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I.
I
I
I
264
Sl. No.
C-DTN- K-DIA
CHEMIS TRY
Paper-1
Time Allowed
Three Hours
I l
INSTRUC TIONS
.... ,..
::>i#'li'l
~~I
q;y
f%"<fl
{';'11'"<1(
~-
OJ>\r it
"'
'R
Section-A
1.
{a)
(c)
(d)
15
15
15
2 . . (a)
C-DTN-K-DlA/40
20
'
1.
('fi)
15
(~)
(TI)
~ <f""i
.3Tf<1 ~ ~ ~
effi
~ 'R ~-m::
WFfi
fi'n
10 "ffi'i it~
~ 3lfuq;
-m
;;mft ~.
(tr)
4i<l<:1
mctt t?
15
fii"'''l
15
!>IICI~ R'l'l
effi ~
it
<f'ff <IIN<f ~?
chl~ <!; I
10+5
2.
('fi) N 2 <1m 0
3lfu9
~an
-it
Hii;l!; t ~ 'W"'!<tl"'
20
I P.T.O.
(b)
(i}
(ii)
Half-change
time
and
initial
concentrations of a reaction are as
follows :
ty, (sec}
a (mm of mercury}
425
354
275
540
941
158
(c)
10
10
kl
~
k_l
+A (rapid equilibrium)
~(product)=
dt
klk2[Aj2
k_r[AJ + k 2
C-DTN-K-DIA/40
20
'
(~)
{i}
<fil~({!
.
ThiiRl"'
.
.
iiFl!Cf>(
s, p om d <t>~
"<fil
~ 3!:!'1R ~ :
eis::ctlt{ f.'lqR1lT4ct
-
a ( mm
t% (flCf>U:S}
425
354
275
540
941
J
'ffiG
<ii1)
158
~<#it~ <flil
t? G<:
@Hi<t> "<filllUHI
cfil~({ I
(Tf)
10
t :
k,
A+A~A
~c._,
+A (<fur B\J<iH)
<;:til~({~
.!!._
(311<;) =
dt
klk2{AJ2
k_dAJ + k 2
C-DTN-K-DIA/40
20
P.T.O.
3.
(a)
(i}
{ii)
A
photochemical
reaction with
quantum efficiency of one shows no
temperature dependence. Explain.
Calculate the number of moles of
HCl{g) produced by the absorption
of one joule of radiant energy of
wavelength 480 nm in the reaction
H 2 (g) +Cl 2 (g) -4 2HCl(g)
if the
quantum
yield
of the
photochemical reaction is 1 - 0 x 1 0 6 .
(b)
10
10
Give
the
postulates
on
which
Langiiluir's
adsorption
isotherm
is
based.
Derive
the
expresston
for
Langmuir's adsorption isotherm. How
does this equation account for the
adsorption at (i) high pressure and
(ii) low pressure?
Show that when a diatomic gas adsorbs
an atom on the surface of a solid, the
Langmuir
adsorption
isotherm
is
modified to
e=
(Kp)'"'
fl + (Kp) v,l
where,
e
K
=
=
kadsorption
kdesorption
p = pressure of gas
20
(c)
20
3.
('f>)
(i)
~"'i"'
<t>to:v:~
(ii)
11"'1~1-<tet~f.i"'
<fit
"G!ffifl
<m-R->h: ;ffl'f ~
~.
tl ~ <fiif'i!Q.t
~ 3Jq'!0'lOI ~ m
WI
10
WI 3mnfto t
GJOi 'R
~~ ~
'R
~- ~ &i"'q> ~<>l
fiJ ~-
10
'llRl'!n 'l"'
<fiiMQ.I ~ <a>:ftq>(O!
~
ruJ
~ ~ ~ llifif( ~ q>(dl
t?
(Kp)'h
9 =
[1 +(Kp)%1
6 = ~ 3li<031i;;J 3Prr
K=k~
kr.h:fiquc
20
("1!)
'<4W"f't'14il<l ~ 3l!!'h<'l4il<l
<ifl'lid ~ 3J;'!qta
<fit
+'llctl (sites)
tof'lt
C-DTN-K-DIA/40
-am
ao:tq>t
~ ~
-m&rn
20
[ P.T.O.
4.
(a)
(b)
{c)
(i)
rate = k[N0] 2 [0 2
(ii)
20
2N0 2
10
10
Section-B
5.
