I'

I.
I
I
I

CS (MAIN) EXAM, 2010

264

Sl. No.

C-DTN- K-DIA

CHEMIS TRY

Paper-1

Time Allowed

Three Hours

I l

Maximum Marks 300

INSTRUC TIONS

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 stated clearly on the
cover of . the answer-bo ok in the space
provided for the purpose. No marks will be
given for the answers written in a medium
other than that specified in the Admission
Certificate .
Candidate s should attempt Question Nos. ~
and S which are compulsor y, and any three
of the remaining questions selectinga t least
one question from each Section'
The number of marks carried by each
question is indicated 'at the end of the
questiOn:
Symbols ' and
notations' ' carry
usual
unles's . otherWise
meanrngs,
indicated.
Coordinate diagrams, !Vherever required,
may be plotted -on the .answer-bo ok itself.
Assume Suitable : data if
considered
necessary and .indicate the same clearly .

.... ,..

::>i#'li'l
~~I

q;y

f%"<fl

~ m-"BB iii fi'm<"t 'l!I

..

{';'11'"<1(

~-

OJ>\r it

"'

'R

Section-A
1.

{a)

Deduce the following equation for a

particle in a one-dimensional box giving
the Haxniltonian explicitly :

\Jfn =A sin( :x)

(b)

(c)

(d)

Also deduce the energy for the system.

15

Using VSEPR theory, predict the shapes

of PC1 2 F 3 and SF4 . Indicate the state of
hybridisation in each case.

15

How do you account for the fact that the

rate of reaction is more than double for
a
ten degree rise of temperature,
whereas
the
number of collisions
1ncreases by only 3-4"/o for the saJTie
rise of temperature?

15

What are meant by phase, component

and degree of freedom? Define Gibbs
phase rule.
A saturated solution of sodium sulphate
with excess salt is at equilibrium with
its vapour in a close vesseL How many
phases, components and degrees of
freedom are there in the system?
10+5

2 . . (a)

Draw the MO energy-level diagram for

N 2 and 0 2 molecules. Predict their
magnetic behaviours and also calculate
the bond orders.

C-DTN-K-DlA/40

20

'

1.

('fi)

f<l<fl;q Cfirn -it Rhl 'fiUT ~ ~ f.is;;R1fula

e+ft ifi(OI effi >mt chl ~ <!; <1m ~fq <'2) f.i>H 'fir ~
3~{51 chl~<!; :
<t'h<:1

15

(~)

<flo ~o ~o tfto -31Ro fB<&HI 'fir llzilI ~ ~

PCl 2 F 3 <1m SF4 "ch1 3ll~Rl 'fir <>il'h<;'l"! <tl~t:tl

l'Jfilifi ~ ~ fiq;(Oi 1Clf"'l 'fir ~ 3~{51 <tJ~I!;I

(TI)

~ <f""i

.3Tf<1 ~ ~ ~

effi

~ 'R ~-m::

WFfi

fi'n

10 "ffi'i it~

~ 3lfuq;

-m

;;mft ~.

"*'14; fi"' gl "ch1 fi&ll it ;n:fi "ffi'i-~ -it ~

3-4% ~

(tr)

4i<l<:1

mctt t?

15

l'l!Cif"'l, "'C<f> <1m {<ld5ldl-~

fii"'''l

15

!>IICI~ R'l'l

effi ~

it

<f'ff <IIN<f ~?

chl~ <!; I

~~>ITs -it Ql~'l>l th4>c 'fir~ klii1'1"1, ~~

<:1 qUI 11m 3l ~q; t, 3l'f.% q]'>J:f it <ill All<!f>!ll if ~ I ~
~ it f<ht~;ft l>llC!f"'lll :, "'c'h ~ {<ld'lol 4>1R<~T

10+5

2.

('fi) N 2 <1m 0

3lfu9

~an

-it

~ 'l!;lio aTio ~-R

Hii;l!; t ~ 'W"'!<tl"'

chl~<t <1m 3!!ail!{

C-DTN -K-DIA /40

'hlR: "ch1 'l:fi

3

Oll<'lt:R 'fir 3!1'h<:1'i

'101'11 *lAiti;l

20

I P.T.O.

(b)

(i}

(ii)

State the essential conditions for

hybridisation. Show diagrammatically the possible geometries from
hybridisation of s, p and d orbitals.
Give examples.

Half-change
time
and
initial
concentrations of a reaction are as
follows :

ty, (sec}

a (mm of mercury}

425

354

275

540

941

158

What is the order of the reaction?

