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l-l8e ftpP'#,. (Abstract) \i.Sc Appliecl Chcmistrr,- syllabus under Choice based Credit Semester System I)rogramme with effect from 2O0B admissions - implemented - orders issued GENERAL AND ACADEMIC BRANCH - I J SECTION No. GA tlJ2i42sl2Oo8 Dated, Calicut University. P.O., 20.Al.2OO9. Read: 1. U.O.No.GAl /.lr I l373l08 dated Ol .07.2008 2. Item No.1 of the minutes of the meeting of the Board of Studies Applied Chemistry held on 27.O8.2OO8 in Item No.2 (xxxvi) of the minutes of the meeting of the Faculty of Science held on 29.O8.2OO8. 4. Item No.ll A(30) of the minutes of the meeting of the Academic Council held on 07.10.2008 ORDER As per paper read as 1 above Choice based Credit Semester System was introduced for all PG regular programmes in the Departments/Schools of this U niversity. The Board of Studies in Applied Chemistry vide paper read as 2 above, consiclered the s-vllabus (Semester I & II) of MSc Applied Chemistry (Choice based Credit Semester System) prepared by the Departmental Council, Department of Chemistry, University of Calicut in tune u.ith the regulations of the Choice based Credit Semester System programme & approved the sarne. The Facult_v- of Science vide paper read as 3 above, endorsed the same and \ w'hich was approved by the Academic Council vide paper read as 4 above. Sanction has therefore been accorded for implementing the syllabus of Ivl.Sc Applied Chemistry 1 and 2 Semesters with effect from 2008 admission. The syllabus has been appended. Orders are issued accordingly. sd/ASSTSTANT REGTSTRAR (G&A-I) For REGISTRAR. 'fo The Head of the Department of Chemistry, University of Calicut Copy to : 1. The Controller of Examinations/EX Section DR (PG) / Exam. Enquiry/ Information Centres/@ & A-l 'F' Sn./G&A III/ CCSS SN,DCMS/SF/FC ForwardedlBy order AQ?^v;Li SBCTION OFFICER l) \Rarnanr\(l&A l\.1 se(liorr\or(ler\a23 08 2l I 2009 tloc Courses ollbred for M Sc Applied Chcrnistry programme under CCSS (.ourse codt: 'fitle Type of thc course ir iir Credits Scnrester I ,-*i 1C0l ACI I C02 lnorganic Chenristry ncil rc03 Organic Chenristry I I I C10,1 Physical Chcnrislry Core J Core ) ;\.CI ACII ICO5 AClt lc06 ACII ICOT Scnrcstcr ,\cll Quantum Chenristry I I l)rar:tical lnorganic I Core 3 Core J Core ., ., l)ractical Organic I Corc l)ractioal I'hvsical I Core ) Crlrc -t Corc 3 2 2c08 Croup 'l'lrcory & Spcutrosct-rpy ACI I 2CO9 Inorganic Chemistry II ACI I 2C t0 Organic Chemistry ACII2CI l'hysical Chenristry I ACTI2CI2 ll ll Core J Core J I)ractical Inorganic II Core 2 ACll2Cl3 l)r'aclical Organio Il Core 2 Aclt 2cr4 l)raictical l'hysical I I Core 2 Scnrester 3 ACII3CI5 lnorganic Chemistry Core 3 ,,\CI I 3C I6 Organ)c Chernistry III Core 4 ACil 3Cr7 [)hysical Chcrnistry lll Core 3 Core 2 III ACI-I 3CIIJ Praclical : Instrunrental methods of Analysis ACII Computational Chcmistry E.lectivc 1 ACI I 3 tr02 lnstrumcntal mcthotls ol'Analysis 1'heory and lnstrumenlation lllective 4 ACI I 3EO3 Organr-rmctallic Chemistry Electivc 4 Acl l -lti0.l Chcnristry of Nano materials ElecLive 4 ACII 3E05 Solid state Chernistry Eler:tivc 4 ACI I 3lj06 Synthctic Organic Chemistry Illectivc ,1 Core lt 3DOI Sernester.{ ACll 4Cl9 Proj ccUDissertation nL-l I 4E07 l3 ACII lE0ti I)ioorganic Chcmistry ACI t 4809 Natural products ACI I 411l0 Industrial catalysis ACH 4Eu Chenr istry o l' Sl,nthetic Poll,nrer Dlcctivc 4 ACtt4El2 Chemistry Dlectivc 4 ACI I 4II I3 ioirrorganic Chemistly o Ele lNatural Polymer ctir e 4 lllcctivc .t ElecLive 4 Elective 4 Fuel Cells Elective 4 ACI 4ll l4 I'hamraceut ical Clrenristry Il]octive 4 ACI 4Ul5 Chenristry of Ceran.ric Materjals Electivc 4 ACI]4EI6 Crecn Chemistry Elcctive 4 ACI'i 4til7 Advanccd Synthcsis and Catalysis- New Synthetic Methodologies llleclive 4 Minimum credits required for a pass Core Courscs (othcr than proj ect/d issertation ) Elective Courses Proj ect/Di sscrtation 'fotal : : :8 -a1 . 4ti 16 lL For Morc Details: llead of the Departmcnt, Departnlent oi'Chcmistry Universityy of ol Calicrrt, Calic Calicut tJnivcrsity [Jnivcrsity P.O., I'].O., 673 635. 635. Kerala. -t- i UMVERSITY OF CALICUT M. Senrester Sc. Applied Chem.istry I Quantum Chemistry ACH IJNIT (3 Credits) 1COT I a) Mathematical concepts Co-ordinate systenr: Cartesian, cylindrical polar and spherical polar co-ordinates and their rclationships. Conrplex nunrbers: Definition, conrplex conjugate, Absolute value of a complex nunrber, contplex functions. Elenrents of operator algebra: Definition of an operator, Linear and nonlinear operators, 'Del' and 'del squared' operators and their expressions in cylindrical and spherical polar coordinates. Eigen flnction andEigen va.lues of an operator, Eigen value equation, Hernritian operators, Eigen functions of conrnruting operators, Well-behaved functions, normarlized and orthogonal 1unctions. b) Brief history of quantum mechanics Plank's quantunt Postulates, Einstein's quantunl theory of radiation, Explanation of plroto electric eff'ect, Milliken's verification of Einstein's photoelectric equation, wave-particle duality of radiation, wave particle duality of particles, de Broglie matter waves, Electron dithaction, Heisenberg's Matrix Mechanics (brief nrention), Schrodinger's wave mechanics, Deduction ofSchrodinger equation flonr classical wave equation. c) Formulation of quantum mechanics - The Postulates of quantum mechanics State function postulate, Operator postulate, Eigen value postulate, Expectation value postulate, Postulate of time dependent Schrodinger Equation of nrotion, Conservative slstenl and tinre-independent Schrodinger aluation, Stationary states, Formulation of a quantunt mechanical problem. UNIT II a) Quantum nrechanics of translational motion The particle in a one-dinrensional box-complete treatment. The particle in a three-dinrensional box (consider rectangular and cubic boxes), Separation of variables, Degeneracy, Symmetry breaking. Treatnrent of nrore than one particle (non-interacting) in a box. Introduction to Tunneling. b) Quantum Mechanics of vibrational motion Harmonic oscillator (complete treatnlent): Method of power series, Hermite equation and Hermite polynornials, Recursion fbrmula, Rodrigue's fbrnrula, Wave functions and energies, Important f'eatures of the problem, Harmonic oscillator and nrolecular vibrations, Threedinrensional harnroni c oscill ator. I.'MT III Quantunr Mechanics of rotational motion Rigid rotator (complete treatment): The wave equation in spherical polar coordinates. Planar rigid rotator (or Particle on a ring), The Phi-equation, Solution of the Phi-equation, Handling of Inraginary wave functions, Wave functions in the real fornr, Polar diagranu. Nonplanar rigid rotator (or particle on a sphere ), Separation of variables, The Phi-equation and the Theta-equation and their solutions, Legendre and Associated Legendre equations, Legendre and Associated Legendre polynontials, Spherical harmonics (Imaginary and real fornrs). Polar diagranu of spherical harnronics. Spherical harmonics as eigen functions of angular montentunl operators L2 and L., Quantization of angular momentun'I, Angular nromentum quantunl numbers, Space qu anti zati on. -o UNIT IV Quantunr Meclranics of Ilydrogen - Likc atonrs P<ltential energy ol'hydrogen-like systenrs. The wave ecluation in spherical polar cooldinatcs, Separal.ion ol varial'rles. The R, Theta and Phi equations and their soltrtions, Laguerre and Associated Laguerre polynonrials, Wave l'uncl.ions and energies ol' hydrogen-like atonrs, Olbitals. Radial lunctions and Radial distrihution lunctions and their pkrts, Angular l'unctions (Spherical harnronics) and their plots, Orhital diagrants. Explanation ol'IJydlogen spectrunr, Fine structure, 'fhe postulate ol-spin by Uhlenbcck and Goudsrrtith, Dirac's Relativistic Schlrxlinger equation lill hydrogen atom and discovery of spin, Flydrogen wave functions including spin or Spin orbitals, Construction of Spin orbiruls lionr Orbitals and Spin lirnctions. UNIT V Many-electron atonrs and approxirnation melhods Many-budy problern, Approxinratit)n nrefthods. Independent ;tarticle nrodel, Distribution of electrons in ntany electron atonrs, St<lner's rule. Variation ntethod, Variation the<lrenr witlr prootl lllustration of variation theorenr using a trial ttnction [e.9., x (a-x) | tbr particle in a lD-box, Variation treatnrent lbr the ground state ol' Ileliunt atonr, Efl-ective nuclear clrarge. Perturbation method, 'finre-independent