{a)
{b)
(c)
15
1S
Explain what
and intensive
Which of the
extensive and
15
(i)
Entropy
(ii)
C-DTN-K-DIA/40
4.
( 'fi)
(<!i)
H2
(7f)
(i)
20
cR>-r
c#ilf'>ll{ 1
'h<:'H
Sl>i1r
20
2N0+0 2
2N0 2
~ ~ ~ = k[NOJ2!0212
~
<hlf'>ll{ f<); ~
~ <fu ~.
(fTq
"it~
~~<R~tl
(ii) ~
'1is q;r
mt ;;n-,
3H<Id"'
(!Of
10
~-<R
"it
q;r-!""
liM'll qftqJ"f
.~ ~?
5.
(<n)
10
l<f;ql ~ ~? IF 5
<f2ll IF 7
e<"<"HiaTI <Fi\
R&~o;<.>,:l
(<!i}
1s
U!li<lOI ~ 3"ll<!;fl, Ln 3 + ~
'W"<iic#il<i
imT 3ll'i .~ ~ ~?
>i I"'I~ ~
f.i'"'lfutf@d :pi~
3fu: <fi'R -~
l1l';ll
(i)
I{'"{T<fl
(ii)
C-DTN-K-DIA/40
<Fi\
{'<l <i"' ?
"it
15
<Fi\
3ll'i
~ <fi'R-~
15
I P.T.O.
(iii) Viscosity
(iv) Chemical potential
(v)
(d)
6.
(a)
Heat capacity
What
lS
meant
by
liquid-junction
potential? Why is KCl salt bridge used
to eliminate it?
Give one example of a concentration cell
with transference.
(i)
(ii)
(c)
15
X-rays
of
C-DTN-K-DIA/40
10
20
20
20
(iii)
~4Hdl
(iv) (I 14Rifi ~
{v)
("1)
di"41 t:ll~dl
tr
~-~ ~
6.
(iti)
tr<'i "'fiT~
3~11!(01 >!l~l{l
15
tll~dl
diutl
l<h>ll ~ ~?
<r<it
"if; f-iqfulfula
<m
kltl
>rm
<fil~((:
Cp -Cv
\!;ifi ~ ~
(<9)
(i)
=[P+(~!)J(~L
"if; ~ t1 klt:l
<fil~l!> I
'"'9f"l 'll
20
(ii) \!;ifi
q;ft4
f?f>RO<?l
-it
3ld(ld<?1
fiMl4 ~"if;
q(J"J::i
>rm
(ll)
er:JO<t<H
"'fiT
!>14'1, s3ll in
<fifTl"' am
20
~ ~ ~ {i41"4'"l<11 "if;
~ !>!<.4'1 ~ 041&11
<fil~l{l
tl!!~d
G'J~l{ I
C-DTN-K-DIA/40
maW 1
l<h(On
3ld(l<?1
3~11!(01
20
11
[ P.T.O.
7.
(a}
(i)
(ii)
Calculate
the
potential of the
following cell. Write down the cell
reaction and indicate the polarities
of the electrodes :
10
Cd 2 + (aq) Cd
Fe Fe + (aq)
(0-004 M)
(0-001 M)
FefFe 2 +
= 0-441 V
0
ECd/Cd2+
(b)
(c)
=0-403V]
20
(d)
integrated
form
of
this
15
(iii} {Cr(enb]Cl 3
(iv) [Fe(CN) 6
(vj
]4-
[Pt{py) 4 ] [PtC1 4
C-DTN-K-DIA/40
12
10
,---------
7.
(q;)
--
(i)
~"'lfclfuld ~ ~
(ii)
~ >lUI"! I <fi1f,;,l.{ I ~
Peri!<!
Fe 2 +(aq)
(<:9)
~ ~
q;J
10
(0001 M)
=0441 V
Fe/Fe 2 +
mo
(Tf)
J;8<t4l:s1
Cd 2 +(aq) Cd
l0004 M)
[ E
"'l<il <it
1!.:4> o ~ o
Ph<
~ ~
H<=iRlful<1
....m
{o ~
<fl"q -~
~. d
fu<l;
d 6 ~ d7
'R 01'1
q;J <i'lT
<im
<fi1 f.;,<; I
w:rrq
20
<:iRn
~?
~.
