I ot 1

PAPER · I
SECTION A

om
I. C• ) Why is it necessary to add bigh cooccnlration of s uppurting elcctwlyle ''"d deat:rJte lh<>
analytosolution bafotoe rccordin.g the polarogram?
(10)
(b) Suggest oxplanatiuns fut· ｾ ＢＧ＠ fact that ga.•es diffuse throu.gh all tho spac•-avoilahle to ｾ ＢＧ ＢＧ ﾷ＠
(10)
(c) Explain types of ｶｾｩ､ｳ＠ possibly present in a crystal lottice, What is lho role of ionic rodii on

.c
deciding geometry of crystalline solid'? What w iU be the ｭ ｡Ｎｾ ｭｵ＠ si1:e <lf an atom/ion that
con occttpy the octnhcdro I 'o id crcotcd hy ltcp nrrangemcnls of 02 ions {radius l)f 0 -2 R )'I
(10)

ce
(d ) Expl•in and illustrate the tei'T!U, dipole- dipole ｍ ｬ ｲＮｾ｣ ｴ ｩｯｮ＠ and ion-dipole attraction, which of
tht:Se ｩ ｾ＠ cornp11ratively slrOJlgcr'l
(tO)
(t) ｉｮｾ＠ solution e>f sodium s ulfate, bow man) componcnLs. ph:c.cs and degree of freedom do you
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expect at the ｾ ｯ ｬ ｩ ｮ ｧ＠ point .md what are they?
( Ill)
2. Ia) A s<:rie• of lines in tbc spectrum of llll.nnie hydrogen lies at the "ovekngtbs 656.-16 nm,
486.27 nm. 434.17 nm, Ｚｾｮ､＠ ｾ＠ 1029 nm. \\1tol i• the ""ovolcngth of Ute next line in ｾＧＢ ｳ･ ｲｩ･ｳ＠ ?
m
What energy is required to ionise the hydrog<m atom when it is in the lower stnte involved in
these traDsition$ '?
(20)
A SJIS cylinder ｾｯ ｮｾＱ ｩ ｮ ｳ＠ 370 g oxygert g3s at 30.0 ｾ ｴｲｮ＠ pressure •nd 25°C 'Moot ｭ｡Ｎ ｾ＠ of
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(b)
oxygen would escape if lirst the cylinder were heated to 75•r· and then vall e "ere held op<m
until the gas pressure was 1.00 atm. the lclilpcrllturc being maintained nt 75' C?
(20)
3. (o ) What changes would you e.xp ecl in lhe polnrogram (reduction of M'" on Dl\•lE in Conlaal
.e

with 0.001 M tv!"' in 0.1 M K,SO,) when

( i) Comploxing ligand of concenlrotion 0.0 1 M ｩ ｾ＠ oddcd to ｾｬ｣＠ ｜ｬｩｕｉ ｹ ｴｾ Ｎ＠

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(ii) Oxdising agonl Cllpllblc io oxidising M•" In higher oxidation state is added to the
;ona l)1e.
(20)
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(b) What is floc degeneracy of the kvc.J of tloe hydrogeu utom tlu.t bn• Uoe • ncrgy.
(i) • R.r
(ii) - R.t 9.
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(iii) -Rw'25'?
(2(1)
4. (o) Brie-lly outline imperfecl:iom; in crystal. C't)'•b l planes cot ｾｴｲ ｯｵｧｨ＠ the crystal a:<<:$ ol (2.1,
3b. c).(a. b. c). (6a. Jb. 3c) ancJ (2a, Ｍｾ ｨ Ｎ＠ -3c). What are their Miller indice>?
(20)
(b) Defi.ne heal copacitr and mol or hen I cnp•city. Colculote the number of Kcal necessary to m ise
ｾＧ Ｂ＠ tempemturc o.r 5().(\ g of a meL11 from 35 •r to 55 •c The motor heal cap.1city ol'the
rueta l is 5.8 caUmolc "C.
(20)
 2 of7
SECTION B
5 (a) Tripositive Lanthanide Ions show characteristic colours in crystalline S<llts These colours are
unaffected by alteration of the anions. Elain.
( 10)
(b) What do you understand b capping n1le? Explain with help of a carbonyl type metal cluster
( 10)
(c) DiiTerenti.ate betwe"n nucleophi licitv and basicity using appropriate exumple.
( 10)