Calculate the rate constant.

(c)

10

10

Lindemann's mechanism for the firstorder reaction is given as follows

A +A

kl
~
k_l

+A (rapid equilibrium)

A __k_,2=--~ product (slow)

Show that

~(product)=
dt

klk2[Aj2
k_r[AJ + k 2

Under what condition will the reaction

show (i} first order and (iij second order?

C-DTN-K-DIA/40

20

'

(~)

{i}

B<f>(O! ~ ~ 3l!CI~<!Cf> qftf~la<ii "Cf>T qufor

<fil~({!
.

ThiiRl"'
.
.

iiFl!Cf>(

s, p om d <t>~

"<fil

(ii) "({<t> ~ ~ ~ 3W qft:<~d"l 'fiT<'! om

~

~ 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

~-~ 3l~fskl ~ ~ ~~H fsii<t!~fu ~

Sl<t>R

t :
k,

A+A~A
~c._,

+A (<fur B\J<iH)

<;:til~({~

.!!._

(311<;) =

dt

klk2{AJ2
k_dAJ + k 2

~~~ii R<!llt!!ll fiJ~~=

(ii) fu<fl;q <hl fZ ?

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

fraction of surface covered

=
=

kadsorption
kdesorption

p = pressure of gas

With proper diagrrun, calculate and

explain briefly the limiting radius ratio
values for tetrahedral and octahedral
sites.
C-DTN-K-DlA/40
6

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

(g)+Cl 2 (g) -42HCI(g) il

480 nm d{t~>4 q,,,.;] ~ "@ ~f.t(Ut ~
H

~ 3Jq'!0'lOI ~ m

HCl{g) ~ l?ict1 <fit ~h!ll

<fit '1"1'11 <fiif-iltt, ~ !>lq>I'II-<IBI<!f.lq> ~

<\ !tiF"!'l "SI"Ifi! 1 0 X 10 6 ~I
(19) ~ ~ ~ <fiif.ill(,
e'ldlq

WI

10

WI 3mnfto t

GJOi 'R

~~ ~

'R

1 ~~~ 3iftl'!i'lt<ol <a"'dlq

~- ~ &i"'q> ~<>l

fiJ ~-

10

'llRl'!n 'l"'

<fiiMQ.I ~ <a>:ftq>(O!
~

ruJ

~ ~ ~ llifif( ~ q>(dl

f.'n::;f G1<l 'R

t?

~ <Htfo;;Q. f<f> ~ f.t<:fl oR:r ~ ~ >R Q<Mr~"' -ilB

~ qvw~ ~ q>(dt t, <R cl'l"% 3iftl'!ilt<ut
e'latq WI il ~tR ~
'iffiiT 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

qof;r. e~fila ~ Hrq><: <ARitt 1

C-DTN-K-DIA/40

-am

ao:tq>t

~ ~

-m&rn
20
[ P.T.O.

4.

(a)

Draw the phase diagram of a simple

eutectic system. Give an example of
such a system.
20

(b)

Using the principle of LCAO, obtain the

normalised wave functions
for the
bonding and the antibonding molecular
orbitals for H~ system.

{c)

(i)

For the reaction

2N0+0 2

rate = k[N0] 2 [0 2

(ii)

20

2N0 2

Explain that the

rate of this
reaction decreases with increase of
temperature.

10

How much will the rate of reaction

change if volume of the vessel is
reduced to
of its original volume?

10

Section-B
5.

{a)

{b)

(c)

What are interhalogen compounds?

How are they classified? Give structures
of IF 5 and IF 7 .

15

How do you explain the magnetic

properties of transition metal ions, Ln 3 +
by the Crystal Field Theory?

1S

Explain what
and intensive
Which of the
extensive and

15

are meant by extensive

properties of a system.
following properties are
which are intensive?

(i)

Entropy

(ii)

Gibbs free energy

C-DTN-K-DIA/40

4.

( 'fi)

(<!i)

1% m<'! "i?f<Rct> mt "Cfil Sll <'I~ ;mW H I~ I{ I i)jt

<f:i "Cfil 1% 3C:It'(UI <ftMI{ I

H2

mr ~ 3Thift:R ~ ~-~ 30lii'U4ct> <noo

~ ~. ~o -.fto ll;o alto fuOG:Fd "Cfil

~. Slet<l ro:4lt><~

(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

aeif> '@ 3il<ld'l