('<)
15
,[CoCl(H 2 0b(N~ 3 ) 4 ]
10
Cl 2
{Pt(py} 4
C-DTN-K-DIA/40
JJPtC1 4 I
13
[ P.T.O.
8.
(a)
(b)
{i)
account
of
S-N
10
(ii)
(i)
12
(ii}
(c)
Give a
short
compounds.
What is D.G
[ R=8-314JK- 1 mol- 1
(d)
20
[Ni(CN} 4
Ni(C0) 4 is tetrahedral.
(ii)
[Fe(CN} 6
[Fe(CN} 6 ) 3
is
diamagnetic,
while
is paramagnetic.
not known.
(iv) [FeF 6 j 3 1s
colourless,
[CoF6]3- is coloured.
C-DTN-K-DIA/40
14
while
8.
(<fi) (i)
(ii)
(<9)
(i)
5f
(fiq
<lel>lR<h
3i;li((UI
(ii)
<F'i1
'"hli"Cl
'
~ eistol
it<'f
\tG <fit
5
~<'i<t{ls
fuTJ:
it<'!
eiS(OI
~
o!fot<h
~(<lo;(
- . -..
<liiNIQ. 1
{jw:"H
Kc =18x10-7
PCI 5 (g)
12
fuTl: . 298 K
'R
= PC1
(gJ'+ Cl 2 (g)
~ ~ ~ O.G" f<h<HI
t?
( R=8314JK- 1 mol- 1
('Q)
~ ~
~-U%<;
f.l'""'lfBfutd
~ ~ <4i)~Q.l
~o "Q.11o "Q.'no
(TT)
'flY tffi! ~?
it<'f
10
20
[Ni(CNJ 4 12 -
~ q>f elldcll>l
Ni(C0} 4 "''~"'h<'f<lil<l
(ii)
[Fe(CN) 6 14 -
t, '"l"'i<h
Sll"d'!lf"'<A>l
t,
'"1"11<6
{Fe(CN) 6 13 - 3ift'""'4il4 ~I
{iii) f.\'q SI"''St>O! "'1!1;04><'1<#il4 ~~<'1 ~ ~I
(iv) [FeF6 j 3 - qohft'l
~.
'"l"'fili ICoF6 13 -
<!ui'Wf> ~I
***
C-DTN-K-DIA/40
15
BS--800
C-DTN-K-D IA
SI!H -'q";f-1
'{?IT'f> : 300
a:i::J{!l'l
:11ril<t>
JfR
&41
am 3#);41 <it;ff if
f'PlT
~I
~ -qlf{:l{,
Mfl<t>l
3&
~ :llf4'il-TT:'f
a:fk s -3JRqJ<f
&u:s it <t>'1-it-Cfi1'1 'l[<i'r m
fiMJ ~
dffi:
<fiMI{ I
~1
:~~r<lq;
<rlit
-31/<tN<t> ~.
d'l<'hJ
Note :
fit
ARfe cfilf.5ttz 1
WWtl{
nwT
---------------------------
SI. No.
I C-DTN-K-DIB
262
CHEMISTRY
Paper II
lnme Allowed : Tflree Hours
INSTRUCTIONS
Each question is printed both in Hindi and in
English.
Answers must be written in the medium
specified in "the Admission Certificate issued
to you, which must be stat~d clearly on the
cover of the 'Clnswer-book in the space
provided for the purpose. Jlfo marks will be
.given for the answers written in a medium
other. than thai specified in the Admission
Certificate.
Candidates should attempt Question Nos. 1
and 5 whick are compulsory, and any three
of the remaining questions selecting at least
Olle question from each Section.
Assume suitable data if considered necessary
and indicate the same clearly.
The number of marks carried . by each
question is indicated at the end of the
question.
Symbols and notations carry usual meaning,
unless otherwise indicated.
~: ~if Cf>T ~4/ <PII<"d< ~ !R"f-Cff it;
q<: gqr ~I
fllgiJ 'Pf
Section 'A'
l Ox6=60
'
(a)
(b)
...NHNH2
v .
(Q)
identify (P) and (Q) and -clearly show isotopically labelled *N.
(c)
(d)
(e)
C-DTN-K-DIB
'
{P] - + [Q]
(Contd.)
..........
en
~us
:
10x6=60
.( i3f) PI i>1 Rt R<1 d <il fi1 C!i t'!;<l il Qq; , at>i t'!;<l il RC!i 3M <II
ma- ~il&~RC!i ~-1 '4~Cfi anf.i4Ct ~d~~
*NHNH2
..