perturbrtion nrethod (non-degenerate cirse only), Illustrttion by applicatiorr to particle in t lD-box with slanted bottonr, Peltur-bation treatnrent ol'l,lre glound state of the helitrnr atonr. I-Iartree-Iiock S el t-Consi stent Fi el d ([-IF-S CF) nrethod. Slater's treatment o1'conrplex atonrs, Slater Orbitals, Slater's rules lbr calculating Slatcr orbitals. UNIT VI ' Elcctron spin and atonric structurc Construction ol' wave tunctions including spin lir many electnrn atoms, Synrnretric and antisyntnretl'ic wave lunctions, Pauli's antisynlnletry principlc, Slatel deternrinants, Pauli's exclusion principle. Vector tnodel ()f fltoms and spectr<tscopic terrns Cotrpling of angular rnomenta, LS and jj- couplings, LS coupling and Spect-nlscopic ternt synrbols fbr aftrnt^s. Brief nrentiort of selection nrle in atonric spectroscol)y. Electronic sPectfunl of hydrogen atotu - the line stllrcture of H* line ol'theBalnrer series. The elcctlrnic spectr-unr ol'IIeliunt and Lithiunr ittonts- Brie[ discussion. UNIT YII Chenrical Bonding I i) Schr<ldinger ecluation lirr a nrolecule, Brlrn - C)ppenheinrer approxinration. ii) Molecular orbiral (MO) rheory MO theory of FIz*. MO theory ol'I'lz. MO treatnrent ol'honronuclear diatonric molecules Li2, Bez, Cz, Nz, Oz, Fz and hetero nuclear diatonric molecules LiH, CO, NO, HF. Correlation diagrants, Noncrossing rule. Spectroscopio ternr synrbols tbr diatonric molecules. iii) Valencc Bond (VB) thcory VB therxy of I{2. VB theory of nrore conrplex nroleculqs: Bonding in BeH2, H2O, NFI,, Orbital overlap. Molecular geonlet-ry, I-Iybridization, Exanrples: Methane, Water, Ethylene, and Acetylene, Multiple bonds, VSEPR theory. UNIT VIII Chcrnical llonding II i) MO theory fbr more conrplex nrolecules - HMO theory of linear conjugated hydrocarbons (Ethylene, Butadicne, Allylic anion), Charge on an atonr, bond order, Calculation of ti'ee valencc. IIMO theory of ar<>matic hydrociutons (benzene). Fornrula lilr the roots of Lhc lluckel deterrrtinarttal equation, Flost-I-Iuckcl cilcle nrnenronic device tbr cyclic: polyenes. hltermolecular I'6rces - Inter molecular lorces - ion dipole, dipole-dipole, ioninduced dipole, dipole-induced di;loie and dispersion interactions - rtathematical ii) expressions - donor-acceptor interactions - Lennard Jones porcntial. REFERENCES 1 . F.L. Pilar, Elententary Quulum Clwmistry, McGraw-Hill, 1968. 2. P.W. Atkins, Molecular qu(uilum nrcchanics,2"d Erlition, Oxfbrd University Press, 1983. 3. M.W. Hanna, Quanlunt ircclutnics in Chemistry,2"d Edition, W.A. Benjamin Inc., 1969. 4. I.N. Levine, Qutuilunt Chenisttl, 5'h Edition, Pearsou Education Inc., 2003. 5. D.A. McQuarlie, Quontum ClwnisttT, University Science Books, I983. 6. J.P. Lowe, Quantunt Chentistry,z"d Edition, Acadenric Press Inc., 1993. 7. A.K. Chandra, Introduction to Quanltutt Clrcmis't17, Tata McGraw-Hill, 1994. 8. L. Pauling and E.B. Wilson, Intrutluction to Qututttutt Mechanics, McGraw-Hill, 1935 (A good source book for nrany derivations). 9. R.L. Flurry, Jr., Quannrm Chenristry, Prentice Hall, 1983. 10. R.K. Prasad, Quttnlunt Chenistry,2"d Edition, New Age International' 2000 11. M.S. Pathania, Quuiunt Clrcmistry uttl Spectroscopy (Problenrs & Solnlions), Vishal Publications, 1984. UNIVERSITY OF CALICUT M. Semester Sc. Applied Chemistry I Inorganic Chemistry I (3 Credits) ACH 1CO2 UNIT I Peliodic properties of elements. Periodic anomalies of the nonmetals and posttransition metals. Octet rule, concepts of resonance and hybridisation, VSEPR nrodel,structure of molecules.Electronegativity and partial ionic character, lattice energy, Born-Lande equation,Fajans and Slater's rules, radius ratio rule,structure of simple solids. UNIT II Acid-Base chemistry - concepts of Bronsted and Lewis, strength of acids and bases, Flard and soft acids and bases.Comparison of softness and hardness, charge/size etTects. The Drago-Wayland equation. Heterogenous acid-base reactions. Surface acids and Super acids. Classification of solvents. Acid base concepts in non-aqueous solvents, levelling effect. Reactions in liquid NHr, SOz, HzSO+ and HF, Molten salts. UNIT III preparation, reactions, structure and bonding, styx numbers, closo, nido, araclino polyliedral structures. Boron cluster compounds. Wade's rule, polyhedral borane anion, carbornes, metalloboranes, metallo carboranes, synthesis, structure and bonding. Borazines and borides Boronhydrides - UNIT IV Polymorphism of C, P and S. Fullerenes and endohedral metallo fullerenes. Silicates and aluminosilicates - structure, molecular sieves - zeolites. Silicones- synthesis structure and uses.Carbides and silicides. Phosphorous-nitrogen, phosphoroussulphur and sulphur-nitrogen compounds-synthesis, structure, bonding and uses. UNIT V Extraction of elements, thermodynamic and kinetic aspects. Reduction of oxide ores Ellingham diagram, reduction potentials, Latimer and Frost diagrams, Pourbaix diagrams. Principles of powder metallurgy. Metallic corosion and passivity. Isopolyand heteropoly anions of Mo and W. Halogens in positive oxidation states, Interhalogens, pseudohalogens and cluster and polyhalides, Metal halides. Noble gas Chemistry - noble gas compounds, formation structure, bonding and stability. UNIT VI Lanthanides and Actinides, sources, extraction and separation, stable oxidation states, oxidation state IV of Ce, Pr and Tb, oxidation state II of Eu, Sm and Yb. The lanthanide-and actinide contractions, difference between 4f and 5f orbitals, separation of lanthanides and actinides, Lanthanide complexes, use of lanthanide complexes. NMR-shift reagents. Uranyl compounds. Trans - actinide elements. Super heavy elements - production and chemistry. h TJNI'T'VII Introductiort 1o coordination chemistry. 'l'ypes ol'ligands, anrbidcrrtate, chelate altcl ntacrocyolio lgarnds ancl complexes, isomcrism ernd nornenclature., I.'oiination corlstatt[s, Iitctors inllLrenoing stabiliLy, nrethods ol' detellrination ol' stability constzlnts. Chelate and rnacrocyclic cll-eots. Verlance bond theory altd its limitarions. TJNIT VIII 'l-hc crystal freld-and ligancl Ileld theorios - Orbilal splitting in octahcdral, tetrahcdral, s(lrretl'e planar, sLluare pyrarnridal ancl triogonal biphyralnidal Ilclds. Signi(icance ot' l0Dq, farctors allecting crystal field splitting, spectrochcmical and nephclauxetic sclies, Jahn-'l'cl cr cll'ect. I ITIIFURIiNCES l. D.l'-. Shrivcr, P.W. Attains and C.ll. Langlbrd, lnorganic Chemistry, Ilt.US. 2. K.F. PLrrcell ancl J.C. Kotz, lnorganic Chcmistly, W.B. Saunders Company. 3. J.E. Lluheey, lnorganio Chenristry - Principles of SLructure and Reactivity. 4. I".A. cl.tto. and G. wilkir-rson, Adv.ocd Inorganic chcmistry. 5. L.V. Azarol], IntrodLrctiorr to Solicls, Mc Graw llill. New york. 6. C. Wullsberg Inorganio chemistry, Viva,2OO2. 7. Il. 1r I)ouglas, D.ll Mo Daniel and J..l Alcxandcr. Conceots and rnodels o[' Inorganic chcrnistry, 3'd Ed., John Wilcy,200l. vvs:rf requ? .aJnemele ebinitcs _ zrsr-f .zbnuoqrnoc lyns.rU .zlneltser ttt'rle-5ll,tlA .::,;,,.. ii:: I'i'lr, jt.,.j:t_Lr ;,,:-; _ .::,.-.,.iLj- "6^ UNIVERSITY OF CALICUT M. Semester Sc. Applied Cltemistry I Organic Chemistry I ACH (3 Credits) 1CO3 UNIT I a) Bonding -M.O. Theory, Electron Delocalization and Aromaticity Molecular Orbitals, Huckel M.O Theory, Qualitative applications of HMO theory to delocalized fl systems (ii) Valance bond theory and Resonance (Including resonance energy and resonance hybrid). (iii) Stability of delocalized zr- systems of (a) butadiene molecule (b) allylic cation, anion and radical by V.B. theory and MO theory. (iv) Stability of cyclic n-systems by HMO- theory. Aromaticity, Antiaromaticity, Mobius twist and aromaticity, Homoaromaticity, Aromaticity of different Annulenes, Aromaticity in charged rings and Aromaticity in fused ring systems. (v) Stability of benzylic systems. a) (i) Hydrogen bonding ( inter and intramolecular ) (ii) Effects of hydrogen bonding on (a) boiling point of liquids, (b) acidity/basicity, ( c) stability of hydrates, (d) Stability of conformational isomers (e) Characteristics of erythro and threo isomers ( to be illustrated with examples in each case) (iii) crown ethers. UNIT II Acidity, Basicity, Solvent effects in Organic Chemistry Acidity and Basicity, Definition of pKa, Lewis acids and Bases, Bronsted acids , and Bases, HSAB principles Soiute solvent interactions, inlemrolecular forces, ion-dipole forces, dipole-dipole forces, dipole induced forces, electron pair donor-electron pair