~-<R

"it

q;r-!""

liM'll qftqJ"f

.~ ~?

5.

(<n)

10

a:f<m-~ctl"''l q'lfi'Jct> <!lfl ma ~? $'1Cfil <'1 1 ffCfi{UI ~

l<f;ql ~ ~? IF 5

<f2ll IF 7

e<"<"HiaTI <Fi\

R&~o;<.>,:l

(<!i}

1s

U!li<lOI ~ 3"ll<!;fl, Ln 3 + ~

fsbe:<:1 !${ Rl"!:J~

(71)

'W"<iic#il<i

imT 3ll'i .~ ~ ~?

l<f;~ mr ~ 'll"~' ~ ~ l1l"'l- {'<la54 ~

~ ~ ~?

>i I"'I~ ~

f.i'"'lfutf@d :pi~

3fu: <fi'R -~

l1l';ll

(i)

I{'"{T<fl

(ii)

fTi iii;>~ <fu :rm ~

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.

What Is meant by heat capacity?

Establish a relationship between heat
capacity at constant pressure and
constant volume; i.e.

Deduce the relationship for an ideal gas.

(b)

(i)

Derive Bragg's equation and show

that nA = 2 d sin a for the reflection of
X-rays from the faces of a crystal.

(ii)

Calculate the interplanar spacing

(d-spacing} in a cubic crystal if the
second-order reflections from such
planes are obtained.
sine = 0 38,
when
A 154 pm are used.

(c)

15

X-rays

of

Discuss the different types of isomerism

exhibited by coordination compound.
Give suitable examples.

C-DTN-K-DIA/40

10

20

20

20

(iii)

~4Hdl

(iv) (I 14Rifi ~

{v)

("1)

di"41 t:ll~dl

tr

~-~ ~

>n dl<"l>f ~? ~tlib 14<?i)q'l ~

KCl <'1""1 ~ "'fiT !>i<i'l'l

~-~ t~iJ<OI

6.

(iti)

a>utl t:~1~a1 "'fiT

'

tr<'i "'fiT~

3~11!(01 >!l~l{l

15

>n dll>f ~? f-i>la 3114<1'1 <~m <:1<i

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

fm Wflifi(OI <ID "'!!<"l'll <fil~l!> <1m ~~lfl;l{ fcfi

f<hiJl l?f>RO<'l "if; <!i<'l'*>J ~ ~-fCh(UI "if; q(I .. J'l
~ n).. = 2dsinS~I

(ii) \!;ifi

q;ft4

f?f>RO<?l

-it

3ld(ld<?1

(d-3idU<?1) ~ >101011 chl~l{,

fiMl4 ~"if;

q(J"J::i

>rm

"4R i)jt <f<?l1

(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

sine = 0. 38, """ 154 pm A.

l<h(On

3ld(l<?1

3~11!(01
20

11

[ P.T.O.

7.

(a}

(i)
(ii)

What is Nernst equation? Explain

the various terms involved.

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]

Find the expression for CFSE of d 5 , d 6

and d 7 systems in weak and strong
octahedral fields in terms of Dq and
P (pairing energy).

20

What is the effect of temperature on the

vapour pressure of a liquid? Derive
Clapeyron-Clausius equation for the
equilibrium between
liquid- vapour
Give
the
equation.

(d)

integrated

form

of

this
15

Write IUPAC names of the following

[CoCl(H 2 0b[NH 3 ) 4 ) Cl 2
(ii) [PtCl(NH 2 CH 3 ) 2 (NH3)Cl]
(i}

(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;)

--

~ w:fl'h<"l "'I'll~?~ 5!'!:!;m ~

(i)

chl f.;, I.{ I

~"'lfclfuld ~ ~

(ii)

~ >lUI"! I <fi1f,;,l.{ I ~

Peri!<!

~<it Rlfult; "~

<!@@ <fi1 f.;, Q; :
Fe

Fe 2 +(aq)

(<:9)

~ ~

q;J

10

(0001 M)

=0441 V

Fe/Fe 2 +

Hiilcl ~ Biilcl 3lf!4icl<fil'l ~ ~' Dq (!~ p

('!flcl'l ~) ~

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

O<j 'il'h mt1

'R 01'1

q;J <i'lT

<im

<fi1 f.;,<; I
w:rrq

20

<:iRn

~?

BlJ><'H . ~ .1W!. <t8<hT'l-

~.

"fi'113!"fl<m e>fl'h<"l ""!:!<'"~" cQf,;,<; : .

('<)

15

H"'lfdfuld ~ ~o <L_o <;fto lJ;o <flo~ f<1fult; :

