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f4ziliJ'l/ DETACHAB LE
(fil4'1 I)
CHEMISTR Y (Paper I) 0000109
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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
4
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.
10
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+.
15
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
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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
I
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.(c)
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
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- - -- - - - - - - - - - - - - - - - -- - - - - - - - - - - - - --
4. (c) A+ B!i c
1
'CflT ACfll&i I
K _l
CfifB (-r) = 20 ,us cr 30
[A] = [B] = 10 M affi
[A] = [B] = 05
K
Find out the equi librium constant for the reaction A+ C
K_l
assurrring the relaxation time {-r) = 20 ,us and 30 ,us for
[A] = [B] = 10 M and
[A] = [B] = 05 M respecti;vely. 10
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
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5. (c) Fe/C0) cfit fu-& I cR fcn Fe q(l=J I'1 18 frr:n:r %I .
9
W1ite the structure of FeiC0) . Show that each Fe atom conform to the 18
9
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
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
Chirr
Explain crystal-field stabilization-ene rgy. What are the factors that affect its
magnitude? 15
5 m-esc-u-chm
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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
m-esc-u-chm 6
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CS (MAIN) Excun.:2016
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CHEMISTRY (PAPER-II)
1 l P.T.O.
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I SECTION-A
Write the resonating structures of azulene and explain why it exhibits dipole
moment (-10 D). 10
(X)
(X}
(I} (II}
4
Explain why hydrolysis of 3-chloro-N-phenylpiper idine (I} is 10 times faster
than cyclohexylchloride (II} : 10
(I} (II}
For the reaction given below, write the structures of major and minor products,
and discuss the mechanism of their formation : 10
e
OH
CH 3- CHC1-CH=CH...,.
2 _ __
2
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(e) (Y) Cfi1 ClllR
CHO
4
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
l)
y[Y)
{X)
2 )1:::.
Identify the intermediat e {X) and the products (Y) and (Z) in the given reaction: 15
l) Amyl nitrate
2 )1:::.
m v 3 [ PT n
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(d) -q (X) cfn :
H2S04 j FeS04
(i} C6H 5 NH2 + C6 H 5 N0 2 + (X)
fl.
0
(ii)
yA NH2NH2
UH
(X)
Q Br
How will you carry out the following conversion? 10
Br
(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
SOCl2
(ii) H3C- CH=CH- CH20H
. .) 1) NH 20H
,,1111 C6 H 5-C=O --'---=-----_,.
I 2) PCI5
CH3
Predict the major products m the following reactions and write the
m echanism :
(i) x
Zn-Cu
10x3=30
m- &se-'D-(371'i'lt/ 2s 4
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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
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)
(i) 6 ----'
(ii) H 5c 6 --v -----7
Write various steps for the following conversions : 15
6
0
5 [P.T.O.
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I SECTION-B
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
m- &se- 'D-(!ril't/25 6
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6. (a)
Cfi1 :
Among the following, identify the compound which can undergo Norrish
type TJ Write the mechanism : 1 ()
(i) CH 3 COCH2CH3
U 32;:m
Write the intermediate and possible products for the following reaction : 10
0
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.
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7. (a) ffi cn1 3ln: mfur :
C6 H 5 C6H 5
') I I H+
(l HsC6-y -y-CH3
OH OH
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
OH OH
(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
C=C
'H
Assign the observed chemical shift values of 122, 188, 413, 581 and 695 for
the following compoun d : 10
H....._ / COOCH2CH3
C=C
H3C/ 'H
m- &se-'D-e: wt/25 8
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8. {a} R"14 -q CfiT Amax 229 nm t? 71URT :
(i) Q (ii) Q
(iii)()
)(
(iv) Ya
.o
Which of the following structures has Amax 229 nm? Give the calculations of
Q y
each : 15
{i) (ii)
(iv}
(v}
(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
CH 3COOCH 2 CH 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
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
2)
(X)
OH
(iii) dJ OH
Pb(OAc) 4
(X)
(i) (X)
(ii) 0 1) NBS
2) hvjheat
(X)
Pb(OAc) 4
(X)
***
10 7BS- 410
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