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UNIVERSITY C}F CALICIJT
(Abstract)
MSc programme in Polymer Chemistry under Credit Setnester System (PG)-Course
structureind Syllabus of Ist and IInd Semestersr-approved -implement: d-with effect
from 2010 admission onwards-Orders issued
GENERAL & ACADEMIC BRI.NCH.IV'J' SECTXONI
Dated, Calicut l.:niversity PO, 24.07.20 I 0
No. GA IY11218619107
Read:1 . U.O.No. GAIV/JI 11373108 dated, 23.07 .2010.
2.ltemno. I of the minutes of the meetirrg of the Board of Studies in Polymer
Chemistry held on 16.06.2010
i oRDEE
As per trniversity Orderi read as fi,rst, Credit Semester System
was
implemented to the PG programmbs in affiliated Arts and Science Colteges and Self
Financing Centrer; of the University with effecl. from 2:010 admission onwards.
The Board of Studies in Polfmer Chemistry,vidr: paper read as second,
decided to restructure the syllabus of MSc prograrnme in Polymer Chemistry as
Credit Semester System (CUCSS-PG)-and finalized the syllabus of CUCSS-PG2010 of Ist and IInd Semesters of MSc Polymer Chernistry, with Course Structure.
The Vice Chancellor approved the minutes subject to ratification by the
Academic Council.
Sanction b; s therefore been accorded fcrr irnplenrenting the Course Structure
and Syllabus of Ist and IInd Semesters of MSc programme in Polymer Chemistry
with effect from 2010 admission.
Orders are issued accordingly. Scheme and Syllabus appended'
sd/DEPUI]Y REGISTRAR (G & A-IV)
lFor REGISTR{.R
To
The Principals of affiliated Colleges offsring IvlSc programme in Polymer
Chemistry
Copy to:
PStoV.C
PA to Registrar
Chairman B/SPolymerChemi s try I CEIE)VDRII I/DR,PG/EGIiEnquiry/System
Administrirtor with a request to upload in the {-lniversity websir'eAnformation
Centres/G,&,A I'F" G' Sns/GAII,III
Forwarded/B
Dti2
aa
Grrv lt*itur"rlo'r '- ak'ul'lo
No'.
0o
Sndi^SY L LA B US_ T H EO
R'' CO U RS ES
UNIVERSITY OF CALICUT
M. Sc. pOlYmBR CHEMISTRY- SEMESTER I
PCI C 0l
INORGA,\IC CHEMISTRY-
I
Credits:
4
MODI_]LE r (8 h)
Acid base theories - strength of zrcids and bases. .;olvent Ieveling ef]ect. hard ancl sofi
acids and hases. super acids. C'henristrv of non-aqueous solvcnts- liquid NHr. SO:.
H2SOr and HF. Heterogeneous acicl- base reactiorrs- sttt'thce aciditr. solid- and molten
acids in indu'rtnal processes.
MODULE rr (n h)
Synthesis. structure. reactions ancl bonding
in boron hydrides. carboranes,
metalloboranes and borazines. Svnthesis. strllcturc and applications of silicones.
Phosphorus- nitrogen. phosphoius- sr,rlphr-rr and sLrlphr-tr- nitrogen ring and chain
compounds- s.r-nthesis. structure. bort.ling ancl applications.
References (N|ODULE I and Il)
i. D. F. Shrirer. P. W. Atkins. Ci. H. Langfbrd. lnorgunit'('hemlrrr.1. ELBS. 1gcx).
2. J. E. Huhee,r-.E.A Keiter. R. I-. Keiter. lnorgunit't:hemi.;lr'1'. Print'iplc.s,.\truc'ture untl
Reacfit,i1', Pearson Edr,rcatiorr. 1 t)90.
3. F. A. Cotton. G. Wilkinson..4rilant'ecl lnrtrgunic'('hemi.stry' 5'r'Edn.. John W'ile1'and
sons. 1988.
MODULE III (20 h)
Crystalline solids. cry-stal systenrs. Bravais lattices. cr'1,stal syllntetr\. s\mmetrY
elements. transitional ancl rotational transitiou svlnnretry. point gl'oups. space ilroups,
indices. Braggs la'nr'. X- rar clittiaction.
Close packing. factors al)'ecting cr.;stal structure. radiurs ratio. coorclinatiot-t number.
lattice energ). Born- Habcr c1'cle. structure of AX. AX2. AO2. AOr. Ar- O;. ABO-I.
AB:O+ t."-pe crystal cletects. r-ror-r- stoichiometry. sltaring of polyheclra. structure of
si
I
icates.
al um i nosi
Ii
cates. tttit I ecttlar
s
i
eves. po I yox-r'an ions.
Electrouic properties of solids. hrancl theory. k- space. Brillouin zones. band structure.
Fermi level. Fermi energv. clensitv of states. nretals. insulators. semiconductors, types
and structurr o1' semiconductors. super cotrductors.
.Alloy,'s. classificatic''n. intennetallic compounds. Hunte Rotherl rLrles.
Solid state reactions, solici-solid. solid-gars and solid-liquid reactions. kinetics. thermal
analysis. borides. carbides. silicides. preparation rind properlis,s. preparative rlethods
in solid state chernistr!.
References
l. A. R. West. Solid Stote L'hcmi.str\.'uncl it.s Applit'crtions..lohn- Wilel. Chilchester. 1984.
2. F. D. Bloss. Crt,.s'tull,;gru1th.t'und (-'r.t'.stuL ('henti.ttrl'. Holt Rcinhart. Winston. New
York. 1971
A. F. Wetls . ,\lruc'ttrttl lnorgtrtic' ('ltctui,slr'1'. ( llarerrdon Press. Oxfbrcl.
A. K. Cialr.vay. ('ht:misti'.i'of .Srr/lrlr. C'hapnrzrn- Hall. l-ondon. lc)67.
.
3.
4.
I 95-1.
Harwood'
Slructur.e and Bortcling irt ,solicl stctte chemistrlt. Elliz
Chichester . 1979.
Universitl'
P. A. Cox. fha Electronic. ,Struc:tL.rrc und ('ht:nti.stt'7' rt solitls. oxlbrd
5. M. F. C. Ladd.
6.
Press.
l.L.Y,Azaroff.Introc]ttcticlntrl,solit]s,McGrarvIIill.1960.
MODULE IV Nuclear ChemistrY (10 h)
value. types of reactionsRadioactiv. J..u, una .qritiuriunr- nuclear reactions- Q
of radiation on materialschemical effects of nuclear transfbrntation, 1- recoil- etl'ects
techniques, tracer
fission and fusion. fusion proclucts and tusion yields- Radioactive
such as G' M'-'
techniques- neutron activation asalysis- couuting techniques
I
,I
I
i
ionization- and proportional counter'
References
l.J.B.Rajam.AtomicPhl''sics.S'CliandandCoPvt'Ltd''1974'
Wiley
2. J. W. T. Spinks. R. J. Wood s. An Introdtrc'tion rc Racliation Chemistry' John
3.
4.
and Sons, 1964.
Age International' 1995'
H. J. Ariikar, Essential.s of Nuclear chemi.stt'1.'+'l'Edn.. New
Book on Alorttic' Energ,v. i'd Edn" East- West Press Pvt' Ltd"
5.
Wiley and Sons'
Friedlander, J. W. Kennedy. lntt'oduction to Rutlirtchcmistry-.lohn
S. Glasston
,
Source
1967.
1981
6.
.
Edn" John
Friedlar-rder, J. W. Kennedy. J. M' Millcr.'Nuc'le ctt' trnd Radiochcntistry,3'd
Wiley and Sons.
1981
.
MODULE v (6 h)
square analysis,
Errors and treatmelt of analytical data. standard deviation. least
test'
statistical treatment of data sets. str-tdetlts tests. colllden e limit, Q
titrations in
Theory of acid- base-, redox-. adsorption- and complexometric indicatorsnon-aqueous solvents.
References
l. G. H. Jeffery, J. Bassett. J. Mepdham. R. C. Denl1'' V'ogel's Text book o/ Quantitative
Chemical Analysi.s,5'l' Edtr'. ELBS' 1989'
2. Skoog. West. Hgller. Funtlutnenttrls o.{.Tnult,lic'ctl ('ltcnti.s/r7. 8tl' Edn.. Thomson and
Brooks.2004.
vI
(10 h)
macrocyclic
Coordinationchemistry formation and stabilitl of complexes. chelate and
effect. The crystat teta and l,i-qand field theories. orbital splitting in octahedral'
series' Jahntetrahedral oni ,quur. planar tletds. spectrocheuical- and nephelauxetic
of
Teller effect. M.O. tlieory- corlrposition of ligand group orbitats. M.O. diagrams
complexes with and without n- bondir-rg'
MODULE
Standard reduction potentials and tl-reir diagrantmatic representation. Ellingharn
diagram. Latimer ar-rd Frost diagranr. Pourbaix cliagram.
2
l1
^
MODYLE
YU tr| nt
Lanthanide:
contractiott.t''u'9 actiniclcs-'\l
,!;,i:.,,.;1:; ;,::;
t.un,,. ri,, ia;;
n
Jll;li
ra
''''' Juttcrirres'
;l:lil::,l"illli,l,
scpi''ari,,, ,rr n rh an ide
lxnirl,',,i..I
erelnelrts'
/
References (
Mor
D. F.
2' J. E. Huhee
and
3. F. A. Co
Sons. l9gg.
Shrir,
]
,,;"'r'r.fil[1:
)
.,.l.itrrsfirrd.
lrrt.,gtrtti
r\ eficr. ln.rgcrr,r
EI-BS. t990.
rtemi,s.tr..t,, principles
-!"'rL \..i.l'!'nistry'.
n. 1990.
,\ttruclure
,unt.cd lnorgunic,
(,hemi,srr1.,,
-5,r, Edn.. .lohn
Wile-v.
Req
_
:
and
MODLILE
\A,'IS
MODULE
I
II
II]
IV
V
VI
VII
E WE IGTITAGTJ FOP.