om
(d) How does ｣ｾｬｩｴｲｯ ｬ＠ regulalclhe pla.•ma l<.we.ls <ll' calc.ium?
(I 0)
(e) Winch of' the following legeuds would fonn dte most stable complex with a tuetal iou, M:
Why?
ｃｈ ＬＭ ｾ ﾷｃ ｈ Ｌ Ｍ ｃ ｈ Ｌ Ｍﾷ ｣ Ｍ ｃｈＬ Ｎ＠ Ｐ ｾ＼［ＭＱ ＧＱ＠
o 6 0 n

.c
rr ｾ＠ o
ｯ ｾ ｾＯ＠ -
and ｣ I Ｍ｣ｈｾ -
ｯ ｴ .Ｌ Ｍｃ ｈ 'ＮＭｃ ｈ Ｌ Ｍ ｾ＠ I

ce
rr u·
( 10)
6 (a) Whal is !he preferred yeometry for the transition state fonned during legend substitution
reaction of a square planar complex indicate with diagram the position of the trans dte ra
leaving and the entering group in the transition slate. What influence does the trans grour
have on the rate of the reaction?
(20)
(b) Compare and conrrasl V.B theory ｾｮ､＠ MO. tlteory Give MO. energy level diagram tor :
m
(i) co,
<ii) H ,'
7 (a) What are the main assumprions on 'vhich an equation for adsorption isotherm has been
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derived by Brunauer, Euuneu and Teller? What are the main drawbacks ofdte dteory?
(20)
(b) Wbar are Ferrodoxins7 Discuss the Cluster structure of Ferrodoxin and the mechanism of
redox lnterconversion of the cluster. 2f1e- 2S and 4Fc-4S.
.e

(10)
8. (a) For the reaction ol' regent A in solution to give product. the following data were obtained .
T, Min (A)
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00,0 0.583
09,0 0343
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12.0 0.257
T./vlm (A)
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14 0 0.223
18.() 0 170
20 0 0 133
24.0 0.118
30.0 0.079

Determine the order 11fthe reactiou

(20)
 3 of7
(b) Explain rclnti·on between energy change, lteat ond work done during a change in the system.
Write different types of process from !'hemodynamic view point and show their l.emp.
dependence.
(20)

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I IFS-2007 4 ul 7

IＭ Ｍｾ
CHEMISTRY
Ｍｾｔ｣ｬＧ］ｲ｟ｪ＠
I
PAPER ·II
SECTION A

om
I. (a) Among the following compotmds A - C. which one does riot dissolve in aq NaOH?
Explain.

.c
II 8 c
(6)
(b) Write down the products formed when l·butyl chloride and diphenylmethyl chloride are

ce
separate!)' renuxed wirh a solurion of 900/o acetone and 10% water. When C I ion is added 1n
the reaction mixture. in the first case !be rate of tlte reactiOn is enhanced whereas in tlte
seoond cas.t it is retarded. Explain,

Oli
'-JvvyOEt HCL H.,O
. I ===.,M ＭＺＷＮ
Et,l'l
ｾ
ra
Ｐ＠
Et,N
Cl 0
(8)
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{d) Write down the products formed in the deamination of both cis and trans 2-amino
cvclobexanols with nitrous aci<L Explain !be formation of all the products
(10)
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Ce) Write down the products formed in the acetolysis of optically pure trans-2-aceroxycy-
dohexyl tosylate and explain the tomtation of the products. Wbat happens when the starting
com 0 pound is ｴｲ･｡ｾＧ＼Ａ＠ the EtOH ?
(6+6+8+ 10 + 10)
2 ca) Find out the major product(sl in the followingreacnons and explain the mechanism involved·
.e

vy'Bu l.DA.THF, -70•C

(i I
8
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C,H,CHO

(ii) )=o Cone. H,SO, l

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!iii) @ ..e

Z6
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U)