(i}

,[CoCl(H 2 0b(N~ 3 ) 4 ]

10

Cl 2

(ii) [PtCl(NH 2 CH 3 h(NH3}Cl]

(iii) [Cr{enh]Cl 3
(iv) {Fe(CN) 6 ] 4 (v}

{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)

Why are Sf elements important?

(i)

Distinguish between chemical cell

and
concentration
cell
giVIng
examples.

Derive an expression for the e.m.f.

of electrode
concentration
cell
without transference.

12

(ii}

(c)

Give a
short
compounds.

For the equilibrium

PC1 5 (g)= PCI 3 [g)+ Cl 2 (g)
at 298 K, Kc = 1 8 x 10-7
for the reaction?

What is D.G

[ R=8-314JK- 1 mol- 1

(d)

20

Give reasons for the following

(i}

[Ni(CN} 4

is a square planar, while

Ni(C0) 4 is tetrahedral.
(ii)

[Fe(CN} 6

[Fe(CN} 6 ) 3

is

diamagnetic,

while

is paramagnetic.

(iii) Low-spin tetrahedral complexes are

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)

S-N <!'Hi'tif>l 'fiT m~ qof'l <4il~Q.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

R'""'IRifutd ~ <hi(OI "'dl~l!. :

(i)

[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

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&41

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~I

~ -qlf{:l{,

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3&

~ :llf4'il-TT:'f

if fiii;>JI >mT ~. a:fk W lfTVP1 "'f>T txn!

3& 3fR- jf<i<t> <1> ?J&-'!11 'R :a-ifiii;d f.lf<fe ~ w
fiii;q, ~ "<tJWl{l >r~-TT;f TR ;o;@mm lfTVP1 $
3-lmnm 3F!l fiii;ifl lfTVP1 if fffiit '11{ 30{ w qit-f ~
=rtf fiidfij I

a:fk s -3JRqJ<f
&u:s it <t>'1-it-Cfi1'1 'l[<i'r m

fiMJ ~

dffi:

<fiMI{ I

~1

<n1 Jr.Fif if it :~~r<l<t>

~'l<t>< Pi;-iff fft;r Jr.Fif $

:~~r<lq;

m <1> ~ A>Irt 3ict> m $ 3RT if ~ 711{ ~ 1

:~~ifl<t> a:fk fl~mm <1> mllF4 3-l2f g, 3F4?fT ARfe ~~
AJwi<t> 31ft&,
-3Jiq'PJ<t> ~. dffi:-j<'hl 'R
C>ltdf&d WMtz I

<rlit

-31/<tN<t> ~.

d'l<'hJ

Note :

fit
ARfe cfilf.5ttz 1

;o;q?iffi 3-lt<t>if <fiT "'<Ff

WWtl{

nwT

English vers1on of the Instructions is

printed on the front cover of this
question paper.

---------------------------

SI. No.

I C-DTN-K-DIB

262

CHEMISTRY
Paper II
lnme Allowed : Tflree Hours

II Maximum Marks : 300j

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

1. Answer the following :

,t:

'

(a)

Whether the following compound is aromatic,

non-aromatic or antiaromatic. Justify.

(b)

In the reaction sequence

...NHNH2

v .

+CH,(C 2H 5)CO--+(P) BF,

(Q)

identify (P) and (Q) and -clearly show isotopically labelled *N.
(c)

Write the major product (X) of the reaction

CH3(CHz)JCHCH3 CH30Na!CzHsOH (X)
I
F
.

(d)

Write the major product formed on treatment

of urea with NaOBr. Also write the name of
the reaction involved.

(e)

Identify intermediate (P) and product (Q) m

the reaction
hv

C-DTN-K-DIB

'

{P] - + [Q]

(Contd.)

..........

en

~us

1. HJ>1ktfud ~ 'd'a<: <IN!~

:
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 (P) cr<rr (Q) <f?t 4~"'11'1 ch1NI~ cr<rr ~'"lt"ltHchlLI

<ll'"lifih<l "N

<if

Rt'll~ 1

(tr) f.li>1Rtrua ~ ~ ~ '.!lL! ~~I<: ex> <if

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)