Q I i t: S ]'IONS
WEIGFI-I.AG
5
---
\J
/
PCl C02
ORGANIC
CHEMISTRy
Credits:
I
4
HYtirttgen Bonding'
tntt'- and intramolec
ac
bonding' Volatilit-v'
Stabilizati or-r of hYdrat
Points of ethancr
nitroPhenol and
strength of nlale
lI
(10 h)
B n.s i c C:'in,j'I p''' i tt
MODULE
th
e
S t u d1' o
l' O r gun i t:
R
c
ttc' t i o,tt'\4 a c h
uni
sm
s
Thermodynamic and
control'
to mechanistic studies'
Applicarion of Experimenr;i lrl?.rin
ri"tiit 'ersus thern-rodynamic
kinetic data. Cr-rrtiur- Ho#.i pri,r.iprt''
Acidit;,Constzrllt'Hatrrtrretaciditl'tltrctitln..Reactir,eintermediatesandtheir
stereochemical correlations'
(labeling experinlents)'
characterization. Isotope eff'ect
theorv. Potential e.nerg,v vs Reaction coStructure and reactivity. Transition state
(incluctive. ntesttnteric, inductorneric. electonieric
ordinate cllr\re. Substittre,t eftects
q,-,oii,o,i'e studv of substitution eftbcts changing with
and Setd eft-ects) on reactiviti,.
study of substitr-rent effects on
mechanism i, Sxl - Sx2 1.eu.tio,.,,. Semiqr.rantitatire
efl'ects on
the aciditv of carbox.vlic acids. er-rantitative correlation of substituent
equation fbr polar
reactir ity,. Linear free energl relationships. Hattnmet and Tafi
effects and Taft's steric substituer-rt L)onstant tbr steric ffbct.
References (MODULE I and II)
1. J. March. .4clt,crncetl Ot'ganic'Chami.str'.t'.4'l'Ecln...lohn tr/iley and sons. 1992.
2. f. H. Lorvr)'. K S.Richardson.lt4at:huni,s'nr und TheorT,'in Organic ()hentistry, Harper
3.
4.
Collins. 1987.
F. A. Carey, R.J.Sr-rndberg. .4rh,cu'tt:ctl Orgunic'('hemistry (Part.s A & B),3'd Edn.,
Plenum Press. 1990.
R. A. Y. Jones. Phy,tit:al ond Mcc:honistit' Organic C'hemisrry, Carnbridge University
Press.1979.
MODULE lll Isomensrr (10 h')
Dissvmntetrv. asymmetry and chiralitr,- sirlple and alternating axis of sl,mmetrvConditions for optical activitr,. Isotopic asymnretric variation ancl specific rotation of
the sanre compound in sigr-r and rrraenitude under clit'lercnt corrclitious. Relatiye and
absolute conliguratiorts. Secluence rulc- R and S notations in crclic auij acvclic
compounds.
4
asvmnretric carbon atoms'
centre'
.Prochiretl
and vapour
liqLricl
solid'
in
bstituents ar-rd their size in
states. Strltctr'tre of substittrtecl hiphenyls
notatiotr' Atropisomers' Restricted
relation to the stabilit-v of optical r-st)lllers. R antl S
Chiralit-v due to tblding of helical
rotation in biphenl'ls - N4olecrtltlt' or'ercroudirig'
Optical isomerism of cotlpor'rncis crlntaitrin
Enantiotopic. Honlottlpic. biaste'eott'rpic hr'
optical isomerism in Biptrcny'ls. Sttttcture
structures.
cotnpounds- R and S notation'
conditions fbr optical activitv in nllenes and spiro
naming- stere.chemistrl
Optical isomerism of nitrolert and sr-rlphLrr compoundsConditions tbr optical acti\ it\'' R and S notatton'
'
compounds rvith one atld rr-iore double
Geometrical isomerisrn - F. antl Z notation of
of detennination of the contiguration of
bor-rds in trcy-clic systelns. lVlethocls
interconversion of geonretrical
geometrical isomers ir-r aclclic ancl c)'clic svstems'
isomers'
,, r , .:- -.- ^..,r r..llamlng
Stereochemistrl' of iildorirnes aud ketoximes ilnes'
ketox
tues and
determ ining coill r gurzititlns of al tlori
-
isomerisnt
-
methods of
References
wite,v and Sons' 19c)2'
1. .T. March. ,4dvancecl orgunic ('lrcnti.st11'..1'l'Edn...lohn
(':nn''p"'n'l''.2'"r Edu ' Ncrv Age International'
2, Nasipuri. ,stererchemi.s,try rl (lrSlr rii,
Eastern'
3. Kalsi. Stct'eochenri.rrr.r' ,r1 {),'gtiltit'contpottntls' wile1"
Suggested Reading
o/' Orgunic' Compottncls. John
E. Eliet- S. H. \\/ilen ' '\tarL'oL'hanti'strt
\fu
iler'. I9t)4'
(16 h)
MODULE IV Conformational '\nal1'sis
Conformaticlnanclconfigurati.,n.lnt.,,.lt".,.,',af1-ectitrgthecontbrmatiotr-dipolar
interaction- bond opposition straitr'
bonding. Sawhorse and Nelvmarn Pl
confbrmatior-rs' Cl ol-rfbrlnttti tl t-ts of ac
dihalide- glycols' chlorohr clritrs' trrc-trt
of c)'cltlhexatrc' col
rc
Conformation
cyclol-rexanes. confilrtltatiot-t
grotlp.
ol'
clecal
Debrominatioti ol dl and nte'so-2'3'
Effect of contormation ()Ir reactir',itr' of stilbene drhalidcs (c1l and me'so) and
dibrornobutane rvith KI. clehl'dr,)g.nution
er)thro- atld threo- 1 -brot-t-to- 1 '2-diphenylpropatl"-^'
,oi" of reirctions - Sn l lrncl Srl reactions of
Effect ot'contbrmatior-r on the coulse "ni
of
sttbstitr'tents' [: I ancl E2 elrnlinations
axial ancl equatorial
(i)'1-t-Butylcyclohexl'ltosllates(c'isanc'ltrun't)'
(ii) 2-Phenvicl'clohexatrols
(iii)N4entlrl,Iattdngottlerrtlrrlclrlorrdes.andbenzetreilc'xachIoriclcs.
EsteriilcationolaxialzrncleqLlatorialalcolro[sarrc]acids-theirhvdroll.sis.
its
oRDanc]CD.Plancanclsingle(.Ecur.,,es-uSeS.Axialha[oketolleruleand
of co.fbrtnation and cor-rligLrration ol
application. Octant rule- Deteimination
Methylcycloheranone-
()RD ctlrves of
ci
s- artd lrttns'decaiones
J-
References
l.
Nasipuri, Stereochentistry o/ Orgtutit'('ompouncl,i'. 2'"iLic1n.. Neu Age International.
2. Ef iel. Allinger. Anggal, Morrison. Conlbrntulionul unaly,.sis'. Wiley International.
3. I. L. Finar. Organic ()hentistry,, L'ot. lt^ 5'r'Edn.. ELBS. 1975.
MODULE Y Reactions of Carbon-Heteromultiple Bonds (6 h)
Addition to carbon-oxygen multiple boncl: Addition of water, alcohols, amines and
h1'drazine. Aldol. Claiser-r. Dieckmann. and Stobbe condensation. Darzen.
Knoevenagel. Wittig, Manrrich and Prins reactions. MPV reduction and Oppenaur
oxidation. Cram's rule. Hydrolysis. alcoholl,'sis and reduction of nitriles. Ritter
reaction and Thorpe condensation. Clemmenson and Wolf- Kishner reduction.
References
1. J. March . Ath:ancecl Organic Chcnti.str'1,-4'l' Edn.. .lohn Wiley' and sons. 1992.
2. N4orrison. Boyd. Orgunic' ('herni s,rr.y,-. Plentice [{all.
3. F. A. Carev. R. J. Sr-rndberg..4dt'uncccl Orgunic'Chenti.stry (Pctrt.s'A & B).3'd Edn..
Plenr,rm Press, 1990.
MODULE Vr (14 h)
i) Electrophilic and Nucleophilic substitutiott in aromatic systems. (7 h)
Friedel-Crafis alkylation and acvlatior-r. Orientatior-r in monosubstitLrted benzene.
Ortho-puru ratio with reference to electronegatir itv and steric factors.
Nucleophilic aromatic substitution. .Aronratic diazonir,rm ions as sy,,nthetic
intermediates. Nr.rcleophilic substitution as illustrated b1, the hydrolysis of 2,4dinitro-chlorobenzene. Ar.nination of pyridine bi,, sodamide (Chichibabin reaction).
Ar1'ne mechanism. Examples. Detection ol benzyne intern-rediate. orientation of
additior-r. Structure of benz1,ne.
ti) Nucleopltilic Substitution ut Suturated Carbon ond Elimination Reactions (7 h)
The fbur types of nucleophilic sLrbstitution reactions based on charges on the
nucieophile and leaving group. Nucelopliilicitl,and size of nucleophile. Eff-ect of
changingthe basic nature of the lear,'ing groLlp. Eff'ect olsolvent polarity - sol.u,ent
etTects on nucleophilic substitution of different charge types due to Ingold y-value
and Dimroth parameter.
Stereochemistrl' of S51 and S52 reactions. Reactions of epoxides and quaternary
ammonium compounds. NeighboLrring group participation- participation of
carboxvlate ion. l-ralogen. hyclroxyl group. acetox\/ group. pheny,,l irroup and n bond.
Elimination at Bridgeheaci carbon - Bredt's rLrle. ('i.r elirninatior.r - pvroll,sis of esters
and Chugev reaction. ElcB mechanisnt
References
1..1. B- Hendrickson. D..1. Crant. Cl. S. Hantrnond. ()rganic Chemi.str1,. McGraw Hill
Intenrational Book Compan),. I 981.
2. Morrison. Boyd. Organit. Chanti.str.l.. prentice Hall.
3. J. iVlarch.Aclvttnt'ed Orgunic'('ltutti,str'.t. -l'r'Ecln...lohn Wilet,alcl Sops. l9c)2.
\
(l
.a
-^
4.
B. Hendrickson. D. .T. Crani. G. S. I-lammond, Organic C'henti.vtrt,. McGraw Hill
Intemational Book Company. 1 98 I
Morrison. Boycl. Orgunic' C'hanti.s'rry'. I'rerttice Hall.