acceptor interactions (EPD/EPA). Solvation and Co-ordination numbers. Classification of Solvents: Solvents with poor hydrogen bonding capability, Solvent with moderate Hydrogen bonding capability, Solvents with Strong Hydrogen bonding capabilities. Classification of solvents according to chemical constitution- Molecular liquids, Ionic liquids and liquid crystals. Classihcation of solvents according to acid-base behavior: - Classification of organic solvents according to Bronsted Acid-Base behavior. Amphiprotic solvents Qlleutral, protogenic and protophilic solvents. Water as an amphiprotic solvent. Aprotic solvents: - Dipolar protophilic solvents, Dipolar Protophobic solvents and inert solvents (examples only). Properties of Hard Lewis acids, Soft Lewis acids, Hard Lewis Bases and Soft Lewis bases- Examples. Classification of solvents in terms of specific Solute/Solvent interaction (Dipolar aprotic solvents, protic solvents and apolar aprotic solvents. Solvent effect on atsorption spectra: - Examples of positive solvatochromic dyes and negative solavtochromic dyes. UNIT III Basic concepts in the Study of organic Reaction Mechanisms Acidity constant, Hammett acidity function, reactive intermediates and their characterization. Isotope effects, stereochemical correlation, Kinetic Vs thermodynamic control. Tralsition state, Potential energy Vs reaction co-ordinates, substituenet ef1-ects (inductive. mesomeric, inductomeric, electromeric and field effects) on reactivity. Quantitative correlation of substituent effects- Linear free enelgy relationships, -+- I-larnntet ccluations, scparation of polar resonance and steric effects and 'l'a11's equations. UNIT IV Stereochemistry Dissynrmetry, asymmetry, chirality-simple and alternating ( mirror ) axis of symmelry- conditions lbr optical activity , isotopic asymmetric variation and specilic rotation of the same compound in sign and magnitude under dilferent conditionsrelative and absolute configurations, - D and L notaLions, - sequence rule- R ancl S systems in cyclio and trcyclio compounds - optioal isomerism of compounds contaitring one or morc asymnretric carbon atoms. Enantiotopic, Ilomotopic , Diastereotopic hydrogen atoms, proohiral oentre. Optical isomerism of compounds haviug no asymmetric carbon atom. Biphenyls: Condition lbr optical activity in biphenyls- number of substituents and their size in relation to the stability of optical isomers, l{&S notation. Atropisomers- Restricted rotation in biphenyls- molecular overcrowding- chirality due to lblding of helical structure. Allenes and Spiro compounds- (structure alone) - Condition fbr optical ar:tivity and R & S notations. Optical isomerism of Nitrogen & Sulphur compounds. Condition fbr opticat activity and R&S notations. Modern theory of the structure of C: C, absenoe of liee rotation in clouble bonds, nomenclature of geometrical isomers, E& Z notation of compounds with one ol'more double bonds in acyclic systems. Stercoohemistry of Aldoximes, and ketoximes. Types of isomers. Methocls of detennining the configuration of geometrical isomers in acyclic systems, interconvertion of geonretrical isomers. UNIT V Conformational Analysis- Part I Dil'ference between configuration and confbrnration. Internal lactors affecling the stability o1'molecules- dipole interaction, bond opposition strain, bond angle sirail. Perspective and Ncwman projections- representation of dil'lerent confbrmaLions. Ccl.rfbrmation of acyclio compounds- lithane, n-butane, alkene dihalides, glycols, chloro hydrines, tartaric acid, crythro and threo isomers, aldhydes and ketones (acetaldehyde, acetone). Interconversion of axial and equatorial bonds in chair confbrmation- clistanoe between the various I{ atoms and C atoms in both chair and boat conformations. Monosubstituted cyclohexane - methyl and t-butyl cyclohexanes- flexible and rigid systems. Conlbrmation o1' disubstitLrted cyclohexanes (1:1; 7:2; 1 :3 and 1 :4). Conlbrmation ol' substitutcd cyclohexanone- 2-bromocyclohexanone, dibromo cyclohexanone, (cis& trans) and 2-bromo-4, 4-dimethyl cyclohexanone. Anchoring groLlp and conlbnnationally biased molecules, Conformations of 1:4 cis and trani disubstituted cyclohexanes in which one of the substituent is t-butyl and their importancc in assessing the reactivity of an axial or equatorial substituent. Conlormations of decaline, adamentane, sucrose and lactosc. UNIT VI Conformational Analysis Part 2 Ef'feot of confbrmatiou on the course and ratc of reactions in (a) Debromination of dl and meso 2, 3-dibromobutane or stilbene dibromide using KI. (b) Semipinacolic deamination of erythro and threo l,2 -diphcnyl- 1-(p-chloro phenyl)-2-amino ethanol. -t (c) Action of methyl magnesium bromide on 2-phenylpropionaldehyde (Stereo of asyrnmetric induction). (d) Dehydrohalogination of (dl and rneso) and erl.threo ttu'eo- bromo-1,2-diphenl,l propane. stilbenedihalide Effect of conformation on the course and rate of reactions in cyclohexane systems illustrated by: (a) SN2 and SN1 reactions for (i) an axial substituent, and (ii) an equatorial substituent in flexible and rigid systems. (b) E1, E2 eliminations illustrated by the following compounds. (i) 4{-Butylcyclohexyl tosylate (cis and trans) (ii) 2Phenylcyclohexanol (cis and trans) (iii) Menthyl and neomenthyl chlorides and benzene hexachlorides. ( c) Pyrolytic elimination of esters ( cis elirnination) (d) Senipinacolic deamination of cis and trans-2-aminocyclohexanol (e) Esterification of axial as well as equatorial hydroxyl and hydrolysis of their esters in rigid and flexible systems. (Compale the rate of esterification of menthol, isomenthol, neomenthol and neoisomenthol). (f) Esterification of axial as well as equatorial carboxyl groups and hydrolysis of their esters. (g) Hydrolysis of axial and equatorial tosylates. (h) Oxidation of secondary axial and equatorial hydroxyl group to ketones by chromic chemical direction acid UNIT VII , Chemistry of Free Radicals Generation and Characterization of free radicals- Stable and persistent free radicalsDetection of free radical intermediates- Structural and stereochemical properties of radical intermediates. Radical ions-Reaction mechanism involving radical intermediates- Free radical substitution and addition reactions- Intramolecular reactions- Rearrangement and fragmentation reactions of free radicals- Electron transfer involving transition metals- Carbenes and Nitrenes- Formation of Singlet and triplet carbenes, addition to double bonds, insertion and rearrangement. UNIT VIII Aromatic Substitution Reactions Aromatic electrophilic substitution: - Mechanism, rate controlling factors, formation of C-C bonds, C-N bonds, C-S bonds and C-halogen bonds. Nucleophilic aromatic substitution by Elimination- Addition , nucleophilic aromatic substitution by Addition- Elimination mechanisms. The benzyne mechanisms, aromatic radical substitution, SRp I mechanism REFERENCES 1. F.A. Carey, R. J. Sundberg- Advanced Organic Chemistry, Plenum Press. 2. T.H. Lowry, K.S. Richardsen- Mechanism and theory in organic Chemistry, Harper Collins, 3. Jerry March- Advanced Organic chegristry McGraw Hill' 4. Nasipuri- Stereo Chemistry of Orgariic Compounds, 1993 Edn. 5. Kalsi- Stereochemistry of Organic compounds Wiley Eastern. 6. E.L.EIiel and S.H.Wilen , Stereochemistry of Organic compounds, Wiley Interscience. 7. P.Y.Bruice, Organic Chemistry, Prentice Hall. 8. Mitland Jones Jr. Organic Chemistry, Norton and Company' 9. RAU Jones: Physicaiand Mechanistic Organic Chemistry, Cambridge University Press. 