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f4ziliJ'l/ DETACHAB LE

(fil4'1 I)
CHEMISTR Y (Paper I) 0000109
(FTlT : -mrr c:rrR: 3icn:250
Time Allowed : ThrP.P. J\llaximum Marks: 250
cpn:rr CfiT rnWiR-lrnct cn1 U41'1g:4Cfl 1
3ttO % 'ciil t w.n 3fu: t I
CiiT "f m"'11 \3m 1
1 5 3lRCII4 .(fqr
'ir.i m"'11 \3m 1

mrr /'mll 3fcn trr+R 7fiZ 1

m"'11 \3m \3"ffi fu-& \lfR Mftcnl -rrm t am:
CfiT 1:R 1:R
\1fl'1T I \3twl fule1
fu-@ \3m 1:R 31 Rl fcRft 3fcn fliWt I
it, cfit, CfiT m 1
\ifGf "(1q1 \3 fWl f@ C1 'i it, CftiT ICl cll Sl 'Cl R1 C1 l1RCfi I
it, \3qgm m CfiT ch'l Ml!\ ch'l Ml!\ 1
m-.,1 "ch'l- ljfti'C "ch'l- I Cf1lCJ it, eft m-;:r "ch'l-1TURT
-rrm it 1 \3m m CfiTCT

Please read each of the following instructions carefully before attempting questions .
. There are EIGHT questions divided into TWO SECTIONS and printed both in
and in ENGLISH.
Candidate has to attempt FIVE .questions in all.
Nos. 1 and 5 are compulsory and out of the remaining, THREE are to be attempted
choosing at least ONE from each Section.
The number of marks carried by a question/part is indicated against it.
Answers must be written in the medium authorized in the Admission Certificate which must be stated
clearly on the cover of this Question-cum-Answer (QCA) Booklet in the space provided. No marks
will be given for answers written in a medium other than the authorized one.
Coordinate diagrams, wherever required, shall be drawn in the space provided for answering
the question itself.
Unless otherwise mentioned, symbols and notations carry their usual standard meanings.
Assume suitable data, if considered necessary, and indicate the same clearly.
Word limit in questions, wherever specified, should be adhered to.
Attempts of questions shall be counted in sequential order. Unless struck off, atte-mpt nf a question
shall ut: even if attempted .partly. Any page or portion of the page left
blank in the Question-cum-Answer Booklet must be clearly struck off.

1 m -esc-u-chm


1. (a) (i) CH4, NH3 3fu: H 20 Chlur 1095, 107 cr 1045 I
c:hlA=ICJ> 1
The bond angles in CH4, NH3 and H 2 0 molecules are 1095, 107 and 1045
respectively. Explain. 5

1. (a) ( i i) BF3 3fu: PF3 3fl!!JIT 3TTTf -en:: M Ra:fuT c8: I

Comment on the dipole moments of BF3 and PF3 molecules. 5

1. (b) 3fi1T CF1l ? fcn -qzyf CO cr N 2 0, 0 K liT

Cf<:IT Wt ?
What is residual entropy? Why certain substances like CO and N 20 are associated
with residual entropy even at 0 K ? l0

l.(c) (i) f5hR:<1 fcrnrrr nA. = 2d sine Cf)f qf{ullli chlMQ\ I

Derive the relation nA. = 2d sine in crystallography. 5

Cii)'Cf'l o1o) cp:rr

What is the perpendicular distance between (110) planes of a cubic unit cell? 5

l.(d) C02 cfiT t!QI?1Cil 31cW1T cfiT q?r chlMC!\ I

t!J:llCfl{UI tigfu mm ?
Explain "continuity of state" with the help of isotherms of C0 2. How is it affirmed
by van der Waals' equation? . 10