.1. Marcl-r. At)vctnced ()r,qurric'CltL't?ti.\tt'.r'. +'l' Edn...lohn Wiley'and Sons. 1992.
F. A. Carcy.R..l Surrdberg. .-1tlt'unc'cd Ot'gunic'('hemi.strt,(Purt.s.,1 ct B).3'd Edn..
Plenum Press. 1990.
.1.
.
5.
6.
7.
Yll Photochenticol
and ElectrochemicalSynlftesrs. (6 h)
reactions. Electrochemical oxidation and reduction
electroorganic
Basic concepts of
reactions. Cathodic reduction ol'urganic fr-urctional groups like halo. nitro etc.
Electrodimerisation and electropolvnrerisation reactions. Electrocherrical sensors.
E lectroox idations.
Industrial applications of organic photoc-hetnistlr
MODULE
.
References
1. A. .1. Frr,. ,S),nthctic' Orgtmit'
2.
3.
[:.'lcc'troc'hetnistr.t'. Harper and
I{orv Publishers. New
York.
R. O. Kan. Orgunic Photc t'hcmi.rrry. N4c Cjrarv Hill.
D. R. Juliarr. Indusrriul .Aspet't.s of Hetuocrclic Photctchenti.stry. (O. Buchardt Ed.).
Wile."- Interscience. Neu, York.
MODTJLE WISE WEIGHTAGE FOR QI.,IES'IIONS
MODULE
WEICiI-ITAGE
I
7
II
7
III
7
IV
ll
,+
VI
l0
VII
l
7
PCI C 03
TH EO RETI CAL CHE\I I STR Y
I
Credits:
\z
4
MODULE r (10 h)
Mathemutical Concepr.r (5 h)
Co-ordinate systems: Cartesian. c-vlindrical polar and spherical polar coordinates and
their relationships. Cornplex uLrnrbers: definition, complex conjr-rgate, absolute value
of a complex number. complex functions. Operzrtor algebra: lir-rear and nonlinear
operators. Hern-ritian operators. clel and del-squared operators. Eigen function and
eigen values of an operator..Eigen l'alue equation. Eigen lunctions of commuting
operators. Well behaved functions. Normalized ar-rd Orthogonal functions.
1)
il) Quttntum Mechanic,s, - A Histor.icul S'ketc'h 15 h)
Blackbody radiation and Planck's quantun'r postr-rlate. Einstein's quanturn theory of
radiation. Milliken's verification of Einstein's photoelectric equation. Wave-pariicle
duality of radiation. Compton effect. Lor-ris de Broglie's matter waves, Electron
diffraction. Heisenbers's matrix mechanics (mention onl1,). Uncertainty principle.
Schreodinger's wave mechanics, Dedr-rction of Schrodinger equation from classical
wat,e equation.
MODULE rr (8 h)
i) Po,stulates of Quantum ll,let:httnic's (4 h)
Detailed discussion of postulates: State firnction postlrlate. Operator postLrlate. Eigen
r"alue postulate, Expectation value postLrlate. Postuiate of time deper-rdent Schrodipger
equation of motion. Cottservative s)'stenr ancl lime-independent Schrodinger equation.
i|) Quantunt Machanic,s' of' Tr.an,s. I utional A,lot ion (1 h)
Particle in a one-dimensional box. inrporlant f'eatures of'the problern, Sy,mmetrv
ol
the rvave functions. Particle in a three-clinrcnsional box, Separation of variables.
Deeereracy- Synrmetrl, brcaki.g. rntrodr,rction to Tunneling.
MODLjLE rlr (10 h)
i) Quantum Mechanic,s ct/'ltibrcrtioncrl Motion (5
h)
Harmonic clscillator (con-rplete treatment): N4ethod of porver series.
Hermite equation
and Hermite polynomials, Recurssion fbmrula. Roclrigue's formula.
Wave functions
and energies. Important features of the problenr. Hannonic oscillator
and molecular
vibrations. fhree-dime.sionar harn.ionic oscillator.
ii) Ouontunt
Mec,hanic,.s of Rotcttionul Motioti (_5 h)
Rigid rotator (complete treatmeut): The rvar,e equation in spherical
polar coordinates.
Planar rigid rotator (or Particle on a ring). fhe Phi-equation.
Soiution of the phiequation, Handling of Imaginar)' wa\/e firnctions. War,,e lunctions
in the real fbrm,
Polar diagrams.
Non-planar rigid rotator (or particle on a spherc). Separation
of r.ariables. The phiequatiot-t and the Theta-ecluatir-rn rrr.rcl thcir solLrtiois.
Legendre and Associated
Legendre equations. Legenclre ancl z\ssocratecl Le_qenclre pit[1,nor-nials,
Spherical
harmonics (lnlaginarl' anci real lbrnrs) Polar dia-urams
of' spherical harm.nics.
Spherical harmonics as eige, firnctions o1'angLrlar ,ronrentun-,
np.rnto., ;-f^;"i.,
Quantisaticln of angular momenttttn. An-sular rlomentuur quantllm numbers.
Space
quar-rtisation.
\
MODULE IV (l t
h)
['ike Atttttts
Quantum hfuchrtnics' ttf' Hv'drogt:nThe wave equatiort in spherical polar
Potential .n..gy of hr,diogen-like s)stems'
'the
R. l-heta and Phi equations and their
coordinates. s]pu.atl.-,n oi . ariables.
and
polynomiais' \t, a-re ..tunctions
solutions. Laguerre and Associated Laguerre
functions ancl Radial clistribution
energies .f h,vdrogen-like atoms. Orbitalsl Radtal
(Spherical harmor.rics) and their plots'
functions and their plots.;\rlgr-rlar tirnctitlns
Orbital diagrams'
l'he postulate of spin byExplanation of tl,vdrogen spectrLtl.n. Fine strLlcture'
Schrodinger cquation fbr h'vdrogen
Uhlenbeck ar-rd Goudsmith. Dirac's Relativistic
atomanddiscoverl,ofspin.Hvdrogenrvar'efunctior-rsinclr-rdingspinorSpirlorbitals.
Constructionofspino,bitol'tl.tlnrorbitalsanclSpinfurrctions'
MODI-TLE V (12 h)
Methods (6 b)
i) Quantum Nlechanics ttf Mctnv- Elecrron ,4tontscmd Approximation
Many-bodyproblem.Approxinlationnrethods.Independentparticlemodel.
Distributionofelectronsintnatlr,electronatoms.stoner'srule.
tlreorernwithproof.lllustrationofvariationtheorem
Variation treatment for
1o-*;1 tbr particle in a 1D-box'
s;.,
h d ( n o n - d e g e n e r at e c a s e
il::'
#'e:Lffi
llX. ru.tl
"
i'vith slanted bottorn'
a lD-hror
only). Illustration bl, application to paiticle ir.i
Perturbationtreatmentof.thegrottndstateol-thel.reliumatom.
method Slater's treatment of complex
Field
tI{F-SCIF)
Hartree-Fock Self:consistent
tbr calculating Slater orbitals'
rr.tles
atoms. Sf ut.,lOrUitats. Stater's
(l h)
Electrort S'pin in NIttnt'-EleL:tt'ol1 '1tttms
-, -^+,.-.^ ,-r.
atoms' Symnretrtc
for man-v electron
spin
construction ol rvave tirnctiorls inclr-rding
i1)
andantisymrnetricwa\'etirrrctiorls.Pauli'santisvnrnretryprinciple,Slater
determinants- Pauli's exc I ltsitl n pri rlci ple'
itt)VectorMoclelo.fAlottl:unclspet.,trtlsc,tlpic'.|erms(3H)
couplings' LS cor"rpling and Spectroscoplc
cor-rpling of angular mornenta. LS and J.latot-t-t - the f-rne structure of
ternl slmbols fJr at.ms. F.lecrronic spectrunr,',tnratog.n
H,, Iine olthe Balnler selres
MODULE Yl Chemicol Bonding / (l i h)
i) Schrodir-rger equatiori fbr a nrolecul
ii) Molecurlar Orbital (MO) theory t4
MO theorY of H1- MO tl-reor1'
molecules L,:' Be:' C:' N:' O:' It'
NO. F{F Correlation clizrgranls'
for diatomic molecules'
Bond (VB) theory'15 h)
Valence
iii)
Boncling in BeHl' H:o'
vB tSeory,of H]. vs tt-,.;,-,.1 ,rf n-,,,r. complex molecules: Examples: Methane'
Hybridization'
NH3. orbital overlap. Molecular geometry.
Water,Ethylene.anclAcet.v.lene.Multiplebonds.VSEPRtheorl,.
MODULE Yll Chemical Bondins /1 (10 h)
, MO Theory.for More C)ontplex iV[oleculcr (6 h)
HMO theolv of lilear conjugated hydrocarbons (Ethylene. Butadiene, Allylic
anion). Charge on an atom, bond order'. Calculation of free valence. HMO theory
of aromatic hydrocarbons (benzene). F-ormula lor the roots of the Huckel
determinantal equatiol, Frctst-Huckel circle mnemonic device for cyclic polyenes.
ii) Intern'tolecular Fot'ccs (5 h)
lntermolecular fbrces - ion ciipole. dipole-dipole. ion-induced dipole. dipoleinduced dipole and dispersion interactions - n'iathematical expressions - donoracceptor interactions - Lennard .lones potential.
References
F. L. Pilar, Elementary Quantunt C)henti'stry^ McGrau'-Hill. 1968.
1.
2, P. W. Atkins. Molecular quanlunt ntec'hanic'.:.2'"1 Edn.. Oxlord Unil'ersity Press, 1983.
3. M. W. Hanna, Quantum ntechcutics in C'hemi,str-r,.2''d Ec1n.. W. A. Benjamin Inc.. 1969.
4. I. N. Levin. Quantum Chcmi.strt,.5'l' Ecln.. Pearson Education Inc.. 2003.
5. D. A. McQuarrie, Quantunt Chenti.strl'. Ur-riversitl' Science Books. 1983.
6. J. P. Lowe, Quantum C)hemistry.2''d Edtl.. Academic Press Inc.. 1993'
7. A. K. Chandra, Introduction to Quantttm C)hemistrl,', Tata McGraw-Hill. 1994.
8. L. Pauling, E. B. Wilson. Introclut:tion to Qtruntunt Mechanics', McGraw-Hil[, 1935 (A
good source book for ntany derivations)
(). R. L. Fturr).Jr., Quanturn Chen-ristr1. Pretrtice Hall. 1c)81.