7 I]MVERSITYOF CALICUT M. Scmester Sc. Applied Chenistry I Physical Chemistry I ACH IJNIT I Thermodynamics (3 Credits) 1CO4 I rhermodynanrics (brief nrention). Thermodynanric criteria for equilibriunr and spontaneity. Third law of therntodynamics - Statement of the law and explanation., Need for the third law, Nernst heat theorem, Apparent exceptions t<l third law, Applications of third law, Determination of absolute entropies using third law. Unattainability of absolute zero. Residual entropy. Deternrination of relations connecting the thermodynanric pa:'tial derivatives by the method of Jacobians (The discussion to be confined to closed thernrodynanric systems). First IINIT II ancl second laws Thermodynamics of II of solutions: Partial molar quantities, Chemical Potential, Variation of Chemical Potential with ten'rperature and Pressure, Partial molar volume and its deternrination, Gibbs-Duhem equation, Thernrodynamics of ideal and real gases and gas mixtures. Fugacities of gases and their determinations, Activity, activity coeftlcient, standard states of substances (for solute and solvents). Duhem-Margules equation and its applications. Therntodynamics of ideal solutions, Deductions of the laws of Raoult, ebullioscopy, cryoscopy and osn'rotic pressure. Non-ideal solutions, Deviations from Raoult's law, Excess functions - excess free energy, excess entroPy, excess enthalPy and Thern.rodynamics excess volume. tlNIT ttl Thermodynamics trI Thermodynanrics of in'eversible processes-Sinrple examples of irreversible processes. General theory of nonequilibrium processes. Entropy production. The phenomenological relations. Onsager reciprocal relations, Application to the theory of diffirsion, therntal diffusion, thermoosnrosis and thermomolecular pressure diff'erence, Electrokinetic eff'ecs. The Gl ansdorf-Pregogi ne equati on. REFERENCES I . S. Glasston e, Thermodynamics for Chemists, East-West, I 973 2. Rajaranr and Kuriokos e, Themotlynamics , East-West, 1986 3. R.P. Rastogi and R.R. Misra, An introtluclion to Chemical lhermodynamics, New Age International 4. D.A. McQuarrie and J.D. Simon, Physical Clrcmistry, A Molecular Approach, University ScienceBooks,1997. K.J.Laidler, J.H.Meiser and B.C.Sanctuary, Physical Chenistry, Houghton Mifflin Conrpany, New York, 2003. 6. Pigoggine, An introtluction to Themtodynamics of ineversible processes,Interscience 7. B.-G. Kyle, Chemical antl Process Therntodynantics,2"o Edn, Prentice Hall of India 8. G. K. Vemulapalli, Plrysical Chemistry, Printice Hall of India 9. H. Margenran and G.M. Murphy, vol. chap. I The Mathematics of Physics and -5. Chenristry. lo - UNIT lV Electrochenristry I Derivation of Debye - IJuckel - Onsagar equation o[ conductivity. Validity of the Debye I-Iuckel - Onsagar equation tilr arlueous and non aqueous solutrorrs. Deviations lionr the Onsagal equation. Signilicance of the degree of dissociation and its detcrnrination. Conductance ration and Onsagar equation. Dispelsion of conducLance with high po(ential gradients. The Debye-IIuckel linriting law and its various-fbrms- Qualitative and quantitative tests of the Dcbye-I{uckel liniting equation. Activity and activity coetTicients in electrrllyic solutions. UNIT V Dlectrochcmistry II Gnlvanic cells. Standard electrode potentials. Revenible cells. Concentration cells wiLh a without transt'erence. Liquid junction potential and its deternrination. Deternrination olsolubility of sparingly soluble salts. 'lenrperature c<leflicient of EMF and determination ol' G, I-I and S. Fuel cells. UNIT VI [,lectrochcnristry III Poltrization, Dissolution and decomposition potentials. Concentration polarizrtion. Deconrptrsitirllt voltage (Potcntial) and its deternrination. Over voltage - I-Iydrogen over voltage, oxygen over voltage, nretal deconr;rosition over voltage and their deterrrrination. Mechanisnt of anodic and cathodic processes (Theories of overvoltage) - Ionic diffusion as llre slow process, Ionic discharge as the slow process. Principles of polarography. The dropping nrcrcury cathode. The half wave potentials. REIERENCLS l. D. A. Mc Innes, 'l'he Principles of electrochenristly, Dover Publications. 2. S. Classtone, Introduction to ElectroclrenrisLry, Van Nostrand. 3. Bockris and Reddy, Modern Aspects and Electnrchenristry Vol. I & II, Acadenric Press. 4. L I Anthropov, Thurretical Electrochcnristr-y, Mir publishers. UNIT VII Crystallinc state I CrysLal syrntnetry. Synrnretry elenrcnts and syntntetry <lperations. Screw axes anfl gli4e planes. Allowed conrbinations oloperations leading to 32 crystal classes. Mathenratical prooI lirr thc non-existence of 5-tilld axis ol'synrnretry fbr crystals. I-Iernrann - Mauguin notaiions. Steleographic Prrljections of sonre sinrple clystal classes (e.g. l, I nt,21nt, 21tnt,222, ntntnt). Trlnslational syrnntetry, screw axes and glide planes. Intro<Iuction to space groups. UNIT VIII Cryslallinc State lI Reciprrrcal lattice. X-rays and internal stnrclure ol' crystals, XRD nreasur-ements. Lauc nlethrxi. Rotating crystal ntethod. Powder nrethod, Scattering factrlr. Intensities of difliactetl X-rays atrd sl.ttctttral analysis, Intensity and its rclation with the atonric arrangenrent. Electron density in c.ystals. Electron density nraps (briel'nrcntion). Fourier synthesis. REIIIRENCES l. D.A. McQuarrie and J.D. Sinron, physical Clrenristry, a nrolecular Uni versi ty Science Books. 2- G.K. Venrula Palli, Physical Chenristry, Prentice IIall. 3. P.W. Atkins, Physical Chenrisrry, EI_BS Oxlirrtl University press. approach, UMVERSITY OF CALICUT M. Semester Sc. Applied Chemistry II Group Theory and Spectroscopy (3 Credits) ACH 2CO8 UNIT I Molecular Symmetry in rlolecules. Identity, Rotation, Exanrples. Point Groups and operations. Rellection, Inversion and Improper rotation their deternrinations. Symmetry elernents and symnretry operations UNIT II Mathematical Groups Mathenratical group - Deflnition, Examples, order of a group' Abelian and cyclic groups, Group Multiplication table. Rearrangement theorem. Sub gloups and classes in group. Similarity r.ranslormation. Conjugate elements. Matrices. Addition and " ol'matrices, Inverse of a matrix. Character of matrix. Diagonal matrix, rnultilrlication Direct sum and direct product of square matrices, Block diagonalized matrices. Solving linear equations by the method of matrices. Matrix tbrm of symmetry operations. Basis. UNIT III Theory of molecular symmetry Representation of groups. Basis. Construction of representations using vectors and atolnic orbitals as basis. The representation generated by using Cartesian co-ordinates positionecl on the atoms of a molecule (SOz and H2O may be taken as examples). Reducible and irreducible representations. Construction of irreducible representations by reducriol (sirnilarity transfbrmation). Great orthogonality theorem (GOT) and properties ol' irreducible representations, Construction of irreducible representations using GOT, Construction of character Table (Czu, Cr,, Czn, C+u). Nomenclature of irreducible represenr.ations - Mulliken symbols, Symmetry species. Derivation of reduction formula using GOT, Reduction of reducible representations (e.g., I.un ) using the reduction Ibrmula, Direct sum and direct product of irreducible representations. Connection between group theory and quanrum mechanics. UNIT fV Application of Group theory to chemical bonding i) Vanishing and nonvanishing integrals. Transition moment integral and selection rules. Overlap integrals and conditions for overlap. ii) Moleculzy orbital treatment of molecules using Group theory. Treatment of HzO, Classification of atomic orbital involved into symmetry species, Group orbital, Symmetry adapted linear combination (SALC), Projection operator, Construction of MOs, Electronic conliguration of HzO, Symmetries of the ground and excited states' Electronic transitions and selection rules, Laporte selection rule tbr centro symmetric molecules. iii) Group theoretical rreatment of hybridization, Construction of hybrid orbital in BFr and CH+, Inverse transfbrmation. -lL - UNIT V Application of Group thcory to molecular vibrations Molccular vibratitlns, SynrmeLry species ol'normal rnodes ol' vibration, Consrruction ol'I-.,,,,. Normal coor-dinates and drawings ol' normal rnodes (e.g., FI2o and NH3), Selection rules lbr IR and Raman activities, Complementary character ol' IR antl Ratnan Sllectra, Detern.rination ol'IR active and Raman active modes ol' ntolecules (e.9., HrO, NHr, CH+, SFo). UNIT VI i) Gencral Theory of Spectra Electro l.nilgnetic radiation and its dil'l'erent regions, Interaction ol' matter with radiation and its el'l'ect on thc energy ol'the molecule. Origin ol'molecular spectra, Theory ol' the origin ol' rotational, vibrational and electrcnic spcctra. Inteniity olspectral lines, Dependence ol' inLensity on population, transiLion probabilities, Ttransition montenI integral, Selcction rules. Line widths, Doppler broatlening, Li l'etirne br oadening. ii) Microwavc spectroscopy Rotation specra ol'diatomic and poly atornic nrolecules, Rigid and nonrigid rotator models, Asymrnetric, symrnetric and spherical tops. lsotope etl'ect on rotad;n spectra, Stark el'fect, Nuclear and electron spin interactions. Rotational transitions and selection rules. Microwave spectrometer - Princillles -Instrunrentation (briel'nrention only). Applications. iii) Vibrational spectroscopy Vibrational