1. (e) BaS04 cfiT f4(Vj?1Ci I :J)01'1Cfl(1 1X1o- lO md 2 dm- 6 t Ba+2 cfiT 3IT'f'i" 'ili<1CflCi I 3FRr
25C 0TY" "Cf<:: 12728 X}0-4 m 2 mho mol- l 3fu: so-2 cfiT 1600X10-4 m2 mho mol- l
wen BaSO4cfiT fcrnn?: :q I(1 Cf)('CI q)f q RCfl<1 'i chl M C!\ I
2 6
The solubility product of BaS04 is 1 x 1o- 10 md dm- . If the ionic conduc-
2 4 2 1
tance at infinite dilution at 25C of Ba+ = 12728 x t.o- m mho mol- and
s6;2 = 160-0 x 10-4m2 mho mol- 1, calculate the specific conductance of BaS04.
2. (a) (i) NO 311!! CfiT 311f?c!Cfl 311W I cf))P!CJ> fcn NO+, CN- cr CO
ttli 3ffi: NO Cfif NO+ fr Cfill t I
Draw the molecular orbital diagram of NO molecule. Show that NO+, eN- and
CO are isoelectronic, and the bond order of NO is lower than that of NO+.
2.(a) (ii) rnos;:1ra cfiT chlMC!\ I Ch1 m

Discuss the theory of absolute reaction rate. How does a cata1ys malcc eaction-
fastcr? 10

m-esc-u-chm 2
2.(b) w if 3ffil'll <iifct dP = ( llH ) <fir mu H'li <11 "'114 f'lT it 1:('li<'l -qzy:f
dT T V:L

-crffi CfJl qfti3ffi CfJl q") 4) {1 'i w:fl Cf)(O I "ChT tt JOi ICf) IJl C1
MCfiruC1 1

dP L1H
Starting with the expressiOn - = for the system consisting of two
dT T(V2 - Vi)
phases of a single substance in chemical equilibrium, derive the integrated form of
the Clausius-Clapeyron equation. 15

2.(c) N2 + 3H2 ---7 2NH3 27C "tR - 2197 Kcal I 50C "tR 3l-t1if5hll l
fchC141 m-m? N 2
, H2 Cf NH3 cR 27C 3fu: lBR "tR
68, 677 Cf 886 cal mol- deg- 1 1
The heat of reaction N 2 + 3H2 ---7 2NH3 at 27C was found to be - 21 97 Kcal. What
will be the heat of reaction at 50C ? The molar heat capacities at constant pressure
and at 27C for N 2, H 2 and NH3 are 68, 677 and 886 cal mol- 1 deg- 1. 10

3.(a) (i) ffi"lrc"l Oll l&:l l chlMC( I 3ftt fcti

fcntt- m "ChT 3lfmm- mlT WIT 1 tt IPOll Cl "CR "ChT CfliT m

Explain the adsorption theory of catalysis. Give one example and indicate the
of adsorption involved. What effect does a catalyst have on an equilibrium
system? 15

3.(a) (ii) 3lJi:qi(1Chl -ChT chlMQ\ 1 Cf p-CW1 3lJi:q i(1Cfi Olli<Sll l 1

3l JI:q 1(1 chi "CR crrq m "ChT quf;; cfl't MQ\ 1

What are semiconductors ? Explain n-type and p-type semiconductors. Discuss

the effect of temperature on semiconductors. 10

3.(b) ? TT" I CfliT

Define "Partial molal property". What is its physical significance ? 15

ch)onll CfliT ? ttQ illC11 \J'LIIfllffill
m -ChT Oll l&:l l chlMQ\ 1
What are the angular wave functions of d-orbitals ? Explain them, including their
geometric signs, with the help of neat and labelled diagrams. 10

4.(a) (i) ( lft lllPlCfi frr<:n:r CfliT ci{ I CfCl i.-CJ:i CfliT %?
Cfil1 CfCl lrcJ:i
"CfiROl I
State and explain Einstein law of photochemical equivalence. What is quantum
yield ? Explain the causes of low quantum yield. 15

3 m-esc-u-chm
- - -- - - - - - - - - - - - - - - - -- - - - - - - - - - - - - --

4.(a) (ii) mJ;:I<fl CfiT cruR cR I CfiT

Discuss the principle of polarographic analysis. Explain the meaning and
significance of half wave potential. 10

4.(b) q?r 3 - Yf<+=t l4l I

-rrit "tR Wcrur I If/ cr lf/ 2 cfu m$ncn cfu dl i<Slll I
Set up the Schrodinger's wave equation in 3-dimension. Comment on the nature of
the equation . and various tem1s involved. Explain the significance of VI and 1{1 .