10. R. K. Prasad, Quantunt C'hemis'tr1'. 2'"1 Edn.. Neu'Age lnternational. 2000
M. S. Pathania. Quantunt ()hemi.str1,' uncl Spcc'tro.y(:opy' (Problem.s & Solutions). Vishal
1 l.
Publications. 1984.
MODULE, WISE WEIGHTAGE, FOR QUESTIONS
MODULE,
WEIGHTAGE
I
1
II
6
III
1
IV
1
8
VI
8
VII
7
l0
^
NI. Sc. POLrY'NlhR L HEN{!S]'R]y'- SEMESTER
PC2 Cl 0.1
ORGANI(' CHEI'I$TRI'
MODULE I Pericyclic Reoctiorrs (10
II
II
( rcdits: -l
h)
Defir-rition and types of pericyclic reactior-rs a)cl,cloaddition and cy'cloreversion
(b) electrocl'clrc ring closurc ancl rin!r openine c) sigmatropic rearrangelnent.
Stereochernistry of pericrclic reactions and theory of molecular orbital s)'mmetry.
Application of theory ol n-iolecLrlar orbital svmn'letrv b,v the method of corelation
diaglam fbr c.vcloaddition ant'l electrocl'slic reactions by both thermal
photochemical paths. Stereochenristn' ol pericl'clic reactions- thermal
and
and
photochemical by methocl ot' trirttsitiotl statc i.lrontittlclt\'.
Stereochentistrv of pericy'clic reactions b1' FMO.
Selection rules. Sont mel et- tlaLr ser. (i ope ancl C l ai sen rearralt gements.
References
1. T. H. Lowr-v. K. S. Richardson. N[cchani.sm tmd'|heory in Orgonic'('hemis'tr1'. Harper
Collins.
2. S. H. Pine. .1. B. Hendrickson. D. .t. (lram. G. S. Harnmond. Organic Chemi,slry. McGraw
Hill International Book Company'. 1981
3. F. A. Carey. R. J. Sundberg,Atlvctnc'etl Or,qttnic'('hentistry (Part.s.4 & B). 3'd Edn.. Plenum
Press. I 990.
.
i)
ll
Chemistr-,- o.[ Free Rdic'uls ond Pltotochemistry (12 h)
Stabilit_v of free raclicals. Forntation ancl detection of fiee rac.licals. Structure and
MODULE
stereochemical properties ot' radrcal intermediates characteristics and reaction
mechanism ir-rvoll,irrg radical intermediates. Free raclical substitution and additiotr
reactions. Rearrangement and fiagnrentaticln reactions. Carbenes and nitrenes.
Fundamental Concepts. Moleculzrr excitation. Jablonski diagran.r anc'l the singlet
and triplet states. Photosensitizatitrrl.
Reactiorrs involving the oleflnic doLrble bonds. reactions of carbon,vl compounds and
reactions of aromatic compounds. Photoreduction. Di-pi-methane rearrangement.
Barton reaction and photo Fries rearrangement. Mechanism of photosynthesis,
photochemistry of d-ves and pigrner1ts. photochemistry of rision.
ii)
References
l. T. H. Lor,rry. K. S. Richardson. llechuni.rm ancl Theory'in ()rganic'('hemis'trt-.
Harper Ctrllins.
2. J. Marct-r.Atlvanc'ctl Orgunit'('henti,stn,.4'l'Edn.. John Wilel'and sons. 1992.
3. F. A. Clarey. R. .1. Sundbers..lth,unt'acl Orgunic Chcmi,stry (Pcu'ts.4 & B).3'd Edn..
Plenum Press. 1990.
4. R. O. Kan^ Orgctnic' Phrttochemistrl'. Mc(iraw Hill.
()rgctnit' Phtttochenti,st.y'Vol. I & 11, Marcel Decker.
-5. O. L. Chapman.
6. F. A. Carey. R. J. Sundberg,.,ltlt,rtncct) Orgcrnit'Chentistry, (Part.s .4 & 81.3'd Edn.,
Plenum Press. 1990.
l1
a
Rearrangements (6 \)
atoms'
Rearrangement involving electron detlcient carbon. nitrogen and ox,vgen
Beckmann.
Wagner-Meerwein. Dienone-plienol. Woltl. Hoffn-rann. Curtius. Lossen.
Schmidt and Baeyer-Villiger rearrangements'
Orten'
Anionic ..u.runj.*ents:-Benzil-benzilic acicl and Favorski rearrangements'
MODULE
lll Molecular
\
Claisen and Fries rearrangements'
References
Longmans,
1. P. Sykes - A Guide Book to Mechanism.s in Organic Chemistry, Orient
2002
2. S. H. Pine, J. B. Hendricksorr- D..l ('raur' G S Hammond. Organic ChemistrY'.
McGrar.v Hill International Book Companl'. I 981 '
and sons, 1992.
3. J. March . Aclvanced Organic Chenti.stt'1;' 4'l' Edn" '[ohr.l Wiley
MODULE lY Organic Spectrosccrpl' ( l8 h)
Application of UV, IR, NMR. and N4S in the strlrcture elucidation of organic
co-pounds. Problem solving approach (l nstrumentation not required)'
{JV: Characteristic absorptior-r ottorganic compounds - Empirical rules for calculating
absorptior-r maxima of dienes aud enones'
alkynes,
1R: Characteristic group absorptions of organic molecules - Alkanes, alkenes,
mononuclear arornatic hydrocarbons. alcohols. phenols. ethers. carbonyl compounds,
amines. amides and nitriles.
Nl7lR. The chemical shift. Local diamagnetic shielding and magnetic equivalence.
Spin-spin coupling ar-rd coupling constants. Cioupling of protons to other nuclei
quadrupole Uroaaening. First and second order spectra. Homotopic, enantiotopic and
diastereotopic protons. Spin decoupling and dor-rble resonance, Vicinal and geminal
coupling in rigid systemi. High resolrtion NMR. 'tC .h.-ical shifis. Correlation
charts. Proton coupled, ofT resonance decoupled and noise- decoupled spectra.
NIS: Determination of molecular nrass. lv'lolecLrlar fbrmula tionl isotope ratio'
Fragmentation pattern in clifterent clzrsscs ol compor-rnds. Modern techrriques of
ionization.
References
l.
R. M. Silversteir-r. G. C. Basslar. l-. C. Morrrll, Spectroscttpic ldentification o.f
Orgunic Compottnd,r. John Wile.'- and Sorls Inc.. 1991.
2. W. Kemp. Organic Speclrt;scr4.,,r 3"1 Edn.. N4cMillan. 1991.
i. P. S. Kalsi, Spectroscopl,of Ot'gunit'()ontprLunds, Neu'Age lrrternational. 1998.
MODULE Y Organic Reactions qnd Mechanrsras (8 h)
Robinson annulation, Birch reductions, h1'droboration, Favorski reaction, Stork
enamine reactior-r, Michael adriition. Sharpless as1'mtnetric epoxidation, HofmannLoffler- Freytag reaction. Shapiro reaction and Ba,ver- Villiger reactiot't.
References
1.
F. A. Care)-,
R
J.Sr-urclberg. Atlt,unc:ad orgunic'C'hctnistry (Purts
A A D,3'd
Edn..
Plenum Press. 1990.
2. Fl. O. House. Principles o/ (h'gtrttic',St n/ht'.r'ri'
3. .1. March, Advancetl Orgctnic'('lretni.stt'1'.,+'l'Ecln.. Jol-rn Wile1, and sons, 1992.
t2
at
a
<
MODULE Yl Helerocyctic Compounds utttl N'uturol Product Chemistry (8 h)
Structure. synthesis and reactior.rs olpvrazole. irnidazole and thiazole. Sy'nthesis
of uracil. thymine. cjvtosine. adc.nine. guanine. cat'feine and pyrazine. Biosl,nthesis of
alkaloids. terpenoids. steroids. carbohvclrtttes and proteins.
'
Reference
1. l. L. I:inar. Orgunic
('hemi.str.t'l'ol ll. -5'l'Edn.. FTLBS. lc)75.
MODULE Yll Synthetic ReogenLs (1() h)
Uses of tlie fbllorving reagents in organic synthesis. Complex metal hydrides.
Gilmar-rs reagent. lithium diisopropy'l anlide (LDA). DCC. 1.3-Dithiane (reactivity
umpolung), trimeth-vlsil1,l iodide. tri-n-but.vl tin hydride. OsOr. DDQ. SeO:.
Woodward and Pre'u,ost l-rydroxl'lation. phase transfer cataly'sts. crow'n ethers and
Merrifield resin. Peterst-rn's s_vnthesis. Wilkinson catalyst and Baker ),east.
References
l. F. A. Carel,. R .l Sunclberg. .7clt;unt'atl Ot'gctnit; Chami.strt'(Pttrts.l & B).3'd Edn..
Plenutn Press. I990
2. H. O. I.louse. Principle ,s o/ Orgunic ,\i1'n77r'ti.t.
3. J. March. Atlyuncetl Or,qcutit'('ltentistrl'.4'l'Edn...lohn Wiley'and sons. 1992.
MODULE WISE WEIGHTAGE FOR QUESTIONS
MODULE
WEIGHTAGE
I
1
II
u
III
+
IV
li
5
VI
6
VII
l
l3
PC2 C
05
PHYSICAL CHEMISTRY
I
Credits:
4
MODULE I Thermodynamics I (t2h)
i) Review of first and secottd lau's.'T'hird law of thermodl,pamics.
need fbrthe third
lau'' Nernst.heat theorem. Apparent exceptions to third
law, Applications of third lar.r,
Determination of absorute entropies. ResidLral entropv.