N aOB T it '<N"''I<:U I <R ~<Iii ~ ',!lL!

Rt Ro1 q <r<rr fi 4 ?l 31M rst;L! 1 CfiT <wr

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)

A mixture of formaldehyde and p-methoxybenzaldehyde 1s treated with cone. KOH.

Write the products of reaction.

2. (a)

Identify (P) to (S) in the reaction sequence

20
KOH (ale.)
(P)
0.

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)

Draw resonating structures for the attack of

S0 3 H+ at different positions of Indole, ~sing
curved arrows. At which position attack occurs
preferentially ? Draw an energy profile
diagram for the position of preferential attack.
20

C-DTN-K-DIB

(Contd.)

(~) 'hRi'l"''rn~~ om p-..rl<il<ffi16l"i1~&~:s1~t~ ~

fil"'fOI Cf>f ~ KOH ~ -d4"'11f<:<1 Mi<11 7f<IT ~I
~ ~ '3c:<i1Gl. <it PIR.<t~ 1
2 . (3f) f.ls:<tfi1fu<1 ~ 3l'f'i>+t

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)

(Gi') 2-i'l>ll1.<1 3 "hl<ti~"''-2,3-"'~""'il:t;?J"'-:s""1<'1= <it H 2 S04 ~

'34"'11ft <t><JI <r<: '3<:<ll<% (X) 9TEf. i'1<11 ~ I (X) cli't
4~"'1H <hlP!~ ~
~ C!i<::

("'! \SC

PI~~~
() 4Rh<1 ~

-.:mCt; <SF"trt cli't Rhlfi"lfcl' <it

<hl PI~ 1 fi q ?I ~ Cf>f "ffl1

20

~ S03H+ ~ ~iH
~ ~-~ 'R 311Sfi ... OI '4;- ~ 3l'"F11Gl fi('tl'11

H('ll Cf>f 9<1lt Cf>(d

'

"~ <11~ll 1 "FA "'~l>'T'-1<1rt1' 'R ~ ~ ~ 31~1Sfi=...

~o=J

mm

~? 3ifu ... '"<l 3i1Sfi ... UI ~ ~ ~ ~ ~ d?"lf

!il'ht~"'' 31RIEI z41RI~ 1

C-DTN-K-DIB

..

::?0
(Contd.)

3. (a)

Answer the following :

15
(i) A student carried out reaction of aniline
with concentrated HNO)~S04 Write
the structure of product/s he is likely to
obtain.
(ii) Write a mechanism to explain the forma. tion of major product in (i).
(iii) If the reaction in {i) is carried out only in
. nitric acid, write an equation for the
formation of No;.

'

(b)

Identify (P) to (R) in the following:-

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

Explain its aromaticity in nitration reaction.

C-DTN-K-DIB

(Contd.)

(ar) f.tA!~Ma ~

:att<

<:1N!tt :

(i) ~ m'!f ~ (tf.i<41'1

' .

eq '>I

15

<frr ~ HN031H2S04 it

<liT 1 '3Ff

:a<:<11 ~; '3<:<11 <~1

*"~ '11 ~ ~ tt ;;it <11? "!mr <iK fl Cfi<:f I

%1.

<liT
.

fsl>llt-Fifu ct>T k!fi:qtt m (i) if "!mr ~

~ ',J<i'll 'd<:<ll~ <if il '11 Jl t I
~ (i) if ~ 4i'h'1 '11'4f{<t> 3Jl!<'f it
eq'>l <liT 1Tt ~~NO! il'11rt <!I <'II e..Oct>(UI

(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)

(ar) H'""'Rlft<~d ~<fir fst;q, fctfu

<ftfitq; I

<FT

~btd

15x3=45

(ii)

(iii)

~0+ PO~CoC~"-_L::.

_ _..

Ph

Ph.

<fir fi<:*l'113it <if '3'1 <fi'l (t<l il R:<:tia I <fir a~ I4 I <ft Nt ~ I

(<if) [6], [10}, [12] <fliT [14] Q;4:_<"il'1

iii 'i l'o:lt <fliT

15
C-DTN-K-DIB

(Contd.)

Section 'B'
5. Answer the following :

I0x6=60

(a) Draw the structure of purine

present in DNA.

nucleotides

(b)

Benzoic acid on reduction with Na in liq NH 3

gives 1,2-dihydroproduct, whereas, anisole
gives 2,5-dihydroproduct. Explain.

(c)

Predict the products and explain the,ir formation

_c_H..:;3_c_o_c_H...:3;,.. A
hv

'

hv