4. (c) A+ B!i c
'CflT ACfll&i I
K _l
CfifB (-r) = 20 ,us cr 30
[A] = [B] = 10 M affi
[A] = [B] = 05
Find out the equi librium constant for the reaction A+ C
assurrring the relaxation time {-r) = 20 ,us and 30 ,us for
[A] = [B] = 10 M and
[A] = [B] = 05 M respecti;vely. 10

@0\S 'B' SECTION 'B'

. .
S.(a) (i) em $r d-3lTRfc:({1 'MY ic.rt cfiT dl i<Sll l I
'f(R q,l- I
Explain the pattern of splitting of d-orbitals in a square-planar ligand field.
Label each energy level properly. 5

S.(a) (ii) [Co(NH3) 6]Cl2 f#itc:&t 3ffi !1!"it$hOI l1f?f jSJCfi'll"1 'CflT

q RCfl<'1'"1 I
Calculate the crystal-field-sta bilization energy and spin-only magnetic moment
of [Co(NH) 6]Cl2 . 5

5. (b) :S I {Cfctl U firtT ( ffi rt:S I rt ) Ch l (Ill) 3f1<:A" trm tl +=! IC! lfl cfiT
m 1 Cfl((On 1

Draw labelled structures of all the possible isomers of dich loro bis (ethylene-
diamine) cobalt (III) ion. Does a meso form exist? Give reason to support your
answer. I0

m -esc-u -chm 4
5. (c) Fe/C0) cfit fu-& I cR fcn Fe q(l=J I'1 18 frr:n:r %I .
W1ite the structure of FeiC0) . Show that each Fe atom conform to the 18
electron rule. 10
S.(d) ;aqip:!l 3fl11 ? -R1?r ?
'ChT I
What do you understand by ali uxit.lati ve alluitlon" reaction ? Ilmv do eo it differ II

from an "insertion-reaction" ? Give one example in each case. 10

S. (e) -mql cfit ;aq::ct1'1 3lCfBlT +3 -mer 3ft\ m-aq::ct1'1

3lCfBlT I fctiNiQ) I
In general, the principal oxidation state of lanthanide elements is +3, but some
elements also exhibit other oxidation states. Explain. 10

6.(a) (i) 4H11Ch Cf1RUT ? m 'ChT I.

IF7 'o/fR cfit fcrfu fu-& 3ft\ rJ I I
W11at are the main reasons for the fonnation of interhalogen compounds?
Give one example of each type. Give the method of formation of IF and draw
its structure. 15

6.(a) (it) qf{CJdT ? cfit tk::ct<i l cr qf{CJJfd l

IW m tiIT 3lt.<:{!f'rJ" m m fcrfu cnr w:fm fcnm \1\TcfT %
'1ll1 1

What are "labile" complexes? Outline the relationship between lability and
electronic structure of a complex. Name the type of methocl. used in the study
of such complexes. 10

6. cb) f5htcC1 Chzo 1 cfit OLI 1<S1 1 ci( 1 q Rli lo1 'ChT 'Ch'0 cr-rB CfiTfi
Explain crystal-field stabilization-ene rgy. What are the factors that affect its
magnitude? 15

6.(c) HklRifula 4lf11ch'i IUPAC <i ll=l 1Cl(1l '1ll1

(i i) "[CO(N02) 3(NH 3) 3]

Write IUPAC nomenclature of the following:

(i) JS [Fe(CN\NO]
(i i) [CO(N0 2) 3 (NH3\ ] 10

5 m-esc-u-chm
7 o(a) (i) mg ChiiSITR&J w ? Ni(C0) 4 cn) cfit fciTcr >mr -M" \ifffiT %?
Ni(C0) 4 311!! -?tcfi %I
What are metal carbonyls? How Ni(C0)4 is obtained by Mond's process?
Show that the molecule Ni(C0)4, has a tetrahedral structure. 15
7o(a) " 3lTCr W 4d 3ffi {tl l4'1 cnT