Detennination of relations connectirrg the therrnodynamic
partial derivatiyes by, the
method of Jacobians (discussion to be confinecl to closecl
theimodl,.namic
systems).
i) T h e r mo cly nam i c s. of ,So lu t io n,s.
Partial molar quantities. cherl1ical potential. variation
of cthemical potential w,ith
temperature and Pressure- Partial molar volume ancl
ru lrr
its uw(vrrrrtrrcrtrull
determination. Gibbs-Duhem
s of icreal atrd re
f
ations. Activitt,.
i
f
solvents). Duhen
solutions. Deduct
cryoscopy and osmotic presslrre. Non_ideal
Excess functions - excess free energr'. excess
entropy,. excess enthalpy und
volume.
MODULE
ll
,
.*..r,
Thermotlynamics 11(g h)
T h e r mo dy nam
ic
s,
o/' I r r ev
equatron.
ersibI
e l,
roc
e s,s. e,s,
versibre processes. General thec'rry of non-equiribrium
tion. 1'he prreno,re.ologicaI relations. onsager reciprocal
e theorl' of drlfusion. therrnar difTusion. trrermoosmosis
and
diff'ere.ce. Erect'okinetic effects. The Gransdorf-_prigogine
i.i1.r. East-West. 1973
4
5.
6'
'
8.
7
International.
3;,1,#i?Xlli;li
Easr-Wesr. l9g6
to (.,hantic,ul fhermoch,ncrntic..;.
,tn
Simon. phy,yi1,6,1 (.hentisrr.y,,
.,1
Neu,Age
Motcctttar Approach. University
K..1. Laidler..l. H. Meiser. B. C. SanctLrar.r. p/r1
ricul (,hcnti.y/ry, HoughtonMifflin
New york. 2003.
Prigogine' An Intrrtdttclion tc-t Thcrntocll,nuntit:.\'
of'rrret.e1.tible prctc,e.s,.re.',, Interscience.
B' G' Ky'le ' Chemical ond Prr,tce.t.s 7-hcrnutdl;narrics'.2"d
Edn., prentice Hall of In.ia.
G. K. Vemulapalli. physical (.hcnti.s.tt.t,.prinrice
Flall of India.
Compan,n-,
conductiorr _ Derivation of Debye_Huckel_
1'e-FIuckel-Onsager equation and corrections.
tior-r. Ctonductance ratio. Deby,e_Falkenhagen
ii) Activitl' and activitl coelficients ,1' electror1,1s5.
Ionic strength. variation of
acti'itv' coefficient u'irh concenrrarion.
ji"ri,ing law
D.,;t;,i;;f
o.b1,.-tt,,.[.i
and
its various fbrnrs. Qualitati,e ancl
c1Lrantitr,i.," ,"iri. of t[e D.t,1,=rj.-or.r li.riting
t4
\
-\
MODIILE lY Electrochemistrv -
II tl0 lr)
Polarization. overvoltase aitrl lroltrrounrphr. Electrolytic polarizirtion. dissolr-rtion and
deposition potentiaIs. concerrtratit'ru polariz-ati<tn. Decorlposition voltage and its
deternri,ati.n. ()r''er
- hrclroge. o'er roltage. oxvgen oi,cnoltage. rnetal
'oltir5rc
deposition tlver vtiltasc anii therr cletermination. 'lheories ol orer r,oltzrge - Ionic
difftrsion its the slou, process - Principles ol polarographr. dropping mercur),
electrode. the half \\'avc potential. Elc'ctr.ode kinetics.
References
1. S. Glasstotte. lnlroclt.tc'lion to Elec'troc'henri,s/r'r', East-West Press Pvt. t.td.. 196-5
2. D. A. Ivlclnnes. The Principle.s of'Elcc'trochcmi.strl', l)over Publications.
3
J. O. M. Bockris. A. K. N. Reddl .l,lodern Elet'troc'ltenti.str1. I\tl luntl II. Klun'er
Acadentic / Plennnt Publishers. 2000.
MODULE Y Surftce Chemistry und Colloirl.s ( l0 h)
Langmuir's unimolecular theorv of adsorption. Aclsorption isotherms. BET equation.
derivation. determination ol sLrrface area ol aclsorbents. heat of adsurption and its
determination. Gibbs aclsorption isothernt.
Colloids: Clolloidal surfhctarnts. classification - cationic. ionic and ionogenic
surf-actants. Micelles - caLrses of micellar formation. Micelle structure.
Deterntination critical micellar concentration stabitizing action of surfactants.
Practical importance of colloidal sLrrlacttrnts - Tannins and dyes.
MODULE Yl Photocheruistry t8l'tl
Radiati"'e and non-racliatii'e transitions
-
chenrilurninescence photoluniinescence,
inesceuce. h io ir,rm inescence. thenno Ium inescence.
fluorescettce, theolr ol'fluorescence. stokes antistokes and resonance tluorescence photosensitization - sensitisc'd fluorescence - qr-renching of t'luorescence. Theory of
quenching of f'luorescence. Principlcs of Lrtilization of solar energv- solar cells.
cathodo lunr inescence.
e
lectrolr-rrn
References
l. F. Daniels. R. A. Albertv. Phlsical ('hcmi.slr.y,. --.'r'Ecln.. Wilev Fastern. 1980.
2. S. Glasstone. Pftr'.ric'ui ('lunti.stn'. l\1ac Vlillan and Conrpanr. 1962.
3. G. Ra1. I-1. Misra. Photoc'hanti r/r'r. Goel PLrblishing House.
4. P. W. Atkins, Phl,sical ('hentistrv.6'r'Edn.. Oxtbrcl [-lniversitv Press. 1998.
5. C. H. Dupeg, R, L. (ihapntan. llctleculur Reac'tions und Photochemi.strl,. Prentice
Hall.
6. Cox. Kemp. I nt r rs cl u t' I or),, P h o I o c' hc mi:' tr1'. lv{cGrar.v Hi I l.
7. P. Suppan, Chenristrv untl Lighr. RSC [-ondon.
Yll lYuc'leor ond Rudiotion Chemistr.y,(14 h)
Nuclear binding energ),. senti entpirical mass equation. stabilitl,rules. ntagic numbers.
nuclear models. shell. licluicl c'lrrtp. f'enli qas. collectire ancl optical models.
Nuclear reactiotrs: Tvpes. cclnsen'ation. reaction cross section. conrpound nucleus
theorl. specific nuclear reactions. photonuclear and therntonuclear reactiols.
Nuclear fission- theorr, of flssion - spontaneous and reduced fission - ueutron capture
cross section anci critical :siz-e. principle ar-rcl rvorking olnuclear power planls. Nuclear
fusion. Neutron activation analysis.
Radiation chenristrt' - interactiun of radiatiorr ',vith matter - processes responsible tbr
energy loss. range and range energ) r'elation. Methods oldetection ancl nreasurernent
MODLILE
15
l,
.
of radiation. Physical and chemical radiation etfects in solids. Radiation chemistry of
water and aqueous ferrous sulphate solutior-r. Dosimetry. Principle and working of
GM counter and scintillation counters.
References
1. Friedlander, J. W. Kennedy, Introduction to Radiochentistry. John Wiley and Sons,
1981
.
2. S. GlassIone. Source Book on .4tontic' Energt,.3''i Edn.. Affiliated East-West Press
Pvt. Ltd., 1967.
3. H. J. Arnikar. Essential.y of'Nt.tc'lear Chemi.s'tr1'.4'l'Etin., Nerv Age International.
New Delhi,1995.
4. J. B. Rajam. Atomic Phys'ics. S. Chand and Co. Pvt. Ltd.. 1974.
5. Friedlander, J. W. Kennedy. J. M. Miller, llLtclear and Radiochemistry.3'd Edn..
John Wiley' and Sons, 1981.
6. J. W. T. Spinks, R. J. Woods. An introduction to Rudiation Chemistry, John Wiley
and Sons. 1964.
MODULE WISE WEIGHTAGE FOR QUESTIONS
MODUI-E
WEIG}{TAC,iE
I
8
II
6
III
7
IV
7
1
VI
5
VII
l0
l6
\7
I
ra
PC2 C
06
THEORETIC,AL CHEMISTRY
II
Credits:
(10
I
4
h)
Muthemotical.Groups
1 Complete
.\ I
MODULE I Molecular symmetrl'uncl
set of
molecules.
i;
operations
svmmetr),
Symmetr-v elements and
Point groups and their systematic identification'
symmetry operations of a molecule.
Abelian and Cyclic groups' Group
Mathematical group. Finite uni'i"t,,'ri,. !.o.,p.
Similarity transformatton'
multiplication iuute. classes in a gror-rp.
of matrices. Inverse of a matrix' Square
Matrix algebra. Addition un,t *,it,iplication
matrix.. Direct product and.direct sum of
matrix, Character of a matrix. oi"g"".r
method
matrix' Solving linear equations b;- the
square matrices. Block Olugonuti,ti
ofmatrices.MatrixrepresentattclnofsymmetryoperationS.