spectra ol' diatomic anrJ poly atomic molecules, Harmgnic oscillator model, Anharrnonicity, Vibrational transitions and selection rules. Morse pol.errtial, Fundanrentals, overtone.s, Hot bands, Combinati<ln bands, Dillerence bands. UNIT VII i) Vibratiou-rotation spcctra ol' diatomic and polyatomic molecules, p,e,R bt'arrches. lR and FTlll specLr-ophotot.netcr - Principlcs - Instrumentation (brief mention only), Applicarions. ii) Raman spcctroscopy Pure rotational, pure vibrational Ranran spectra, Vibrational-rotational Raman spectra, Selection rules, Mutual exclusion principle. Rarnan spectrophotometer- principles Instrumentation (briel'mention only), Laser Ranran spectroscopy, Applications. iii) Electronic spcctroscopy Basic principles, Beer - Lambert law, Molar extinction coel'licient, Intensity nl. electronic transitions. Types ol' electronic transitions. Franck - Condon principle, Ground and excited electronic states ol' diatomic molecules. Electronic *pectra ol polyatomic nrolecules, Chromophores. The lhte ol' electronically exciied state species- Vibrational re laxation, External conversion, Internal conversion, Fluorescence, Phosphorcscence. Jablonski diagram. Electronic spectra of conjugated molecules - dissociation and predissociatron spectra. UV-Visible spectruphotometer - Principles Applications. - Instrumentation (briel'mention only). UNIT VTII i) NMR spectroscopy Magnetic proPerties oI nuclei, Theory and rneasurement techniques, Solvents used, Cherrrical shilt and lactors inlluencing chernical shi l't, Shielding ell'ects, Spin-spin interac[ion, Coupling constant, Factors inlluencing coupling constant. EII'ects of chemical exchange, Fluxional nrolecules, Hindered rotation on NMR spectrum, Karl's relationships, NMR specrrolneter- Principles and instruntentation (briefl mention only). Uuttipte NMR spectroscopy (briet' account). Applications of NMR spectroscopy to structure elucidation o1' simple organic and inorganic molecules. FTNMR. ii) ESR spectroscopy Theory an{ ,reaior.nl.nt techniques, hyperfine interactions, Equivalent and nonequivalent protons, Kramer's theorem. ESR spectrometer- Principles instrumentationlbrief mention only). Applications in structure elucidation ol'simple molecules. iii) Mossbauer spectroscoPY The Mossbauer effect. Inslrumentation (brief mention only). Hyperfine interactions, isorner shilt, electric quadruple and magnetic hyrerhne interactions' Applications' iv) Mass SpectrometrY Basic prirrciples, Instrumentation (brief nrention only) - Mass spectrometer, ions, interpreiation of mass spectra, resolution, exact masses of nuclides, molecular Diels retro isotope ions. Fragmentation processes - Mclaflerty rearrangements, of heats of evaluation and Aklei liagmentation. Applicaiion in structure elucidation sublimation and ionization potential. REFERENCES l. F.A. Corton, Cltentical applications of Group Theory,2'd Edidon, Wiley Eastern, 2. 3. 4. 1971. Jail'e and Orchin, S)'mtnetry in Clrctnistry' Wiley Eastern' L.H. Hall, Group Tirory and symnetrs^ in Chentistry" McGraw Hill Appliccrtions' R. McWeen y, iy,rurctry': An Intror)uctiott to Group Theory and its Pergamon Press, London, 1963' 5.P'H.Walton,BeginnittgGrot,tpTheoryforChemistry,oxfordUniversityPress Inc., New York, 1998. 6.A.W.Joshi,El,ementsofGroupTheoryforPlD,5lgisrs,NewAgelnt.ernational Publishers, I 997. . 8. 7 Press' 1998 ' P.W' Atkins ' Physicttl Chendstry"6'h Edition' Oxford University Wiley Eastern' Etlition' 5'h F. Daniels and R'A' Alberty, Ph1'51gtt1 Chemistry' r 980. g.D.A.McQuarrieandJ.D'simon,PltysicalClrcnistry,AMolecularApproach, UniversitY Science Books, 1997' Houghton K.J.Laidler, J.H.Meiser and B.c.Sanctuary, Plrysical chemistry, Mifflin ComPanY, New York, 2003' Tata McGraw Hill, I l. c.N. Banweit, ir,rrdn,r"ntals of Moleatktr spectroscctpy, New Delhi, 1994. 1962. 12. G.M. Barrow , Introtlttctirln to Molecular Spectroscopy, McGraw Hill,Analysis' 4'h 13. H.H. Willard, L.L. Merit and J.A. Dean, Irtstrtrntental Metlrctls of Edition, Affiliated East-West Press Pvt' Ltd'' 1965' l4.N.Sathyanarayana,Eleclronicabsorpliottspectroscop),andrelatedtechniclues, 10. UniversitY Press, 2000. Press Phyflirol ntethotls in Inorganic chenristry" Afflliated East-west 15. R.S. Drago, Pvt. Ltd., 1977' lL{ - UNIVBRSITY OF CALICUT M. Semester Sc. Applied Chemistry II Inorganic Chemistry fI (3 Credits) ACH 2CO9 UNIT I Molecular orbital Theory - Composition of ligand group orbitals. MO diagrams for complexes with and without pi-bonding. Electronic spectra of complexes - Terms of dn configurations, selection rules for d-d transitions. Effect of weak ligand fields on RS terms in octahedral-and tetrahedral complexes. Orgel diagrams, spectra of 3d metal complexes, calculation of Dq, B and B conelation diagram. Tanabe and Sugano diagrams. Charge transfer spectra. Spectra of f block elements. UNIT II , UNIT Magnetic properties of transition metal complexes - Types of magnetic properties. Paramagnetism - the Curie and Curie-Weiss law. The pJ, p;fs and p spin-only .r,pr.rrions, quenching of orbital moment in metal complexes, spin-orbit coupling, temperature independent paramagnetism. Antiferromagnetism-types and exchange path ways. Magnetic properties of f-block elements. Determination of magnetic moment by Gouy method. Applications of spectral and magnetic properties in coordinationchemistrY. III photochemical reactions of metal complexes. Prompt-and delayed reactions' Excited states of metal complexes - intralignd, ligand field, charge transfer and delocalized states. Charge transier excited states and redox processes, communication between excited state-s, radical pair models. Properties of ligand field excited states, rules for photosubstituiion, phoio-aquation and ligand exchange reactions. Photo-isomerisation ald photo-recimization. Photo-substitution mechanisms. Metal complex sensitizers, chemical actinometry and photo-chromism' UNIT IV Reaction mechanisms of metal complexes, Classification, rate laws, Metal and ligand substitutiol reactions in octahedral complexes - A, D and I mechanisms and associated energetics aquation and base hydrolysis, stereochemical changes, isomerisation und recemisation. Fuoss - Eigen equation and factors determining A a1d D mechanisms. Lability and inertness of the complexes, trans-effect, its theories and applications, the cis-efiect. Reactions of coordinated ligands : hydrolysis, acid dissociation, uidol condensation, trans amination, template effect and macrocyclisation. UNIT V classification, outer-sphere electron transfer, chemical activation, Marcus theory and thermodynmics. Inner-sphere electron transfer kinetics, effect of the natuie of metal and ligand, bridging group effects. Metal-ligand redox reactions. Two electrons-, inner-sphere electron transfer processes. Redox reaction mechanisms - UNIT VI Organometallio compouns. Classification and nomenolature. 'fhe l6 and l8 elcctron rulcs, cleclron counting -covalent and ionic models. Carbon n- donors. Main group organonletallics-alkyl and aryl groupsl ,2,72, 13,14 and l5,synthesis structure ancl applications. Synlhesis structure and bonding in metal oarbonyls. Transition mctal to carbon multiple bond- the metal carbenes and oerrbynes. UNIT VII l'r'ansition metal complexes with chain n donor ligands-synthesis, structure, bontling and applications of complexes ol'ethylene,allyl, butadiene and acetylene. Complexe.s of ring n donor [igands-synthesis, structure ,bonding and reactions of typical conrplexes of cyclobutadiene, C5l-15-, C6I16, Ci-b and Csl-Is2-. Irluxional organometallios. UNIT VIII Applications ol'organometallic compounds in organic synthesis and homogeneous catalysis. Complex fbrmation and activation of FI2, N2, Or, NO by transition metals. Catalytic steps, Oxidative addition, reductive elirnination and insertion reactio,s Carbonylation by Collman's reagent. Llydrozirconation of alkenes an6 alkynes. I-lomogeneous caLalysis - llydrogenation, hydrosilation and isomerisation ol.alklnes, alkyne, cycloaclditions and polymerisastion, Zeigler-Natta catalysis, hydrofbrmylatioi ol alkencs, Monsanto acetic acid plocess and Wackcr p.o""... M"taf complexes in enantioselective synthesi s. REFEITENCES l. 2' D.1". Shriver, P.W. Attains and C.ll. Langfbrd, Inorganio Chemistry, ELBS. K.t'-. Pr-rrcell and J.C. Kotz,lnorganic Chemistry, W.B. Saunders Ctmpa,y. 3' J'E' Fluheey, Inorganic Chemistry Principles Lf Structure and Ileactivity. 4- lr.A. cotton and G. wilkinson, Advnced hiorganio chemistry. 