What do you understand by "Lanthanide contraction"? How does it affect the
chemistry of 4d and 5d block elements. 1 0
7o(b) fto(tslf*lrt 3l11J CfiT crufrr chlMCJ> I
CfiT fclct{OI I .
Describe the important structural features of "Ferredoxin molecule". What is its
role in photosynthesis ? 15
7o(c) (II), "iT tll"llctllcf)
cnr 1 snfir1q; -qzyt cnr \3Y1'ffi
til"ll ct ll c41 <:tl "ChT >rm 1 cnr crufrr c:hl M0:
Starting with [PtC14f -, prepare diammine dichloro platinum (II). Name the isomer
formed. Choose the relevant starting material and write all the steps to get the other
geometrical isomer of the above product. .} 0

8o (a) (i) ? cr 3ffi: if 3lN w

cfit W% ? cfit 011<41 chtMCJ> I
What are low-spin and high-spin complexes ? Indicate spin states of CoFt and
complexes. Explain their magnetic character. 15
(ii) w% ? cf>l cr cnr crufrr
What is peroxomonosulphuric acid? Give its method of preparation, properties
and structure. 10
80(b) "Cttictffi4'trtl&l" 3l11J W %? nmr cfit fiQiliCi I -B" cnr
"Y"ffi ?
What are "Fluxional" molecules ? How does nmr spectroscopy help the detection
of fluxional character? 15
8 o(c) 1g rn cfiT m 1 atm 31i\ 273 K 0129 dm3 '11 Tm CfiT 3lTlRFf
311!! 162x lo- 10 m2
CfiT q RCh&l '1 I
Volume of nitrogen gas at 1 atm and 273 K required to cover 1 g of silica gel is
0129 dm3 . Calculate the surface area of the gel if each nitrogen molecule occupies _
an area on0.2x10- !0 m 2 . 10

m-esc-u-chm 6
CS (MAIN) Excun.:2016

m Prt8R1R9<1 q;1
Gl -q 1 arns m TfQ; GR)-q
3w:ftGcm q;l 1 m
13fu 5





* 311%

M 'Fn% 3fR w


3B1 fu"@ TfQ; "11( cnW

\iffiT 3ilcWlCfl m, q;l m Cffi TfQ; %I
(fCfi 1" m, m liT1"Cf) -q 1

m >r<mn TfOR1 1 3lifffii -B TfQ; m q;1 l1PfT eft -aB CfiTZT 1"
Tf<n m1 !!f?c!Cfll -q TfQ; cnW mrT q;l q;g


I Time Allowed : Three Hours I Maximum Marks : 250 I

(Please read each of the following instructions carefully before attempting questions)
There are EIGHT qu estions divided in two Sections and p1inlttl bolh in HINDI and
Candidate has to attempt FIVE questions in all.
Question Nos. 1 and 5 are compu lsory and out of the remaining, THREE are to be attempted
choosing at least ONE question from each Section.
The number of marks carried by a question/part is indicated against it.
Answers must be written in the medium authorized in the Admission Certificate which
must be stated clearly on the cover of this Qu estion-cum-Answer (QCA) Booklet in the
space provided. No m arks will be given for answers written in medium other than the
authorized one.
Coordinate diagrams, wherever required, shall be drawn in the space provided for answering
the question itself.
Uhless othe,rw1se mentioned, symbols and notations have their usual standard meanings.
Assume suitable data, if considered necessary, and indicate the same clearly.
Attempts of questions s h all be counted in sequ ential order. Unless struck off, attempt of a
question shall be counted even if attempted partly. Any page or portion nf thP page left blank
in the Question-cum-Answer Booklet must be clearly struck off.

1 l P.T.O.