(
n)
Theory of MoleculalSymryetr-r'' 10
^ .,
Representattons *sing vectors.
a repret:,111:':''
Representa,ion t.lf grotrps' Basis tor
(HzO
positioned on th. u,o't of molecule
atomic orbitals ard Cartesian coorclinates
of
and iiretlucible represe"t"l]"-1:,.-:onstruction
as example) as the basis . ReAucit',te
Great
(qualitative demonstratioll only)'
irredr.rcible representation by ,.dt'ttiun
j tno derivation.l, construction of irreducible
orthogonality theorem tGOT
as
of character tables (Czv' Cl:v' Cun and Cqv
representation using C}OT. Conrir,ttion
Symmetry
representatrons-Mulliken s-vmbols'
examples). No*.niuture of irreducible
using GOT' Reduction of reducible
MODULE
ll
species. Derivation or ..au.iion formula
representations.(e.g..f..n,.)usingthered-uctiontbrmula.Directsumanddirect
and
Connection between group theory
product of irrecluciblt representations'
quantum mechanics'
- / ( l0 h)
MODULE lll Appticutions of G'!!tl Theory
moment
i) Vanishrig una non]va,i,shing integrals. Transition
tntegrr al and selection
for overlap'
rules. Overl"ap integrals and cor.rditio-ns
ii)Mot,.ut.n.nt'ofH,o.Classitrcationatomicorbitalsinvolvedintosymmetry,
q-v,nmetr)' adapted linear combination (SALC)' Projectiorl
species. Group orbitals.
co.tiguration 9f H2O' Symmetries of the
operaror. Conr*u.,io , of MOs. aiectronic
and selection rules' l-aporte selection
ground and .*.it.(.l states. Fllectronic transitions
iule for centro symnretric molecules'
I/ (10 h)
MODULE lY Apptications of Group Theoryof
cH'r' Inverse transformation and construction
i)Treatment hybridization in BFr and
orbitals'
of normal modes of
iii Molecular vibrations' Symmetry specresdrawings
of normal modes (e'g'' HzO
and
Construction of 1.,]n. Normal coordinat"s
of
Raman activitiei, complementary character
and NHt). Selection rules for tR and
IRandRamanSpectra.DeterminationoflRactiveandRamanactivemodesof
molecules (e'g', HrO' NHr' CH+ ' SFo)
hybrid
MODULEV (11h)
I
General Theory ol
vibration'
Speclra
regions, Interacttot-t of matter with
et."tro*ugnetic'radiation and its different
of the molecule. origin of molecular spectra'
radiation and its ef-fbct on rhe energy
and electronic spectra' Intensity of
Theory of the origin of ,o,uiionat.- r,iu.ational
on population' transition probabilities'
spectral Iines. Dependence of intensity
t1
a
Transition moment integral. Selection rules. Line widths. Doppler broadening,
Lifetime broadening.
i) Micr ou, av e Spe c tr o s c rtPl'
Rotation spectra of diatomic and polyatornic molecules. Rigid and non-rigid rotator
models, Asymmetric, symmetric and spherical tops. Isotope effect on rotation spectra.
Stark effect, Nuclear and electron spin interactions. Rotational transitions and
selection rules. Microwave spectrometer Principles & Instrumentation.
i
Applications.
l1t) V ibr at ional Spe ct r o s c op);
Vibrational spectra of diatomic and polyatomic molecules, Harmonic oscillator
model, Anharmonicity. Vibrational transitior-ts and selection rules. Morse potential,
Fundamentals, Overtones. Hot bands, Combination bands, Difference bands.
MODULE vI (11 h)
i) Vibration-rotation spectra of diaton'ric and polyatomic molecules, P,Q,R branches.
IR and FTIR spectrophotometer - Principles & lnstrumentation. Applications.
ii) Ramun,Spec tros copy
Pure rotational, pure vibrational Raman spectra. Vibrational-rotational Raman spectra,
Selection rules, Mutual exclusion principle.
Raman spectrophotometer- Principles & Instrumentation, Laser Raman spectroscopy,
Applications.
i i i) El e c tr o nic Sp e c tr t).s c oP):
Basic principles, Beer - Lantbert lar,i'. N{olar extinction coefficient. Intensit}' of
electronic transitions. Types o1' electronic transitions. Franck - Condon principle,
Ground and excited electronic states of diatornic nrolecules. Electronic spectra of
polyatomic molecules, Chronrophores. T'he tate of electronically excited state
species- Vibrational relaxation, External conversion, Internal conversion.
Fluorescence, Phosphorescerlce. Jablonski diagram. Electronic spectra of conjugated
molecules - dissociation and predissociation spectra.
UV-Visible spectrophotometer - Principles & Instrumentation. Applications.
MODULE VII ( l0 h)
i) NMR Spectroscopy
'fheory nnd measurement techniques. Solvents used.
Magnetic properties of nuclei,
Chemical shift and factors influencirrg chemical shift. Shielding effects, Spin-spin
interaction, Coupling constant, Factors influencing coupling constant, Effects of
chemical exchange, Fluxiorral rnolecules, Hindered rotation on NMR spectrum, Karl's
relationships. NMR spectrometer- Principles and instrumentation. Multiple NMR
spectroscopy (brief account). Applications of NMR spectroscopy to structure
elucidation of simple organic arrd inorganic molecules. FT NMR.
ii)
ESR Spectroscopy
Theory and measurement techniqtres. Hyperfine interactions. Equivalent
nonequivalent protons. Kramer's theorem. ESR spectrometer- Principles
and
and
instrumentation. Applications irr structure elucidation of simple molecr"rles.
iii) Mo.ss Bauer speL'tro.tcoPY
The Moss Bauer effect. Instrumcntatior-r. H1'perfine interactions, ist'rmer shifl, electric
quadruple and magnetic hyperfirle interactions. Applications.
iv) Nlass Spe ctrom
e
trll
Basic principles. lnstrumentation - Mass spcctrolleter, interpretation of mass spectra.
resolution. exact masses of r-ruclides. ntolecular ions. isotope ions. Fragmentation
18
t
l.
processes - lt4cl-affertt rearrangements- retro Diels - Alder fragmentation.
Application in structure elucidation and evaluatioll of heats of sublimation and
ionization potential.
/
Peferences
1.
F. A. Cotto n. Chemical applic'arions of Group Theory.2'"i Edn.. Wiley' Eastern. 1971
2. Jaffe, Orchin. Symmetry in L'hemi^t/r/, Wiley E,astern.
3. [.. H. Hall, Group Theory antl .symmetry in Chemi s/ry. McGraw Hill
4. R. McWeeny.,symmetry'An Introduction to Group Theory and it.s ApplicationsPergamon Press. London, 1963.
5. P. H. Walton^ Beginninpi Group TheorT'jbr Chemi.rrry. Oxford LJr-riversit-v- Press Inc..
.
New York. 1998.
6. A. W. Joshi, Elentent,s of GroLtp Theory .for Physici.s't.s', New Age International
Publishers. 1997.
7. P. W. Atkins. Physical Chemistry.6'r' Edn.. Oxford Universitl, Press, 1998.
8. F. Daniels. R. A. Alberry. Pltllsicul Chemistrt,,5't' Edn., Wiley Eastern, 1980.
9. D. A. Mc Quarrie, J. D. Simon.Ph1,.5'ico\ Chemi.stry, A Moleculor Approacft. University
Science Books. 1997.
10. K. J. Laidler, J. H. Meiser. B. C. Sanctuary. Phy.sical C'hemisrry, Houghton Mifflin
Compan-v-. Neu' York. 2003.
11. C. N. Banwell. Fundamental,s of Molecular Spectr<tscopy, Tata McGraw Hill, New
Delhi, 1994.
12. G. M. Barrow, Inrroduction to Nlolecttlar Spectroscopy. McGraw Hill. 1962.
13. H. H. Willard. L.L. Merritt. J. A. Dean, In,gtrumenttal lvlethods of ilnalT:si,r, 4'h Edn..
Affiliated East-West Press Pvt. I-td.. 1965.
14. N. Sathyanarayana, Elet:tronic' ,4b.srtrptbn Spectro,scrspy' and Reluted Technique's.
University Press, 2000.
15. R. S. Drago. Ph_,-,sicctl Jvlcthotl.t in Inorgunic C'hemi,stry, Affiliated tlast-West Press Pvt.
Ltd..1977.
MODULE WISE WEIGHTAGE ITOR QUESTIONS
MODULE
WEIGHTAGE
I
II
1
III
l
IV
1
1
VI
8
VII
l
l9
a.
SVLLAB\iS - PRACTICAL COURSES ( I &
PCI & PC2 P 0l
ll Semesters)
IN)RGANIC CHEMISTRY Credits: 4
\
MODULE I
Separation and identitrcation of tbLrr rnetarl iorts of which two are less familiar
elements like W, Se, Te, Mo. Cle. Th, T'i. 7.r.Y,lJ ancl Li. (Eliminating acid radicals
not present). Confin-nation b1' spot tests.
MODULE 1I
Volumetric Determinations usin g:
a) EDTA (Al. Ba, Ca. Cu. Fe. Ni. Co. l-rardness of water. etc.)
b) Estimations, involving quantitative separation of suitable binary mixtures of ions
Cu2*. Ni2*, Fe3*, Zn2*. Ca2*. Mg2*. Cr2O7l-. Ila. Ag. etc. in solution by volumetric,
gravimetric, colorimetric and electroanalytical methods.
c) Analysis of ores and allol,s like dolomite. galena, ilmenite, tnonazite, feldspar and
kaoline and two alloys.
MODULE
III
Colorimetric determiuation of chromiur-n, iron, manganese, nickel, and titanium using
either Dubosque or photoelectric colorimeter.
References
l.
2.
3.
4.
G.H. Jeffery. J. Bassett, J' Mendharn' R C' Denttl'' l"ogel's Text book o./'Quantitative
Chemical Analysis.5'r' Edn., ELBS. 1 989.
D A Skoog, D M West. Anall;ticul C'heni.stry. An Introcluclion, 4'l' Edn., CBS
Publishing Japan Ltd.. 1986.
E. J. Meehan, S. Bruckenstein. l. M. Kolthoft. E. B. Sandell. Quantitative C.hemical
Analy.sis,4'h Ecln., The Macmillan Company. 1 969.
R. A. Day (Jr). A. L. Undenvood. Quuntitative Analysis,6'l'Edn., Prentice Hall of
lndia. 1993.
20
,\
PCI & PCz
/
MODULE
I
MODULE
ll Quotitutive
MODULE
lll
P
02
ORGA^|IC CHEMISTRY Credits:
4
Laboratory Techniques
Methods o1'separation and purification of organic compounds - fi-actional. steam and
low-pressure di stil lation s. fiactional cry,512l l l ration and subl i mation
Orgonic Analysi.s
Separation and identification of the con-lponents ol organic binar.v rnixtures (at least
ten) b.v semimicro analytical techniques. Determination of M.P/B.P of the separated
components. Separation of orqanic mirtures using paper. thin Iar er ancl column
chromatography. Detennination of Rf valLre.
Orgonic Preporations
Preparation of about flfteen organic compounds (at least six dor-rble stage- including
photocheniical reactions) illr.rstrating inrportant svnthetic methods and reactions such
as Friedel-Crafls reaction. Cirignard. Perkin. Reimer-Tiemann. Sandmeyer. and
Canntzzaro reactior-rs. CIaisen. Aldol. and benzoin condensations. Selective reduction
in polynitro aromatic compounds: diazocoupling. phthalein fusion. etc.