5. l-.v. Azaroif, Introdtrction to Solids, Mc Graw ltill. New yort<. 6. G. Wulf.sberg Inorganio chemistry, Viva, 2002. 7. A.E. Martell, Coordination Chemistry Vol.l. 8. R.L- Dutta and A, Shyamar, Elements of Magnetochemistry. 9. R-s. Drago.' physicar Methods in l,organic -hemistry. - rt-.- UNIVERSITY OF CALICUT M. Sc. Applied Chemistry Semester II Organic Chemistry II (3 Credits) ACH 2CIO UNIT I Reactions of Carbonyl ComPounds Reactivity of carbonyl groups in aldehydes, ketones, carboxylic acids, esters and acid chlorides with nucleophilic reagents ( Carbon, Hydrogen and Nitrogen nucleophiles).Carbonyl o-iubstitution reactions:- Keto- enol tautomerism. Reactivity of enols, mechanism of o-substitution reactions. o-Halogenation of aldehydes, ketons and carboxylic acids. Hell- Volhard- Zelinski reaction. Acidity of a hydrogen atom- enolate ion formation. Reactivity of enolate ions. Halogenation of enolate ions- haloform reaction. Alkylation of enolate ions. Aldol and related reactions, Claisen ester condensation, Darzen reaction, Dieckmann, Perkin and Prins reactions. Mannich reaction. Alkylation using enamine. Alkylation of carbon nucleophiles by conjugate addition, Michael reaction, Robinson anulation, The enamine and imine anion. Phosphorous ylides and Wittig Reaction UNIT II Pericyclic Reactions Definition alcl types of reactions classified as pericyclic reactions- (a) Cycloaddition and cycloconversion'(b) Electrocyclic ring closure and ring opening (c) Sigmatropic of rearrangemenls. Gi Cheletropic reactions (e) Group transfers. Stereochemistry pericyciic reactions and theory of molecular orbital symmetry M.O. Syrnmetry by the method of correlation diagram by both t paths. Stereochemistry of Pericyclic reactions- thermal and pho Transition state aromaticitY" of Frontier Basic principles of perturbation molecular orbital (PMO) theory, Significance Molecular or.bitals, Stereochemistry of pericyclic reactions by the "Frontier molecular orbital (FMO) method". (a) Selection rules; Application of selection rules in pericyclic reactions involving rearangements Charged systems unO (U) 3 and 5 membered lings and Claisen and Cope Detailed siudy of Diels-Alder reaction, Sommelet- Hauser Itearrangement REFERENCBS 1. T.H. Lowry, K.S. Richardsen- Mechanism and theory in Organic Chemistry, Harper' 2. F.A. Carey, R.J.Sundberg- Advanced organic chemistry, Plenum Prss. UNIT III Chemistry of Natural Products primary and secondary metabolites- Chemical classification of Natural produotsof alkaloidsAlkaloids- Classification based on ring structure- Medicinal importance elucidation struoture reagentsGeneral metho<is of isolation- TLC identification by spray of methods General based on degradative reaotions- Synthesis of Quinine, Terpinoids- Isolation and structure elucidation- TLC identification using spray reagentsand insect classification - Importance of Tepnoids as flavour and fragrance compounds biosynthetic pathway to repellents ( an overview) . Syntheiis of Camphor - Chemistry of using spray reagenls mono and di-terpenoids. Steioids classification - TLC identification Synthesis of - lmportan.. oi steroids in physiology and medicine - steroid hormones- t1- Oestrogen- Conversion of Cholesterol to Testosterone - Biosynthetic pathway of cholesterol- Flavanoids as natural colouring materials- Chenristry of flar.-,rer, Isol'lavones and Coumarins, IIEFERENCES l. I. L. Finar, Organic Clremistry, Vol.2, Longman. 2. N.lL. Krishnaswami, Chemistry of Natural Products, University Press. UNIT IV Photochcmistry General Principles, Jablonski diagram, Photosensitization, orbital symmetry considerations related to photochemical reactions, photochemistry ol' carbonyl compounds. Photochemistry of visions, photochemistry o1' alkenes, Patterno Buchi reaotion, Photochemistry of aromatic compounds, photochernical ."u.rong"*ents, Di-n- methanc rearrangement, aromatic reanangement, Barton reaction, rearrangement, Norrish l and Chen-ristry of singlet oxygen II photo-I.-ries reactions. Atmospheric photochemistry, phoiosynthcsis. IIEITERENCES l. F-.A. carey, R.J.Sundberg- Advanced organic chemistry, plenum press. 2. P.O. Kan- Organic photochemistry, Mc Graw [-Iill. UNIT V Named Organic Reactions of carbocations, carbanions, Migratiou to synthetic applications of the following I and semipinacol, Dienone - phenol, Wolf. Fries, F-ischer_ Hepp, Demjanov, aptitude in rearrangements Named reactions: Favorski reaction, Stork reaction, Hollmann- Loelller"rru-ir" Irreytag reaction, Shapiro reaotion, Woodward and Prevost hydroxylation, Stobbc condensation, Gomberg- Beohmann reaetion, Vilsrneir reaction, peterson reaction ancl Wohl-Zeigler reaction REFEITENCES l. Jerry March- Advanced organic chemistry McGraw I-Iilr. nic Chemistry. ngman. Prentice Hall. c Applications of Named Reactions in ess, 2005. UNIT VI Oxidation -Reduction Reactions oxidation o1'alcohols to aldehydes, Ketones or Carboxylic acids. oxidation ol. aldehycles and ketones. Flydroxylation of alkenes, oxidative cleavage of Carbon-Carbon double bonds, Addition of oxygen to Carbon-Carbon double bonds, oxidative cleavage of alkynes, reactions of alkenes with singlet oxygen. Allylic Oxidation, Muffat Oxidation, Swern oxidation, oxidative coupling of l'lienols. Rlduction reactions. Reduction ol. It double a1d triple bonds with catalytic hydrogenation, Stereochemistry and selectivity. Reductions using LAH, NaBH4, diimide and Lindlar catalyst REFERENCES 1. F.A. Carey, R.J.Sundberg- Advanced Organic Chemistry, Plenum Press. 2. R.O.C. Norman and J.H. Cox, Principles of Organic Synthesis, Chapman & Hall. 3. W. Carruthers, Some modern methods of Organic Synthesis, Cambridge Uni. Press. 4. H.O. Flouse, Modem Synthetic Reactions, Benjamin Cummins. UNIT VII Biomolecules: Amiono acids, Peptides, Proteins, Nucleic acids, Lipids and Carbohydrates. Natural and unnatural amino acids, Making Peptide bonds- General strategies The Eight stages of peptide synthesis, Amino group Protection and de-protection methods( Nproiection- Cb, o, Z, N- Protection Boc, Mechanism of Boc Cleavage, N- protection Frro., Other Fmoc reagents, Mechanism of Fmoc deprotection). Carboxyl protection methods- As esters, as hydrazides. Peptide bond formation- a coupling cycle. Standard Peptide coupling reagents (Carbodimides, Halopyridinium salts,-(Mukaiyama method) phosphonium, imidazolium and uronium reagents). Mechanism of DCC coupling. Solid Fhur. peptide synthesis- The Melrifield method. Solid phase peptide synthesis- Fmoc method. Fmoc resins (examples only). Advantages of solid phase synthesis. Protein biosylthesis. The role RNA and DNA in protein biosynthesis. Nucleic acid Structure(DNA and RNA). Bases and Base pairing, Codons and anti codons. Sequence in protein biosynthesis (Transcription, Transalation and replication). Polymerase Chain reaction (PCR), applications of PCR. Recombinant DNA Technology and its applications. Cloning (introductory discussion only). Structure of Oils, fats and Waxes. Introduction to phospholipids, sphingolipids and glycolipids. -arbohydrate- Stereochemistry and Configuration of glucose, mannose, xylose, galactose, arabinose and ribose. Oligosaccrides and polysaccarides. Starch, Glycogen, Cellulose, Chitin, Industrial applications of polysaccarides. REFERENCES 1. Jerry March- Advanced Organic chemistry McGraw Hill' 2. P.Y. Bruice, Organic Chemistry, Prentice Hall. 3. J. Clayden, et. al., Organic Chemistry, Oxford University Press' 4. I. L. Finar, Organic Chemistry, Yol.2, Longman. UNIT VIII Heterocyclic Chemistry Aromatic heterocycles and nonaromatic heterocycles. Five membered ring compounds with ole heteroatom. Synthesis of pyrrole, Furan, Thiophene, Indole, Benzothiophene. Six mernbered rilg compounds. Quinoline, Isoquinoline, Pyrylium salts, 2H -pyran- 2ones, 4H-pyran -4-ones.Five and six membered ring with two or more heteroatoms pyrimdines and purines, quinazoline, oxazine, Thiazene, Imidazole. REFERENCES 1. J.A.Joule 2. Gilchrist, and K .Miller,. Heterocyclic Chemistry. Heterocyclic Chemistry. l! li I -\ UMVERSITY OF CALICUT M. Semester II Sc. Applied Chemistry Physical Chemistry II (3 Credits) ACH 2C11 IINIT I Statistical Thermodynamics I Basic Principles, Permutations. Probability distribution of particles in energy states. Micro states and nlacro states. Statistical weight. Most probable distribution. Therntodynantic probability and entropy. Boltznrann distribution law. The partition function and its relation to