(l)KOBu'
(2) Raney Ni
Me,CO

(iv) ＨｉＩ ｈ ｃｾ＠ McOR

JiCHO C2) PPh,,, Be"'e"' (S) Aq.HJ
(3) "svLi, n!F
(4) C,H100
 5vi 7

(b) Predict Ihe product of the following ｲｾ｡｣ｴｩｯｮ＠ (strong absorp1ion band at 17 I s·• em) when the
following compound Is bcalc<:l
CH,
ｾ ｾ ｾ＠
•
(8 I 5)
3 Fmd out iJte produci.S in the following cases and ex plain the nwchamsnt mvolved inthereHction .
(8 > 5)

om
(I)

ｾ＠ ｣ ］ｾＢ｣＠
--4

.c
I &O"C
(II)
MoO

ce
( I)CH,L DCM
(Ill)
(2) PhLi, El,O
ra
(I )TsCI. Pyridine
(2) CoCO,
m
H H
(v) ｐ ｨ Ｍ｢ Ｍ ｾ Ｍ ｍ｣＠
H6 bH
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Ia) Find oul the product Wllh ab$Oiute configuration in ｴｨｾ＠ following reaction. What is ｬ ｨｾ＠
mechaoism cuvolved in U1c reaction ? Explain the stereocbemical outcome or t!Je reaction .
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Pb +'\ie AJCO,Ii

(h) Find oul !he product in the following reaction sequence and give !he mechani>m of the
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re.acuon .

ｍｾ ｎ ｟ＮｎｈＬ＠ 6
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• AcQH

J
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(c) l'ind out /1 and B in the followint; reacti on sequence where a. Beckmann rearrangement is
ｯｰ･ｲｾｴｩｮｧ Ｎ＠ bplain che mechanism involved in 1hc re.acri<1n

NH,OH.HCI. NnOAo A
OTIPS McOH
Me rv
ｔｳｃｾ＠ Et,N, DMAP {cat) fl
DCM
TsCI = p·toluenesulfonyl choloride
DMAP = N, N-dimcthylammo pyridine
 h 1Ji 7
(d) Fmd o ut B and C w1tb absolute config.wat10n of the chtral center m the rollowmg. roocuon
Explam Ihe mechan1sm involvcxl in the reaction
Me
C ｾｏｃｬＬ＠ 1-1 -..l SQCI, /J
Pyriduw- ｾＮｲＢｯｮ＠
t 'or

SECTION 8

om
5. (n) How are cham growth polymers -produced? ShO"-v that der>ending on the monomer. the
1mtmlor cnr1 be a "'"dtcal, nn ac1d or an anion for the polymer'ISSt10n of monomeric spectes by
ｲｮ､ｩ｣ｾＮ＠ canon1c o r an1onic 'nechanism. respectively
(b) (i ) What is Ziegler-Nattn catalyst ? Explam the mechmusm for che ]1(1lymensalion of
propylene usiog U11s cataJysL

.c
(ii) fl><plain isotaot1c. s)'lld,ooaclic and atactiC forms of polymers taki11g example of
polyprotw lene.
(<) What product would you expect to obtain from catalytic hydrogenaoon of natural rubber?
Would the produot be syndioacuc. ｡ｴＳｃ ｬＱ ｾ＠ or ISotacl:lc 'I

ce
(d) (i) Show that ur11cil can form strong hydrogen bonds 10 adenine.
( i i) What RNA base sequence is complement try ro the foJJowing DNA base ｳｾｵ･ｮ｣＿＠
6, (a) ( 1i The mreraction of an unparrcd e lectrbn wiU1 14N causes a spJjtting of three bn es whtle
wuh Mn1t QtV<"S stx lines Why?