MODULE lY Quantitative Organic Analysis.
Estimation of nitrogen b.v KjeldahI method. estimation of hydroxl'l and carbonyl
groups. determination of iodine nunrber and saponification valr-re of oils F.stirnation
of reducing slrgar. anrines. phenols. esters. r,itamins (A and C ). clrugs (aspirin.
paracetaruol).
References
1. B. S. Fr,rrnis. A. J. flannaford. P. U'. C. Smith. A. R. Tatchell. L'ogel'.s T-cxtbook o/'
Pructic'ul ( )'ganic (.hemistr.y'. ELBSrLorrgrnan. I 989.
2. Fieser. Experiment.s' in Orgunit' ('hemi.strt'
3. Mann. Saunders. Praclicol Orgunic' ('hemistry.1957.
4. Dey, Sitaraman. Govindachari. I Lahurcrtorl' Nfunucrl o/ Organic Chemi.str.t,.3'd Edn..
1957.
5. Cheronics an Fatrikin Senti-micro Orgonit: Anolysis.
6. A. .1. Vogel. Oualitotive Orgunit' 1psl1t.;t,\
l. P. R Singh. D. C Gupta. K. S. Ba.ipal. Experintcnral Organic' Chemi.strl'. L'itl. I and II.
I 980.
8. R. Srinivasan. Ed. Photochamical .Sy'nthe.si,s. Vol. I and IL
21
I
PCl & PC2 P 03
PHYSICAL CHEMISTRY Credits:
4
MODULE I Colligative Properties
l. Molecular weight from depression by transition method- cooling curve method.
2. Molecular weight by cryoscopic method.
3. Molecular weight Rast method.
MODULE ll Viscosity
L Determination of viscosity
of pure liquids
(water. methanol. ethanol.
gl.n-cerol.
benzene. nitrobenzene, carbon tetrachloride).
2.
Determination
3.
water-alcohol).
Determination of molecular weight of a polymer (polystyrene in toluene).
of
composition
of binary liquid mixtures (benzene-nitrobenzene,
MODULE lll Co nductivity Experime nts
1. Equivalent conductance of a weak acid- r'erification of Ostwald's dilution lawcalculation of dissociation constant.
2. Equivalent conductance of strong electrolytes (KCI). Verification of Onsagar
3.
4.
5.
equation.
Activity coefficient of Zn in 0.002M ZnSO+ using Debye-Huckel limiting law.
Solubility product of a sparingly soluble salt (e.g.. AgCl. BaS0q)
Conductometric titrations
(a) HCI vs NaOH
(b) (HCl + CH3ClOOil) r,s NaOH
(c) AgNOr vs KCL
MODULE lY Potentiometry
l.
2.
3.
4.
5.
6.
Electrode potentials of Zn ancl Ag electrodes iu 0.1 M and 0.001 M solutions at 25 oC
and determinatior-r of standard potentials.
Mean activity coefficient of an electroanalyte at diff.erent molalities by EMF method.
Dissociation constant of acetic acid by potentiometric titration.
Determination of strength of the given HCI solution b,v differential potentiometric
titration.
Dissociation constant of acetic acid in DMSO. DMF. acetone and dioxane by titrating
with NaOH.
Potentiometric titration.
i)
Mixture of chloride and iodide.
ii) Mixture of HCI and CIJTCOOH.
MODULE Y Chemicol Kinetics
L Specific reaction rate of acid catalvsed hydrolysis of methyl acetate.
2. Temperature coefficient and energ) of activation of hydrolysis of methyl
Determination of Arrhenius parameters.
3. Saponification of ethyl acetate (titration/conductance rnetllod).
4. Inl'ersion of cane sugar in presence o1'HCl br polarinretrl.
5. Iodination of acetone- deterrninatr on of order.
acetate.
MODULE Yl Adsorption (3 experinrents)
l. Verification of Freundlich and LangmrLir aclsorption isotherms.
22
I
2.
/
Determination of concentratipn o1'acetic acid/oxalic acid using Freundlich and
Langmuir adsorptiott isothentrs
MODULE
1.
Yll Phase Equilibria
Phase diagram
Phase diagram
of a simple eutectic svstenl.
of a binar,v solid svstem fbrming a compound'
2.
3. Phenol-water system. aniline-r,vater systel11.
4. Ternary liquid S),stern with one pair of partially'
miscible liquids (DMSO-benzene-water.
acetone-chloroform-water. etc. ).
References
1. A. Finlay. J. A. Kitchener, Prnctirol pfiysicul c'hemi.s'tr_v, Longman.
2. A. M. James. Prctc,tical Phy'5ic.til (hentistr)'. J. A. Churchit Ltd.. 1961.
C. D. Cornu'ell. J. E. Harriman.
3. F. Daniel. J. W. Willianrs. P. Bender. R. A. Albert.v.
q70'
Experimental l'hy.sical (' hemis'r t'7'- McGraw Hill. 1
4. W. G. Palmer. Experimentul Ph.v'sical ('han'tistry'.2'"1 Edn.. Cambridge t)nir,'ersit-''- Press'
1962.
5.
D. P. Shoemaker. C. W. Garlancl. Exparimanrcrl Phy.sictrl ('hemistry. IVlcGraw Hil[.
Z)
a
QUESTION PAPERS
MODEL ONLY
FIRST SEMESTER M
SC
(POLYMER CHEMISTRY) DEGREE EXAMINATION
PCI C 01 INORGANIC CHEMISTRY
Time: 3
\
-I
Max: 36 Weightage
Hours
Part A
(Answer all questions. Each question has I weightage)
1.
Arrange the following in the order of acid strength'
a) BCl3,
BI:.
BFr b) SnClz,
Sr-rClr
2. BzO: is acidic. AlzO: is amphoteric and Se:Or is basic' Why?
3. Calculate the maximum radius ratio of an atotn A to flt in the simple
cubic lattice
ofan atom B
4. Explain the term K- space. What is its significance?.
5. What is meant by packing fiaction'/ How does it predict
the stability or other wise
a nucleus.
6.
How,do the d orbital split when a transition rnetal ion is placed in octahedral
crystal field of ligands.
7.
Choose the stronger acid or base in the lbllowing pair
a)
b)
CH:NHz or NH3 in reaction with H.
Pyridine or 2-nrethyl pyridine in reaction with tri methyl boron
8. Wh1, lanthanides exercise oxidation states other than + 3
9. Name three types of determinate errors.
10. On what f-actors does the
11
solubility of a precipitate depend
. What are phosph azines? Draw structure
12. State and explain Jahn- Tellar
of Hexachloro cyclotriphosphazine.
eff-ect.
13. What is meant by confidence limit? What is its significance'?
14. What are radio active tracers'l Mention two applications.
Part B
(Answer an-v seven questions. Each question has 2 weightage)
15. Calculate the binding energ)'per nucleon o1-oxygen sOl6 which has a mass
of
'+
-\
:1.007277
15.994910 a.r-1.u. Mass of neutrgn.. 1.00866,5 a.m.Lr. mass o{'protot-t
a.m.u and tnass of electron
/
:
0.0(10-541t6 a.ul-u.
16. Explain why a strong acid like FINO] behaves as a base in HF.
17. Explain the dift-erent steps involved in the tbrmation of silicones'
18. Why strong oxidizing agents do not exist in tiquid NI{j'
19. Write short note on nepl'relauxetic series.
20. Distinguish between nuclear fission reaction and nuclear fusion reaction.
21. What are Latimer diagram? Explain how a Latimer diagram is converted into
reduction half - cell reaction in acid solution?
22. Define Fermi level. Show that it is located half way between the highest fllled level
and lowest unfllled level.
23. What
are carboranes? How are boranes and carboranes classified'J
24. Describe caretully the Q test rvhich is applied fbr rejection or retention
of
an
anomalous result.
Part C
(Answerany,twtlquestlons.Eachquestionhas4weightage)
25. Discuss the various types olsemiconductors and their applications'
26. Give a brief account of imperf-ections
21. How
ir-r
solids and various types of def-ects.
pi bonding?
is the MO diagrarn for an octalieclral complex modifled on including
Explain why CN-and
Cl
occur in opposite ends of the spectrochemical series.
28. Describe briefly the ion exchange and
soh.'ent extraction separation
of lanthanides'
25
MODEL ONLY
FIRS,I SEMESTER M Sc (POLYIVIER CHEMISTRY) DEGREE EXAMINATION
PCl C 03 THEORETICAL CHEMISTRY-I
Max: 36 Weightage
Time: 3hours
(Answer all
Part A
Questions. Each question has
I
weightage)
1. What you understand by conlmutator operatof?
2. Show that sin 2x is not an eigen function of the operator d/dx but of d2ldx2.
3. What do yor.r understand b1' Flernritian operator'?
4. Which of the functions sin3x.6cos4x. -sx2 are eigen functions of d2ldx2?
5.
lf A^ :
3x2 and
B"
:
d/clx then shou' that A^ B^
I
B" A"
6. For a particle in a cubic box of edge 1.. How many states have energies in
the range zero and l6h2l8mL7?
7. Sketch the molecular orbital scheme fbr N2
8. What do you under stand bv the term hybrid orbitals?
9. State and explain uncertainty principle.
10. Deduce spectroscopic term symbol for F2molecule.
11. On the basis of MO theorl,predict on the relative stability of 02, ()2*
and O2'12. Write dor.vn the Harniltonian operators fbr electrons in He- and He.
13. Calculate the zero poir-rt kinetic energv of COz urolecule moving in side a
cube of length 20 A"
14. Draw
y
2functions
and ry
for 2s and 2p orbitals.
Part B
(Answer an.v seven Questions. Each question has 2 weightage)
15.
Briefly explain Slater's treatment of ci'rmplex atoms.
16. Out Iine the valence bond treatntent olbonding in H2
17. Explain the basic postr,rlates of Fluchels MO theorv.
18. Discuss about Hernrite polvnomials.
19. Write a short note on Self-Consistent Field n.rethod.
20. Write briefl,v tl-re Pauli's exclusion principle.
26
la
,^
21 . Appl1"
Schrodinger wave
eq Lration
fbr a particle in one dimensional box and
fir-rd eigen functions.