the thern)odynanric functions. UNIT II Statistical Thermodynamics II The pert'ect gas. Factorization of the partition tunction into the translational, rotational, vibrational, and electronic parts. Evaluation of partition functions and the thenrrodynantic n-ronatonric and diatomic gases. The system partition function (canonical partition function) and its relation to molecular partition function. Sackur - Tetrode equation. Heat capacity. The anontalous heat capacity ofHydrogen. Ortho and para hydrogen. functions. Ideal Statistical Themodynamics III Heat capacity. Heat capacities of solids, Classical and quantum theories, Einsteins theory of atomic crystals and Debye's modification. Heat capacities of gases - classical and quantum theories. The anomalous heat capacity of hydrogen, ortho and para hydrogen. Imperfect Gases. The virial expression and the virial coefficients. Relation between the virial coefficients and the cluster integrals. IIMT III LINIT Mtatistical Thermodyn amics IV Quantum statistics - The ideal Fermi Gas. Fermi - Dirac distribution law. Energy and pressure of Fernri Gas. Gas Degeneracy. Applicatron to electrons in nretals. The ideal Bose gas. Bose-Einstein distribution law. Energy and Pressure of an ideal Bose gas. Gas Degeneracy. Bose-Einstein condensation. Application to liquid helium. REFERBNCES l. G.S. Rush Brook Statistical Mechanics, Oxford University Press. 2. T.L. Hi I l, Introducti on to S tati stical Thermodyn ami cs, Addi son Wesl ey. 3. K. Huary, Statistical Mechanics Thermodynanrics and Kinetics, John Wiley. 4. F.C. Andrew, Equilibrium Statistical Mechanics, John Wiley. 5. O.K. Rice, Statistical Mechanics, Thernrodynamics and Kinetics, W.H. Freeman and Co. LINIT V The Liquid State X-ray difliaction studies of simple liquids. Short range order. Radial distribution function. Configurational Partition function for liquids. Theories of the liquid state. Lattice theory, The cell or liee volume theory, The simple hole theory. Order-disorder theory. LennardJones theory of melting. Communal entropy of liquids. -La \-j REFERENCLS l. J.A. Barker, Lattice theories of the liquid state, Perganxrn Press. 2. I. Prigrgine, MolccularTheory of solutions, North HollandPublishing Co. 3. O.K. Rice, Statistical Mechanics'l'hernrodynanrics and Kinetics, W.H. Fleentan and Co. 4. Molewyr I-Iughes, Physical Chenristry, Canrbridge University Press. UNIT VI Solid State Chcmistry I Electrtnic Stu.rcture of solids. Classilication oi solids into conductor, seruiconduct<lls and insulators- Prepu'ation, prlperties and industrial inrportance of Senriconductors. Intpert'ections in solids. Point, line and plane det'ects, Electrons and holes. Nonstoichionretry. UNIT VII Solid State Chenristry II Inrpert'ection and Physical propemies ol solids (Briel' survcy) Electrical propet'ties - Electrical conductivity, I-Iall etl'ect, dielectric properties, piezoelectricity, l'erroelectricity and conductivity. Super conductivity, Meisner effect, Briel' discnssion of Co<lper theory ol'superconductrvtty Optical properties - Photoconductivity, lunrinescence, coluur centers, lasers, refractisn, birefi'ingence. Magnetic properties - dianragnetisnr, Paranragnetism t'erro mangnetisnr, antit'errlnrtgnetisnr and f'erri nragnetisnt. Thernral properties - thernral conductivity and specific heat. Mechanical propertie;: Strength of real crystals as contpared with an i<Ieal crystal, dillcrent .strengtheni ng nrechan is nu. REFERENCES I. I-.V. Azaroll, Introduction to solids, McGraw-Hill. 2. A. K. Galway, Clrenristly ol'Solids, Chapnran and Hall. 3. N. B. Ilanna, Solid State Chenrisrry, Prentice Ilall 4. G. M. Barrow, Physical Chenristry, McGraw - IIill. -5. W. J. Moore, Physical Chenristry, Prentice Hall 6. A. R. Wesr, Solid srare chenristry, John Wiley. UNIT VIII Photochemistry Laws of Photochemistry. Quantunr yield and its tletermination. Et't'ect of tenrperature, wavelength ilnd intensity of radiation on photochemical leactions. Kinds of photochenrical reactions. Kinetics ol' photochemical chain reactions. Hz-Brz reaction. Hz-Clz reaction. Photolysis ol'NI'I3. Excinrers and Exciplexes. photosensitiz.ation by FIg. Photo-physical phenonrena. Radiative and non-radiative t-ransitiorrs. Jablonski tliagranr. Fluorescence. Phosphorescence. Lunrinescence. Chenrilurninescence. Thernrolurrrinescence. The Ruby Laser. REFERENCES l. D. A. McQuarrie and J.D. Simon, Physiurl Chenristry, A nrolecular approach, Univer.sity Science Books. 2.G.K. Venrulapalli, Physical Chenristry, Prcntice-I-Iall of India. LINIT.IERSI7} OF CAL| CLIT Pmctical Inorgank Clvmistry Semester- I ( 2Credits) ACH| C 05 Qualitative analysis Separation and identification of two metal ions of which one is less familiar elements tike,W,Tl, Se, Ce,Th, I. V,Zr,TiJ,Mo,Li. Quantitative Estimation. Volumetric estimation of the following cations using EDTA. Ca, Ni, Co. Al, Ba, Cu and Fe. Practical Inorganic Chemi@ Semester-Il ( 2Credits) ACII2 ! C I]. Colurimetric determination of metal ions. Iron, Chromium, Manganese, Nickel, Titanium and Vanadium- fl Separation and estimation of binary mi.rlures of metal ions in solution.Copper- Nickel, Ferric iron,zinc,calciunu lvlagnesium, Barium and Silver. IIl Analysis of Ores, Alloys,Cement and Soil. I|I Prepa.ration and charactgrization ofmetal complexes' REFERENCES. A.I.Vogel. A text book of Macro and Sememicroqualitative inorganic anal-vsis V. V Ramanujam, I-norganic Semimicro Qualitative Analysis. AI.Vogel. Atext book of Quantitative inorganic analysis D.P. Agarwat and R.C. Saxena Advanced Inorganic Chemistry Practicals- I ZL. I jNl\/1,)ltSI'l'Y ()lf /l/.,tr'., Scrricslcr (lr\l,l('t j'l' lltltl i rt l (' h r t tt is' t ry I llr-ltciicrrl Ol'g:rrric I(2 ('r-ctliis) 1't('lli. i i - i .;r ilrir':rttir'1''l't't'it lr i{l ,. 1r('s : l\li'{lio,ls ol sc;ltntlion iirtrl l)ulil'iciitiolt ol'olgitrric t'orrrlrtrrrrrtls ll'trclitlrrirl, ijlt.itrrr lrirrl lorr l)rr'::sur'i.'r.listilllrliorr. llrtctiotutl cr'1,:itlrllizlttion itlt,.l strblirrtlrtiorr. 2. tJ rr:r I Ii rr { ivt' ( ) r'grr rr it',,\rr it l.1,sis: (.)ttirrttitlttivt' St:;iitnttiiirt ol'()r'lliurie binirr'.1, l)li\lul'L':i [r.y Sctrrirrrit'r'o irrrlrll,ticlrl t.-.rlrnit;rrt':;. N'leit.';ttt'ettte ttt:; ol'l'lr1'sir.:irl c()n:.iti-urts irrrtl pr',-:pirlirliorr tll'tlt-'r'ivittives -1" l'r'r1li'r'lrliorr ol' ()r'g.:rnic ('onr;lilunrls: l'tclil.tttttiotts ol'ltltottt liltccrr tlrglttric eorrr;'rorrrtls irr rvlriclt irt lcirst livc ol tltcrrr irrvolre:; tttittirtlttrtt It\o :i.1'tttltr:lic :;lcps (irrcltrtlirrg plrotticlrclrricirl rrrt'tlrotls). l'rrrrl'ir.lrtiorr ol' l)r'r)tl llcts [rt t't1'l;tltllizitliott, rlir;tillirtirln rurtl irviriltrtrle clrntrnirtup,r'lltlrir: rrri-.tlrorls. ('lututt:lctizittiort ol'lrll isolirtr'tl ltnrtlrrcls bl, lrrrirlylicirl lrrrrl sltt'clr-irl rrrcllrotls (lr'l'-lli. ll\/ Yis t i('-N'|51. N'lt'ltirrg lioirrl/ lloilirrg l'trirrt tlctelrrrinllion rrrril 'l'(iA lrrirlysis)- llltrstrrrrii,t. utitllrlrlt':1. llr it'tlt'l ('r'ir lis reitt:tiolt, l)e t liirr l'circlir)n. lie irncr - 'l'ittrrrrrrrrr lt.lrt.tior)Slttt,lriiel'ct' t't'rtt'tiott, (.'iutrrizzlrltl lcilcli()n. z\ltlol leirr'Iiorr, N,lirrrrrielr reirt:tiori. l)irr.ztilit irtirin iltltl l)iirz,leorr;llilrq l'circtiorrs. llcrrzoirr corrtlcrrsirlirirrs iurrl sclct:tivr. t'r'rltrt'ti0rr t ll' 1rtil.1 ItlII(, iil i)t) rirIic r.()rrt1)()un(ls Itrlcr't'rrt't's: L,\.1. Vtige l. .,\ 'li.rt llooli rrl'l)r'lre tit'irl ( )ig11;1ir' ('lrctrrislt.l, I lricslcr'. l,s1relirircrrt.s in ()l'girnic ('henristr-1, i. Nlirrrrr irntl Srrtlrrlt.r's. l)r'iu..ticirl ( )rgirnic ('lrentislr.t, -1. l)er'. Silirrrutlttt itttrl (itivirttllrclrirri. A l.lrtroritkrly IVlirntrirl ol'()r'girnic (-'lrt.rrristr-1 5. ('lrcloiris irntl lilitriliirt. :iollii-lltirl.tl or-grrnic intill-\,sis (r. .\.1. \zog.e'1. (-)Lrrrlillrlivc ()r'giurir: Arrrll,sis /. l'. (i. Sirrglr. l).fi. (ltt;ttit lrtttl l'..S. llrripirl. li.rpclirncrrtal Olgirrric rrnrl ll.l9tiO l'i li. Slirrivirsln. lrtl. l)lrtitoclrcrrrielrl I IN I \i ('lrr:rrristrr'. Vtrls. Syrrtlrt'sis Vols. lirnrl ll tillst'l'Y ()tf C,\t,tcl l't' ll 1.,9t:. . lppliul ('lt rttri.ttry L1 I Srnreslcl Il l)r'uclicitl Org:rrric (2 Cletlils) ..\('l'l l. {Jir:rrrtii:itivr: ( lrgrrlric -.\nitl-t -- _ si-s: I '.tirtrtiott'ul Nitt'ouctt b\ I.,.i ,.'lrlitltl ntctltotl:;. cslilrtitti()lt ril' ltr rltrrrr I itrtil t irrlrrrtn I !rr)ul):,. l)cl.