(11)
(h )
SOtl,ltiOn
ra
Pred ict d1e number o f lines m the ESR spectrum of naphthalene radical anion

2. 2- l)lJnoU,oxycyclopropSJ'Ionc 11nJergocs nng-openms 1vhen !lll11Cked by motho.,dc ton

having followmg spectml properties
10
m
IR 1740 em" 1 ' \S) 1l!ld 1160 cm' 1 ( s): 1 ' H-NMR, IR 1740 em ' (s) and 1 16(1 em (s) '1-1 -N:MR
J .6 (J I I . s), I .2 (91 1. s) UV, transparent above 200 nm: mass .nh ll6, 85. 59. 31 53 6
(311. s), 1.2 (911, s) UV, tJ.-ausparent above 200 nm , mass ｾｮｦｺ＠ I 16, 85. 59. 31 .
Deduce I he SlnlCLure of the product a.1d sug!_!est a mechanism f()r us fom1ation
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(d) The 11-1-NM R spectrum of ethy l 2-butenoatc (eohyl CJUtonate) shows the following signals.
Ｘｾ Ｖ Ｎ ＹＵ＠ Ｈ ､ｱ Ｎｪ ｾ ｬ＠ 16, 6.8 1-lz, llH), 5.8 1
(dq,J ｾ＠ 16, I. 7 liz, I ll ). 4. 13 (q, J 7.0 tl7, 2ll) 1.88
(dd /' 6.&, l 7 Hz. 3H) and 1.24 (t, J 7.0 Hz, 31-f)
.e

Assign lhesc-t) values{() V3J'IOUS hydrogens and lelt 1f I he double bond IS cis 0 1' lrnns. O·ro.w f-1
1
11 -NMR spectrum of the compo<md and tndicatc u,.., .nten1Ciing protons w1th the help of./
values.
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(8+12-8- 12)
7. (a) Give the stmctures of the products from the following photochemical reactions and ｾｶ･＠ \be-
n\echam-sm of fonnmton of products:
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(I) ｾＱＬ＠ _tu:.,.

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 7 o!'7
(b) !7Uid out the products in the followmg reaction sequences and Cl'plnln lim foml!lhon of the
ｰｲｯｊｵ｣ｴｳｾｈ＠
(i) mCPBA
DCM, rt

(II) 0 • Q rt
OCM

om
(c)
(•ii)
0
Predict l11e frequency •hill oru•e curlx•nyl absorption m the followmg aldehydes:
CHO CHO CHO

66 if

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ce
(I) (il) (iii)
( 18+ 18+4)
l•) l>xplnin the FMO method ol' analysts of thermal [I , 3] <.:-shil'l. II. 5] <.:-shill nnd 13: 31
si !''"' ou tropic reu !Tungc me u1
(b) Find out. A and Bon the t'o lhlw>ng rcucuun setJUtnce and ｣ｾｰ ｬ ｵｩｮ＠
ra
thoir t<muuu<1n. Whut is the
t'tlusc of e>\trnordinury tnermul stability t>f 1\ so thai it is isolublo in solutwn 'I

("'y"'o 340-360 •c
m
II l1 l Toluatc +A
ＧＭＯｽＮｾ｣ｯ＠ o
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ｔ･ ｴ ｲＮｴｹｾｮｯ｣ｨｬ･＠
..r
11
n
tel Explain why cyclouddition or t"o molecules of ethyluna is thcrmuJiy uot allowed
td) Write Jnwn the mnjCir product in 01e following renctioo and "'' rlnin the mechnni$m (If th"
.e

rellchon

Ｈ ｾＬ＠ tl )KCN
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cz> R,o·
ｾ ｂｲ＠
Me
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(12+13 +5+1V)
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