+CI-1J(C 2H 5 )CO
(P)
Bl',
(Q)
<if
Rt'll~ 1
Rtruq
CH 3 (CH 2 ))CHCH 3
l
F
( <:") <W:L! I
'3~1 c:
CfiT
<if
CH 3 0Na/C 2 H 5 0H .
(X)
m-
. ~dl~ I
-(C!i) mm'>T (P) <r<lT (Q) '3<"11<: ~ ;fFf <iT~~
if
4~'<~1<~
ch1Niq
~
~
C-DTN-K-DIB
hv
--'--+[P] -~ [Q]
'
(Contd.)
(f)
2. (a)
H2/Ni
2-3 atm
293 K
H202
(R) - - - - ( Q )
HCOOH
(S}
(b)
2-Methyl-3-phenyl-2,3-butanediol on treatment
with H 2 S04 gives a major product (X). Identify
(X) and write a mechanism to explain its
formation. Also write the name of reaction
involved.
20
(c)
C-DTN-K-DIB
(Contd.)
4 15'<~t<t
C6 H 5
. .
<hl PI~
it
~ (S)
(P)
cli't
20
CH-CH3
I.
'
KOH (ale.)
,;:,
.I
(P)
. H2/ Ni
2-3 atm
293K
HCOOH
H1/Ni
tO atm
400 K
(S)
("'! \SC
PI~~~
() 4Rh<1 ~
20
~ S03H+ ~ ~iH
~ ~-~ 'R 311Sfi ... OI '4;- ~ 3l'"F11Gl fi('tl'11
mm
C-DTN-K-DIB
..
::?0
(Contd.)
3. (a)
'
(b)
15
(i) OCH3
(P)
(ii) H20/H+
OH
(Q)
H3C;Q
COCH3
(R)
(c)
Write the
following:
.
H,c.-
resonance
structures
of
the
15
/CH=C-0
N~
~N-O
(Contd.)
(ar) f.tA!~Ma ~
:att<
<:1N!tt :
' .
eq '>I
15
<frr ~ HN031H2S04 it
<liT 1 '3Ff
%1.
<liT
.
(ii) ~
(iii)
~~tt I
(il") f.tA!f<:t~a it
<P>
~ (R)
(fql
q~"!tAt:t :
15
(P)
(i) OCH3
(ii) H20/H+
OH
H3c~.
anh.AICI3
(Q)
COCH3
(R)
C-DTN-K-DIB
(Contd.)
C-DTN-K-DIB
(Contd.)
HCI
( P)
peroxide
(ii)
CH3 -CH =
CH2
(iii)
trans-2-butene
4.
CCI 4
-~---..-
Br2
peroxide
(Q)
[RJ-<(S)
(T)
<ftfitq; I
<FT
~btd
15x3=45
(ii)
(iii)
~0+ PO~CoC~"-_L::.
_ _..
Ph
Ph.
15
C-DTN-K-DIB
(Contd.)
Section 'B'
5. Answer the following :
I0x6=60
nucleotides
(b)
(c)
_c_H..:;3_c_o_c_H...:3;,.. A
hv
'
hv
(e)
(f)
C-DTN-K-DIB
10
(Contd.)
10x6=60
<Rr riti"'<"'l"""'ITI
Gl"'l~ll I
(Gr) Gl<'"ill~'h
NH 3
i'r Na <;JI%a
31G"''4'1
iJ>'i'1flli.1
chl MQO
<it fqfS2
<fiMQO 1
CH COCH3
3
--=-----+A
hv
':i""Fi ~<i'h
(J) ~~I
>:rR ~>t~ii
"hT
re.
C-DTN-K-DIB
11
(Contd.)
li. (a)
(i) Define
PVC
Phenolics
Aminoresins
Polypropylene
Teflon
Alkyd resin
Nylan
Polyethylene
Po Iyster
Polystyrene .
(c)
C-DTN-K-DIB
12
(Contd.)
it it "ffl'f
.
. Rti'11 Pl'ffi .
Q;flt;;i'u M"'
q!<;jl s(lq <'il"'
(ii) ~if
<\filo::t
it f
~'l~<t ~it ~
qlPIR:<.l"'
tim~
10+5=15
'44'1<ttfi (N\'1
tifi'l=tft
<N ''tdl~ 1 '4tt1.<ffil "l:Ni"'' ~ '!'i'll <w;i'll ~ Cfir
:a<'cl<..<! 4il Mt:t 1
.