-rrtrirrirti()lt ol ltttlittu' nul)tt)cl'trtirl Slrl)()ltilirlrti()ii \itlLrc ol'oil:,. l::;tirniiti(,lls oi'tt.tltr.'irrr! r,uliu- irnii)c5. plrcrrols- fslci's. rilitttrirrs (.,\ irrrrl (')irntl l)r'trp:, t.,\slririrr lrrrtl l'lLtlrc:ctitr'troI ) r Strrtlt'rl- I)t'siiinctl NIultistcll S.r rrlhcsis;rt'o.ice I: lrr ilic :,ccorrtl sclrrcslur cltclt sttttlcrrt rr ill ltitr e to tlt'r clop lr tttttltistcl r s--\ nlltr:is ploit't't lirrrilciI lrlirrt:ilrlllr [r.t cost. sirlct_t rrrLtl uvitilabilitl ol trlrtcriirl:;.'l'hc Plln:;lroulrl eiirrIirirr irt Ir--lst lirtrr :'i ntlrctic str:lls. Strbscrlttcntl\,. thc sttrtlcnts slioultl otrtirin llrril tirr n lilr:rirtule l')l()tut:(,ls lilr'thr:' inilir irlual .stclls. ,,\lict' tlisctrssion \\ ith ['ircullt ntul]r[)r'ts. tl)u\ cln :;uu'1. itttll,irrg on lheir ottrr pt'uicc1s. Ihe'srnllrcsis rrill bc 1-lcllirrrrtutl ()\('r'tlrrcc [() iirttr ticel-s. llrr-:trrrlcnts slrortltl uonclLr(le thcir'ploicut rrith ir 1-llcsc'rttltiol ol'tht'r'c:;rrlts irt tltc ctttl ol'tli(' :;rlrrcstcr'. l:r'trlulrli()lt ol the stttrlcnt ltto;cct riill lircLrs noI tinlt' orr Iltc );u('('rs\lirl :,r rillir.r:is trl'lhc till'gcl r.titrlccttlu' bttl also. tltt:ir plirttnirig- sl,ill lritl l)iittLnil\ tlicr lriir c :,lr()\\ r) ili trttutrlcsltooting ttrtcl tltc ttreril ol' tlrc ri.\l)cl'inrcnlul irrtr[ sl)L-ullill lcclutitlrrc:; tlrrr lrirvr rrscrl lor'pttlilieirtitirt anrl chalttctclizittirrti, I lrlt'r'i'r t t't's: l. .\.1. \/ogcl- .\ I crl [Jrrok ol'l'r'uctit:al Or-uanic ('[rentistt',\' ,1. I ic:;tcr'- l:,r1,,.:rinrcrrts in ()r'ganic Chenristr'1' l\ lirnn arirl ljirrrntle rs- l)r'itctical Olgirnic L'hentts;tr'\' -1 . :1 . I)r'r - Sitlrriuttrrlt irurl (itlvintlircIrali. ;\ I-alrot'irtot'i, I\4ittittirl ol'()r'uauic ('ltr:trrislry ('h,-'r'oris lrr.l lrlrtril'in- Scrni-nricnr ()r'gauic ;\rtrrl) sis -i. (r r\.1. \/ogt'1. (-)rrirlilirtire ()t'girtiic Antrl-\'sts 1. l'. (i. Sirr;rlr. l).S. (iLrl-itir ancl li.S. litrjpLrl. l:rperinrctrtirl Olgitnic C'ltcrrri:,tt'1'" \/,rls itrrrl ll - l()80 lJ. Ii Srinivlr:irrt. l:t[. l)ltoltichcnticltl St'ttlliesis \iol.s. lantl ll Z\ I SIINITiS'tEI{ Solrr I I'II YSI(JAL C]}IfiN{ ISTTTY LAI} I bility l. Dcfcluriuation o1'lleat ol-solulion ll'onr sttlLrbilitl, i1n1', (An-iurtlniLtnr oxalulc attcl sttccittic acid). N'lolcculur u'eight I I)cterntinution o1- rroleculal u,eight lionr rlepressiott in fieezirrg poiltt. [Silthcnll -Nap-rhtlralcrrc cooIing cLrrve nretlroil. l. l)ctcrntinatiorr o['rnolecular \veiBhl fi'oni tlepression in tlatisitiort point. tiooling cLlrve nrr-'1hod. (-' r'1'osco I pic S ttrtly I)cte mtirtatit-rtl tll- ct'1'6sg11pic cotrstatrts rrsing u'atet' trttt'l benzene as solvettts. ol stllvetlts and nrolecLrlar u'eight ol' uctt.t volatile sltbslatlct's fir'_l,oscopic stLtcll' o1' the reaction. 2KI + I-lglz ) I(:l-lgl+ . in \vater atttl cletet'tllinatiotr ol conccntrittirrn ol' KI soltttittti. I)cterrttination ol- cle gree ol' dissociaticln allci hellce Vant l-lofl' Iac-tor ol' an cIectl'oIt'te b)' cri'osct-r1'ric niethocl. l. l, (lonductortrett'y ('e11clur:t6pr:tric tit;atitr6s o1'clispiaceurerrt ancl precipitaliott reetctiotrs - ll('l vs Na(lll, lllC'l + I lO,A,c) r's NaOIl. AgNOr vs l(Cl. l. Dcterltipatigp o1'[tluiyaleut concluctance of strong electrolytes (l(Cl). Velilrcatiort ol'Ottsagilr' 'cclttittion. i. f)etcr.niination ot'[:quivalent conductance ol weak acid - verillcatiolt ttl Ostrvalcls i]iltrtion lari caI c tt I itt itttt o l' cl isst'rc i at i otr coustatlt. -{. I)crernrinalion of Activity coelficient of Zn in 0.002M ZnS04 using Delil'e-l-lucliel linliting lau. (AgCl, BaSOI). -i. I)i:terrrriuerti6p o1'solubilitl,product o1'sparingly soltrble salts 6. Detcrntinalior-r ol'erluivalent conductance o1'rveak acids and hettce the clissocialion cotlstatrt. 7. [)cte,1i1atigp ot'pil o1'bufJ'er solutions u,ith a p) l meter atid evalttatiotr t'rl'PI(,, r'altte ol'acicls. l. Itcfritctoltt cttl' l. r\,al),sis ol.1biriarl,nrixture altcl cleteulinalion o1'molar reI't'acliott ol'a solicl arlcl I'he ct-rttlllosititltl ol cltltl'oliirrualtd acetotle irl its azeotropic nlixtLtle by reli'actometrl'' \/ is co u t ctt')' bilar-1, ptixture o['tu,o rtrisciirle liquids lry visconretrl' atrd the relatiorl lretu'ce'll viscosity ol-a soltrtion ancl thc' electlical eondttctivib'' 1. Stucll, ol'r,ariatiort glyiscosity of a liquid rvit[ tetrrperature. l. .l'ri Anirll,sii l)istribution Litu' l. DistribLttion coelllcietll ol'12 lretweetl CCI'l 1. StLrdy ol'cquilibrium l(l + 12 ) Kl3 --j. [)etelntirtatitltl o1' cotrcetrLt'atiotl +. Deter.riratio, of cl i stlib Lrt Itcf'ct'e n i ort ttr zirrcl of KI scl]trtiorl the association constarrt Ii'O' oI a caiboxl'lic acid ilt ittl orgtttlic solYetit b1' thc etlttlcl. ccs l. z\ liincllal,, I)r'actical Phlsical Chenristrl', Lollgtlrau's Creetl & Co" 1971' l. r\ Nl .lanres. Practical Plii,sical Clienristrl'..1 A Chulchill [-td.- 1q61' I It .A,\lber.tr et. al. Irxpeliurental Phy,sical Cheltiistl'r'. N4cCjrau'I-iill.. l9-)6 -l \\,C i)alrtrer. Exlteritrierrtal Phl,sical Cheuristrl'. Canrbridge [)rliversity l)t'ess- 2'"1 L-.t1.- ]t)(,-1. 5 I) I Slroenralier.anrl C \\/ Carland. Erpelimenrs in Phl'sical Clrenristr'}'- N{c(irau'IIill- l97l .-L9 sltNll,lsl'Ett ('lrrrnical l(irretics ;t'' "' '-: It PItYStCAL ciltiNIls't'ttY [,At] tl \7 "' ' L I(inertics ol'itcicl catalysccl hyclrolysis ol'rncthyl acrrtatc attcl clctcnrinatiorr ol- (a) orrlcr untl rltc cttnstant. (b) I{clative strcttgth ol'two lcicls, c) [rnclgy ol'activirtion. l. l)ctclrrrinution ol'tenrlteruturc cocf'llcient and cncrg)/ ol- aclivntiorr ol'ltyrlro[ysis ol'rrrc(ltyl lcctirtc. I)ctcl'nrinution ol' Arlhcrritrs llarantetcrs. 3. Srrpor r i llcatiorr ethyl acctatc (litlatiotr/corrductarrce nrc.thocl). '[. Irrvclsiorr ol'canc sLrgiir irr lllescnce ot'I l('l lry Polarinrctr'1,. 5. lodirtirtiott tll'acc(ottc in acid trc-cliutr - [)etelrrrirrution ol'olclcr o[-rerrctiuu witlr rcsltcct to iorliric rrnrl itcctone. (r. [)ctclrnirration ol'dcgrcc'ol'lryclnrlysis ol'C'll3CoONa antl Nll,rCl. 7. l)ctcrrtrirttttitln rtf lryrlnrlysis constanl. ol'aniline hyclroclrloride. li. l;irst ittttl scc:tlncl ot't[rt'l<inetics ol'r'cactiou lrctwecnr polassirrm PelsulPhirLc arrcl l(1. Atlsol'ptioll l. Vcrillclrtittrt o['llrcttrtcllich lrrtd Langrnrrir aclsorptiou isothclurs. 1. [)ctcrltlitlitLiotl tll' cottcetttration ol' acctic acitl/oxaIic acicl using lireunrllich ancl arlsolpt itlt l.arrgrnrrir. isothet'uts. -i.'l'o sttrcll'lltc ltclsor;rLiott ol'iorline on chalc:tlal ll'ont alcohttlic sclltrti6p l)lrirsc cr1uilihl'ia l. l'lrase: tliitgrant ttl'a sint;-rlc cutectic systeur 2. l)lurse cliagrarn ol'a binar'1, solitl systern lirnning a conrpouncl -1. N'ltrlttttl rlriscibility cttrvc ol'a [rinary liqLrid syslcnr (phenol-rvaler') - cliLical s6lrrtisl Ir:r'rrpcprtur-t: (('S'l';- lrl'lcct ol-inrptrritics (Na('1. KCl, succinic acicl. salicylic rrcidl on llrc ('Sl'6['*,,tcr.phcrrol systctn) 4. 'lcl'ttltry liqtritl systcttt tviLlt onc llail of paltially nrisciblc liqLritls. (DlVlSO-bclzerrc-rv.tcr.. rrcctor tc-chloro lbl'rrr- rvatcr.. ctc. ). 5. L'tltrstt'ttctiort ol'plrase cliugratnr ol'tr tr.vo cornponenl systenr by tlrcnrrtrl analysis. l)olcnliourctr-y l. l)otcttIitltttctric titrations ol'acitl vs base in ptrltiirl rrncl non-aclrrotrs nrctlit. ')- l)otctttitittte tt'ic titrirtion ol'halides in nrixture5 ( (ll , ll1 alcl I ) rvith sil'cr-rri1r-iilc:. -1. I)ctcrtttittatiotr ol'1r'ansport uurnl'rcl tll'ior-rs by eurf nretlrocl 1Ag',t'cl?',NO,2-,!i()1r-. ctc.) 4. l,lcctRrdc lltttetltiitls ttl'Z.tt, Ag ancl Clu.in solutions ol'dil'l'cren1 nrolalities at 119rp le6r1-rc:r-irtr1.c and tlctcrrnination ol'thcil slanclarcl clectroclc potcrrtials. IVlcan activity coelllcictrt of an elecl,rolyte art ditl'creltt niolalities tr1, l-iMli nrelhocl. -5(r. l)issor:iutiort r:otrsllpt oI CI-l]COOll in DMSO, DMp, acetotrc and tlioxin by litrating rvitlr NaOIl. 7- l)ctcrrrrilrttti<tll ol'strettgtlt ttl'thc givcri llCl solLrtion by clillbrclttial ltstcstiorpctric titrlti,q. lJ. l)issociittiott cottstanI ttl'trcctic acid b1, polcntiornctric titratiorr ntethoil. llcl'crcrrccs l. A Irinrl lay. I)r'acLical Ilhl,sical Chc:nl1511'1,, [,orrgnran's (irecrr & co.. l()72, I l\ IVI .llrtrcs, [)r'ucticirl lrlrysical ('hcnrist11,..l A L]hur-chill t.tcl., 1961, i. li r\ Albcrt;'ct. al. l')x;.rct'inrettLal I'}hysicirl (.llrcrrris;try. IVIcCirarv Ilill., l9-5(r -+. W (i l)altttct', l-ixltcrirncntal l)lrysical CIc6tistpy. Cilstbriilgc [.Jgivcrsit), 1)r.ess,2,,,l Iicl., l9(r.1. 5. l) I"slrocrralicr irrrrl (' \\/ Garlarrd. Ilx;rcrinrc:nls in r)hl,sioal chcnristr-y, IVIcor-all, Ilill. 1974. 2u