan,London1986.14.F.W.SearsandG.L.Salinger,AnIntroductiontoThermodynamics,KineticTheoryofGasesandStatistical

Mechanics”,Addisonwisely,1963.15.L.K.Nash,“ElementsofStatisticalThermodynamics”,AddisonWesleyPublishingCo.1965.16.McQuarrie,“StatisticalMechanics”,OrientLongman,2008.17.G.WCastellan,“PhysicalChemistry”,Addison-LesleyPublishing.18.P.W.Atkins,”PhysicalChemistry”,OxfordUniversityPress.19.B.Widom,StatisticalMechanics–AconciseIntroductionforChemists.CambridgeUniversityPress.20.D.Chandler.IntroductiontoModernStatisticalMechanics,OxfordUniversityPress.21.D.A.Skoog,D.M.WestandF.J.Holler,”FundamentalsofAnalyticalChemistry”SaundersCollege.22.Puri,Sharma,Pathania,”PrinciplesopfphysicalChemistry”Vishalpublishingcompany.23.GurdeepRaj“AdvancedPhysicalChemistry”GOELPublishingHouse,Meerut.24.F.W.SearsandG.L.Sailinger”Thermodynamics,KineticTheory,andStatisticalThermodynamics”Third

edition.NarosapublishingHouse,NewDelhi.

19PCH34: Inorganic Chemistry Practicals -II

Total-125 h

Course Outcome:CO1.Enable the students to estimate the binarymixtures ofmetallic ions by volumetric and gravimetricmethodsCO2.Toacquiretheskilltoanalysesomecommonalloysandores.

1. Estimationofsimplemixtureofions(involvingquantitativeseparation)byvolumetricandGravimetricmethods.

2. Analysisoftypicalalloysandores3. Ionexchangeseparationofbinarymixtures.4. SpectralInterpretationofmetalcomplexesusingIR,UV-Vis.spectraldata.Supplementaryinformation

like metal estimation, CHN analysis, conductivity measurements and magnetic measurements to beprovidedtothestudents.AssessmentisbasedonarrivingatthestructureofthecomplexandassignmentofIRspectralbands.

5. InterpretationofTGandDTAcurvesofmetaloxalatehydrates.Assessmentisbasedontheidentificationofvariousstages.

References1. A.I.Vogel,ATextBookofQuantitativeinorganicAnalysis,Longman,4thedition,1978.2. A.I.WeiningandW.P.Schoder,TechnicalMethodsofOreanalysis,11thedition,1954.3. W.R.SchoderandA.R.Powell,AnalysisofMineralsandOresofRareElements,3rdedition,1956.4. Willard,MerritandDean,InstrumentalMethodsofAnalysis,7thedition,1986.5. W.W.Wendlandt,ThermalMethodsofAnalysis,Inter-Science,NewYork,1964.6. B.A.SkoogandD.M.west,PrinciplesofInstrumentalAnalysis,SaundersCollege,4thedition,1991.7. R.S.Drago,PhysicalMethodsinInorganicChemistry,VanNostrand,1992.8. K.Nakamoto, Infrared andRamanSpectra of Inorganic andCoordinatonCompounds, JohnWiley&

Sons,6thedition,2008.9. E.A.O.Ebsworth,Structuralmethodsinchemistry,BlackwellScientificPublications,2ndedition,1991.10.D.F.Shriver,P.W.AtkinsandC.H.Langford,InorganicChemistry,ELBS,1990.11.A.K.Galway,ChemistryofSolids,ChapmanandHall,1967.12.N.B.Hanna,SolidStateChemistry,PrenticeHall,1967.

31

19PCH35: ORGANIC PRACTICALS-II

Total 125 h

Course Outcome:CO1.TogaintheskilltoprepareorganiccompoundsusinggreenerprotocolsCO2.Enablethestudentstoprepareorganiccompoundsviatwostepsyntheticsequences•Toknowaboutenzyme/coenzymecatalysedreactions

A. Volumetric estimation of1)Aniline2)Phenol3)glucose4)Ascorbicacid5)AspirinB. Colorimetric estimation6)paracetamolwithpotassiumferricyanide7)proteinbybiuretmethod8)Ascorbicacidbyfolin-phenolreagentorphosphortungsticacidmethodsC. Spectral identification9)UV, IR,1HNMR,13CNMR,EImass spectral identificationofOrganiccompounds froma libraryof

organiccompounds(Eachstudentshavetorecordthespectralanalysisofaminimumof40compounds)D. Separations of mixtures by Paper Chromatography10)IdentificationofaminoacidsE. Single stage preparation of organic compounds by green chemistry11)Preparationofp-bromoacetanilideusingCAN12)Radicalcoupling–1,1-Bis-2-napthol13)Synthesisofdihydropyrimidinone14)Synthesisofdibenzalacetone-withlithiumhydroxide15)Photoreductionofbenzophenonetobenzopinacol(notforendsemesterevaluation) Theboardofexaminershavetochoosethecombinationofavolumetricestimation,acolorimetricestimation, agreen synthesisORpaper chromatographyand spectral analysis.Thechoiceof experimentsshouldchangeeveryyear.

References1. B.S.Furniss,“Vogel’stextbookofpracticalorganicchemistry,”5thEdition,Longman,1989.2. D.L.Pavia,G.M.Lampman,G.S.KrizandR.G.Engel,“Amicroscaleapproachtoorganiclaboratory

techniques,”WadsworthPublishing,5thEdition,2012.3. R.K.Bansal,“LaboratorymanualoforganicChemistry,”WileyEastern,19944. N.K.Vishnoi,“AdvancedPracticalOrganicChemistry,”3rdEdition,Vikas5. F.G.MannandB.C.Saunders,“PracticalOrganicChemistry,”PearsonEducation,20096. J.B.Cohen,“Practicalorganicchemistry,”ForgottenBooks,20157. P.FShalz,Journal of Chemical Education1996,173:267.8. Monographongreenlaboratoryexperiments,DST,GovernmentofIndia,pp1-79.9. Forspectraldataoforganiccompounds,see:http://sdbs.riodb.aist.go.jp/sdbs/cgi-bin/direct_frame_top.

cgi

19PCH36: PHYSICAL PRACTICALS –II

125 h

Course Outcome:Enable the students to determine the various physical properties using simple instrumentalmethods likepolarimetry,refractometryetc.

ConductometryDeterminationofstrengthofstrongandweakacidsinamixtureDeterminationofstrengthofaweakacid.Determinationofsolubilityproductofasparinglysolublesalt(PbSO4,BaSO4etc.)Hyd