15
(~)
fi1'11PI'1
qffi
( <{)
'd('l I~
em- PI Rl\!; I
f.s "'1 PI Rl a it
Cfi lhl
q;r
cfit
10
A ~ B
oq 4'1 g fst;q I
<fiT qti'"ll f.s o::t tim arM'<iT &II 'i'Q I 4\l M"" I
2xl0=20
C-DTN-K-DIB
13.
(Contd.)
(ii)
0
CH,CH2 -
ll
hv
C-. CH2CH2CHCH, - - - +
I.
CH3
(b)
{c)
CH 2CH 3
CH2CH3
I
H-C-OI-1
I
I
I
H-C-OH
H - - c - OH
HO-C-H
C-DTN-K-DIB
CH 3
CH,
(A)
(B)
14
(Contd.)
7 .
(
(ar)
Yii>l'lRetl!H'fi
~B>um
i
~ 'dit<f <fiT fiN"'Ill fi';JfZq~ ~ ~
'3~@ cflM~ fcn Y~'fi if ~ m '11f<>IT Ystl
(I 31'4<11 II) ~ I
15
(i)
f.h="'MMd
hv
(ii)
0
CH3 CH 2
II
C -
"v
CH 1 CH 2 CI-ICH3 - - - +
CH3
Sl'fii'!IV!tll"'
9>"11
fclfu
. 15
CH 2 CH3
I
I
H-C-OH
I
- H - : - C - OH
I
I
HO-C- H
I
H-C-OH
. '
CH3
(A)
,C-DTN-K-DIB
CH3
(B)
15
(Contd.)
(d)
CH3
I
l
CHNH,
I .
CH,OH
(ii)
(e)
0
0
(ii)
0
CHO
CH3
CH1
C-DTN-K-DIB
CHO
16
(Contd.)
..
(G") ~ 41P1Cfl<i'r "ldl~lt ~ HI04 "'l1'ffi(Cfi(UI it~
eil<I ~ am ~""I <m ai'IPftll ~ ?
10
(i)
CH3
I
CHNH:;
I
CH 2 0H'
(ii) .
CH2NHz
I
CH2
I
CH20H
(q;)
~
~ ~<i<f; ~
.
10
(i)
(ii) .
CH3
CHO
Cl:f,
C-DTN-K-DIB
CHO
17
(Contd.)
..
8. (a)
Infrared
spectrum
NMR
spectrum.
Mass
spectrum
m/e at 117
(c)
Room
temperature
NMR spectrum of
acetylacetone exhibits two close by peaks at
8 = 197 and 214 ppm. Explain the reason
for their origin. What other peaks will be
observed.
10
(d)
C-DTN-K-DIB
18
s.
3l q'('ffi
'
fG~'l
o ~ 31(2H), 48(1H),
51(1H),
58(1H), 71(5H).
m/e~l17
l::ciq'il"'
~'IC:'i
~ <3<""1'11
9114'*'
~~'il
~ 4~'ll R<at{
Q:ruc:I"<'IG:+il"-1'1
- ef?lqo;c: f.lJW: 8
~ I '3'1
f.lJW:
<~>
~.
lMr?
10
f4 Q
Yffi ~ I
cfil M C{ I
3fi'1:f
if
10 .
3{1'1
C-DTN-K-DIB
m 3!N-
q;r
'*' ~ q;r
Q:ru?.1'1
if;
- 3o
'
Wif'JT
I0 .
19
C-DTN-K-DIB
<f11t4<1 fC:I::nH
!r-!01- q-sr II
! 'LOfl"q; : 3 00 !
<ilif if wrr '& 1
!n-;ff it> ~ ~ 1TTVPT if fi'riit ~ "'1/ffl~
Mtl<til d<-Ht..if "'NCh mr-'f?r if f<t>4t 1f"4T ~.
afh: ;rtf 1TTVPT i'f>T ~ di'ilt..'l ~- :ifd<li it>
9f'-'i<ti !nif
fflr<;J afh:
ajiJ;;f't
mm
wu:s
aik 5 <Hf.i<m[ ~I
iillcnl !n-;if
if it
~ if ~ 1f"4T
i'f>T
iff I
tlfl{l'"4
aN~.
'Jfiif
act>
'