1. (a) 3@fcft Cf11 $ 3fR fcf; (-1 0 D) Chl

>rGffia qmn I

Write the resonating structures of azulene and explain why it exhibits dipole
moment (-10 D). 10


Identify the major product (X} and discuss its stereochemistry : 10


(c) (II) 'WRT N-'?flPf('lfqqf{,g)Oj (I) CfiT 10 4 cfu4

(I} (II}
Explain why hydrolysis of 3-chloro-N-phenylpiper idine (I} is 10 times faster
than cyclohexylchloride (II} : 10

(I} (II}

(d) AA 'Q\Ci Cf11 $ o2n cfiT

CH 3- CHCl-CH=CH 2

For the reaction given below, write the structures of major and minor products,
and discuss the mechanism of their formation : 10
CH 3- CHC1-CH=CH...,.
2 _ __

(e) (Y) Cfi1 ClllR


Give the structures of (X) and (Y) : 10

N0 2

2. (a) 3ifug {"161lldl -B fc@ffi m3TI l!Rlcfi'l<J
\3'164 PI Rlcfi'l <l -ij f.l<:ifuf f.ll1fuT '1:1 "11 I

In the sulfonation of naphthalen e, discuss the formation of kinetically and

thermodyna mically controlled products under different conditions with energy
level diagram. 15

(b) f.18 (Y) d'm (Z) :


2 )1:::.

Identify the intermediat e {X) and the products (Y) and (Z) in the given reaction: 15

l) Amyl nitrate

2 )1:::.

Discuss the stereospecif icity of addition of singlet and triplet carbenes to

ci.s- 2-pt:n Le::ut:. 10

m v 3 [ PT n

(d) -q (X) cfn :
H2S04 j FeS04
(i} C6H 5 NH2 + C6 H 5 N0 2 + (X)


Identify (X) in the reactions given below : 10

(i) CGHsNH 2 + C6 H 5 N0 2 + (X) H /FeS0 4 Quinoline

3. (a) {iliqj(l{OJ Cfi1 3TI'1 fcRl Cfli4Tf."4<1

Q Br
How will you carry out the following conversion? 10

(bJ o -BT o -eft o o o c1 ffm- lJ,Ci ?ffi- -q c1 81 CRUT8.11"fffi cfn

Discuss the stereoselectivity of products in the reaction of MCPBA with cis- and
trans-butene. 10

(ii) H3C- CH=CH- CH20H

. .) 1) NH 20H
,,1111 C6 H 5-C=O --'---=-----_,.
I 2) PCI5
Predict the major products m the following reactions and write the
m echanism :
(i) x

(ii) H3C- CH=CH- CH20H

. . .) 1) NH2 0H
(111 C6H5 - C=O - --=-----_,.
2) PC15

m- &se-'D-(371'i'lt/ 2s 4
4. (a) (i) q;r Bfcmf.!Cfl 1:R Gl >rrn
q;r -quR
Stobbe condensation of acetophenone with succinic acid gives two
products. Write their structure and stereochemistry . 10

(ii) i\ A1Cl 3 Gl iRTffi t I

q;r $ 3W1 m1
Phenyl acetate reacts with AlC1 3 in an inert solvent to give two isomers.
Write their structures and indicate how you will separate them. 5

(b) f.rR Cfil i\ CfffiUT :


0 0 0 0 e
D 0
(i) (ii) (iii) (iv) (v)
Classify the following as aromatic, non-aromatic and anti-aromatic. Give
reasons : 10

0 0 0 0 e
D 0
(i) (ii) (iii) (iv) (v)

(c) q;r 3iTcffi'ICfl<OI 1:R 5 'Gf.ffi

Glucose on periodic acid oxidation gives 5 molecules of formic acid, whereas

fructose gives only 3 molecules of formic acid. Explain with reactions. 10

(dJ f.rR \C\4ia<on fclfmJ lfG1 q;r $ :

(i) 6 ----'
(ii) H 5c 6 --v -----7
Write various steps for the following conversions : 15


(i) ----' Nylon-6

(ii) -----7 Riphe:nyl

5 [P.T.O.