/
22. Explain the essential f'eatures of MO and VB treatment of Hr molecule.
23. Enumerate the experimental proof fbr the uncertaintv principlc.
24. Write a note on L.aguerre and associated Laguerre polynomials
Part C
(Answer anv two Questions. Each question has -lweightage)
25. Treat the pi-bondin-u in benzene within the fiame work of Hr-rckel MO theory.
26. Write a detailed account of variation method. How is it different fiom
perturbation method'l
27.Wrrte short note
on
a) Radial distribtrtion curves b) Operators
28. Solve Schrddinger eqLratioll for a particle in three dimensional box. solve it
and get expression fbr the energ-v- olelectrons.
2l
aa
\
MODEL ONLY
SECOND SEMESTER M Sc (POLYMER CHEMISTRY) DEGREE EXAMINATION
PC2 C 04
Time:
-
ORGANIC CHEMISTRY
3hrs
-
II
Max: 36 Weightage
Part A
(Answer all questions. Each question has
l. Would
1
weightage)
the photochemical cyclisation of the following diene give cis or trans product?
Explain.
CHs
I
Z'a
l-
hv
YN
CHs
2, Write the stereostructure of the compound obtained by the Diels-Alder reaction of
dimethylmaleate with butadiene.
3. What is ortho effect in aromatic electrophilic substitution reaction?
4. Alkylation of Benzene with MeI by Freidel - Crafis reaction gives toluene.However, a
similar reaction to obtain n-propylbenzene using r-propyl iodide hardly succeeds.Explain
why.
5. Predict the products
cr
and propose mechanism in the tbllowing
(")
NaNHz ? Y
.?
liq NH3
6. Write an),two reactions of nitrenes.
7.
which butoxide, r-Buo-K* or n-Buo-K* is the best to prepare l-pentene fiom
MeCH(OTos)
-
CH2 CHzMe under E2 conditions? Why?
8. A benzyl radical is more
9. Explain wh1'
11-,.
stable than an ethyl radical.Give reason.
E2 elimination rate of trans- 4- r- butylcyclohexyl tosylate is different
from that of its cis- isomer.
10. Is the
following reaction, at a bridgehead position. a leasible one?Comment
,/,Br
_
7],coons
- s Brz_
rl5
.(K,
/--)--/
D-_/
I
l. Predict the products in the fbllowing
28
hv
lsobutene + Benzophenone
?
12. Provide mechanistic rationalization
---> fbr the tbllorving reaction.
/
13.
N-methylbenzamide does not undergo l{of}lnann rearrangement.C}ive reason.
14. Is Fries rearransenterrt is tentperatlrre clependentTErplain
Part B
(Answer any seven questions. Each question has 2 weightages)
15. Write an account of the mechanism of Cope rearrangement and explain using examples
why it is classified as a [3.3] sigmatropic rearrangement.
16. Write briefl.u-' on
(i) ElcB mechanism of elimination and
(ii) mechanism and stereochemistrr, of Chugev reaction.
17. (a) Why the reactivity of the diene is increased
b,v-
electron releasing substituents?
(b) Cycloaddition of an unsymmetrically sr-rbstitr-rted diene and dienophile can in
principle lead to regeoisomers.Write the structures of the products by takrng
examples.
18. Give the stereochemistry of the products formed when
(a) cis, trans-2.4- hexadiene reacts thennallv and
(b)
tr
ans', t r an,s -2.4
19. (a) Complete the
- hexadi ene reacts photoch em i cal I i
.
following equation. give its name and mechanism.
EIONa
C3HTCHCICOCH2Me
(b) Hoi.v u,ill ),ou convert the fbltowing?
No
ryo
AzC
cH"
J i.
H2C.
(^
,.
CH2
oHl
1
H2C
^
(.
-CH2
H2
H2
20. Write briefly on the structure and reactivity of singlet and triplet Carbenes.
29
.a
v
the rate of SN2
21. How does the branching on o and B- carbon atonr of alk.vl halide aff-ect
reaction?
22. Deduce the mechanism of Woltf rearrangement.Discuss its utility in An-rdt-E,istert
\
synthesis.
23. Discuss the (i) photochemistry of vision and
(ii) mechanism of di-n24. Derive the
n-retl-rane rearrangement'
w-H rules for thermal electrocyclisation of 4n and 4n+2 systems.
Part C
(Answeranytrvoquesttons.E,achquestionhas4weightages)
25. Write an account of (i) Photopolymerisatiol reactions and
(ii) the different mechanisms of arotnatic substitutions'
26. (i) What is Favorskii reaction?
(ii) which side reaction occurs with Favorskii rearrangement?
(iii) What is quasi- Favorskii
rearrangetnent?
27. Using correlation diagram approacl-r. derive the selection rules for thermal
electrocyclisation in 4zr and 6n electron systems'
28. Write an account of (i) photopolymerisation reactions and
(i
i) the diffbrent mechanisms ol aromatic nucleophilic substitutions.
30
a
A.
MODE,L ONLY
SECOND SEMESTER M Sc (POLYMi:.R CHEIVIISTRY)
DEGREE EXAMTNATION
PC2 C
05
PHYSIC]AL CHEMISTRY
Time: 3 hours
I
Max: 36 Weightage
Part A
(Answer all questions. Each question has
I
weightage)
L Explain the term residual entrop).
2. What is Debye Falkenhagen effect?
3. Explain the term isosteric heat of adsorption
4. What are the major products of rvater railiolysis?
5. Explain with example an ideal non porarisabre erectrode
6. Define phenomenological coefficient. Explain
it's significance
7. Distinguish between inter system crossing and internal conversion
8.
write down Debye Hucker limiting law and explain the terms
9. Define excess enthalpl,. What is it's significance?
10. What is meant by che*iluminiscence?
Gi'e
one example.
1l' Calculate the ionic strength of a solution containing 0.001 mole Calcium
phosphate.
12. Explain thernral osmosis.
13. Explain the term thermal neutrons.
14. Distinguish between Stokes and anti Stokes lines.
Part B
(Answer anv seven questions. Each question has 2 weightage)
15. Derive Duhem Margr,rles equation.
16. Derive
17. Write
what is it's importance?
Gibb's adsorption isotherm.
Ilkovic equation. Explain it's signiticance.
18. Write a note on
colloidal surfactants.
19. Explain how irreversible process generates entropy.
20. Discuss briefly the theort, olfluorescence.
21. Explain the principle and working of a solar cell.
22.How will vou determine the surface area of an adsorbent'l
3t
6,
!
v
23. Discuss the shell model of nucleus.
24. Explain the term dosimetry. Describe the firnction of a Fricke Dosimeter.
Part
[]
(Answer any two questions. Each question has 4 weightage)
25. Derive Debye Huckel Onsagar equation.
26. Give an account of determination of thermodynarnic partial derivatives by the method of
Jacobians
27. Write notes on
a) Polarography
b) Activity and activity coetficient
28. Describe the principle and working of a scintillation counter
32
MODEI, ONLY
SECOND SEMESTER NI Sc (POI-YMER C]HEN,IISTRY) DEGREIl EXAN,IIN,A,TION
PC2 C 06 - THEORlrl lCAt- CHEMISTR\'-II
Time:
3hours
Max: 36 Weightage
Part A
(Answer all Questions. Each question has 1 weightage)
I
l.
Shorv that
2.
Assign Schoenflies symbol of point grolrps to a) CoH+Rz (ortho). b) ci.r- butadiene c)
So2
= C:.
PCls
d)
cH2:
cHz
3. Explain pre dissociation spectrum
4. Explain the Lande splitting factor (g).
5. Explain w'ith examples, coniugate operations.
6. Generate the matrix representatiorr of C,r operatron.
7. What are the factors responsible for lif-etime broadening'?
8. What is Stark effect'l
9. What are prolate and ohlate molecttles? Give examples.
10. Stokes lines are nrore intense than antistokes lines. Why?
11. Calculate energy in wave numbers per mol for a radiation
12. Delete o1, front
D.h point group. What would be the resultant point group?
13. What do you mean
14. Explain the
of wave length 500nm.
b1' resonance Raman spectrum?
origin o1'laser.
Part B
(Answer an) seven Questions. Each question has 2 '"veightage)
15. Shorv that E. C.r. Crr. o,,. o,'.and ou"tbrm a mathematical group.
16. Constrr-rct the character table tbr Cl;, point group bl"Lrsing GOT.
17. Write a shirt note on MLrllikan's notations fbr irreducible represctttatious.
18. Explain the liagmentatiort pattent
19. Reduce the representation
fr.
of ketones on the basis of EIMS.
You are provided with the chalacter table.
JJ
il
aa
-,
a'
20. what is meant by PeR bra,ches of rines? How are
they formed,/
21. How will you determine the dissociation energy of
a diatomic molecule from
vibration spectrum? Explain.
22. Explain the terms: a) Vanishing
integrals b) overlap integrals c) Exchange integrals
23. Explain the electronic spectra
conjr_rgatecl ntolecules.
of
24. HCI shows absorption at 2990cm-1. Calculate the
fbrce constant of the molecule.
Part C
(Answer any two euestiorrs. Eacrr qr-restion rras 4
weightage)
25. Get the representation of nonlal nrodes of vibration
of NH.r molecule. predict the IR and Raman
activity'of these modes. Character table is siven.
Ctu
AI
A2
E
Rz
(Tx. Ty)
(Rx.Ry)
(*'-y', *y)
(*',y')
26' Comment on the rotational spectrum of polyatomic molecules.
How is it helpful in the
determination of different bond lcngths in a polriatom'c nrolecule?
27 ' Find the molecr-rlar orbital of HCHo. c2, character
table is given beiow. comment on the various
electronic transitions in this moleculc.
34
li
l.
t
\
AI
I
Tz
-l
-l
Rz
xy
-l
Tr.
XZ
I
A2
I
BI
-l
I
-t
-t
I
Rr
T1'. Rx
yz
B2
28. Discuss briefly the principle of electron paramagnetic resonance spectroscopy.
3-s
I
raa
t
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