5. {a) -q 1,5-fuqz f.r1s:r


Give the Woodward-Iloffmann rule for sigmatropic rearrangement for 1,5-shift

involving hydrogen in pentadiene. Illustrate with FMO approach. 10

Write the major product (X) in the reaction given below and explain its
formation : 10

How will you carry out the following conversion? Write the steps involved in it: 10

(d) CH3 (CH 2 b - C==C-(CH 2 bCH 3 3"fR NH 3 -q "4i1

Discuss the stereospecificity of reduction ofCH 3 (CH 2 b-C=C-(CH 2 ) 2 CH 3 to

alkene with sodium and liquid NH 3 . 10

(e) KOH -q m q,l

Write various products formed from the reaction of 3-bromo-2,3-dimethyl-

pentane. with alcoholic. K.OH....lndicate the relative yield of the products. 10

m- &se- 'D-(!ril't/25 6
6. (a)
Cfi1 :

Among the following, identify the compound which can undergo Norrish
type TJ Write the mechanism : 1 ()

(i) CH 3 COCH2CH3

(ii) CH 3 COCH 2CH2CH(CH3b

(b) f.t8 % -qt<rcrcff -B\1ci Cfi1 quR :


U 32;:m
Write the intermediate and possible products for the following reaction : 10
U 32;vnm

Write the structures of repeating units of Nylon- 6,6 and Terylene. How are they
prepared? 10

Discuss the forces responsible for the stability of double helical structure of
DNA. 10

How ca.n ci3 a.nd tran.s- 1,3-cyclohexa.ne diul Le:: t.lisliug ui:shed using IR spectra? Iu

7 [ :P.'l'.O.
7. (a) ffi cn1 3ln: mfur :

C6 H 5 C6H 5
') I I H+
(l HsC6-y -y-CH3

Identify the major products m the following reactions and discuss their
formation : 15
C 6H 5 C6 H5
I I H+
(lj H5C6-y-y-C H3

(b) H8 :
(i) CH 2 =CH-CH =CH-CH =CH 2
(ii) CH 3 -CH 2-CH=C= CH 2
(iii) 2 CH2=CH 2

Write the product for the electrocyc lic reaction of the following : 15
(i) CH 2 =CH-CH= CH-CH= CH 2
(ii) CH 3 -CH 2-CH=C= CH2
(iii) 2 CH 2 =CH2

Give any two types of synthetic rubber and write the preparati on of monomer ic
units. 10

(d) ffi <frfTrcn 122, 188, 413, 581 695 <ltllllRCh ftr:R lll-l1 Cfi1

H....._ / COOCH2CH3

Assign the observed chemical shift values of 122, 188, 413, 581 and 695 for
the following compoun d : 10
H....._ / COOCH2CH3
H3C/ 'H

m- &se-'D-e: wt/25 8
8. {a} R"14 -q CfiT Amax 229 nm t? 71URT :

(i) Q (ii) Q

(iv) Ya

Which of the following structures has Amax 229 nm? Give the calculations of

Q y
each : 15

{i) (ii)



(b) f.r=1-q M+ -1 cfi1 m Cfi\ "fftfii1T i, m/(' lllTil
frc;f era

(i} CH 3 CH 2 CH 2 CH 2 CHO
(ii} CH 3 CHOHCH 2 CH 2 CH 3
(iii} CH 3 CH 2 COCH 2 CH 3


Identify the compound, which can give M+ -1 peak among the following.
Discuss its fragmentation pattem with m/ e values : 10
(i} CH 3 CH 2 CH 2 CH 2 CHO
(ii} CH 3 CHOHCH 2 CH 2 CH3
(iii} CH 3 CH 2 COCH 2 CH 3

(iv} CH 3 COOCH 2 CH 2 CH 3

'llt- zse v e?t1Jt/25 9 [ P.T.O.

(c) f.ll4 it Cf)T 31fu9 miRt Ch1 aft\ it

(ii) p-

Draw structures, label equivalent protons and indicate the number of signals
in each of the following : 10
(i) Mesitylene
(ii) p-ethylbenzene
(iii) Isopropylbenzene

(ii) 0 1) NBS


(iii) dJ OH
Pb(OAc) 4

Identify the major product (X) formed in the following reactions : 15

(i) (X)

(ii) 0 1) NBS
2) hvjheat

Pb(OAc) 4


10 7BS- 410