(d) What chariges do you expect in the electronic

spectrum of acetoacetic ester in hexane and
ether.
1

(e)

H NMR spectrum recorded for CH3 -CH= CH2

at 90 MHz gave coupling constant (J) of 5 Hz
for vinyl protons. If spectrum is recorded at
500 MHz, write the expected value of co!Jpiing
.,
constant.

(f)

What is the range of fingerprint region in infrared spectrum. Write

the. range in which
.
carbonyl group normally absorbs.

C-DTN-K-DIB

10

(Contd.)

10x6=60

<a1 > m- ~ 1:1; if

R~ '"i 1"' 9f<"1 4ff"~41 c: 1~1

<Rr riti"'<"'l"""'ITI

Gl"'l~ll I
(Gr) Gl<'"ill~'h

3fl'<'f CfiT s;q

NH 3

i'r Na <;JI%a

31G"''4'1

~ G1:" 1,2-Q:>QI~il '3(qp~ '9TH~ ~- 'ilGf Pcf;

iJ>'i'1flli.1

2,5-Q:~I~.j'J '3(<11G ~ ~, fqtS<!

. ( ~) '3(<11~1 <m 31'!'"11"1 w11~ll <NT '3"14> \l'qo1

chl MQO

<it fqfS2

<fiMQO 1

CH COCH3

3
--=-----+A

hv

(G) ~<N\"1 'C(Cf~ if i);ruili);ruQq; QOR< it ~~<f?tH'h

~ 'f?'"i if 3Wf fct>fl q f<:<l d'1 <fir amn 'h<d ~ 7
(en) CH3 -CH = CH2 CfiT 90 MHz G1:" 1 ~ 1:ff 'Q!f3IT'C
~ 'f?'"i ~ f4 "'I ~<1 si'Jil"' 4>- ~ 5 Hz CfiT

':i""Fi ~<i'h

(J) ~~I

>:rR ~>t~ii

"hT

500 MHz '1< f4i4 I ;::;rr>i 'Ci'Gf ':!ii"' ~ CfiT

311>11Ha +wr Gldl'4ll 1

() 31<l<:tt> ~~ii if '<>i']fi't ID'f ~ q;r q<:m f<ta"'l

~ ~ I CfQ q'(Jl;J fi1 lOt M fl ii if> I <i!l'f.i <1 cr<f

re.

fll'"il""'d: 31Cr.li'!ttOJ 'h'Cdl ~I

C-DTN-K-DIB

11

(Contd.)

li. (a)

(i) Define

thennoplast and thermosets.

Which are thennoplast among the
following?

PVC
Phenolics
Aminoresins
Polypropylene

Teflon
Alkyd resin
Nylan
Polyethylene
Po Iyster
Polystyrene .

(ii) Differentiate between LDPE and HDPE.

10+5=15
(b)

Give the synthetic route of epoxy resin based

on bisphenoi-A. Mention the principal fields of
applications of epoxy resins.
15

(c)

Write the product formed in the oxidation of .

quinoline by Cr03
10

(d) Identify A and B and discuss the selectivity of

the reagents
2xl0=20

C-DTN-K-DIB

12

(Contd.)

6. (ar) (i) "ffl'f ~~~4 tim."ffi'f ~<fiT~ 4\lN\~ 1

f.s10i1PIR<t~

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 ~

"' I Q <'11 '1

q'j PI I{RO<

qlPIR:<.l"'
tim~

if it {if ai<R: em-~

10+5=15

(<if) ~t4i'l'11<1..:A 'R ~

'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

( <{)

<iir. Cr03 ilT<T l:ill<'#il<fi(OI ~ 'R <SI"'~

'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.)

7. (a) Write the structures of possible products of

following
photochemical
reactions
and
mention the type of Norrish process (I or II) in
each.
15
(i)
hv

(ii)

0
CH,CH2 -

ll

hv

C-. CH2CH2CHCH, - - - +

I.

CH3

(b)

Photochemical (2 + 2) addition of benzophenone with cis- and trans~2-butene yield a

mixture of same products. Explain their
formation with the mechanism.
15

{c)

Which among the following.(A or B)is formed

when Pent-2-ene is oxidised by Os04 and
NaHS0 3 ? Explain its formation with the
mechanism.
10

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

<;;r > "''"'111 N>o?~ '1

Sl'fii'!IV!tll"'

~ *~ '"'"~ !\'! ~ m&r-2 -4'-li '1 it

(2 + 2) . fli<'li<\ 'R ~ d<'il~'i Cf>T

fli "'or 'ffi1 m<rr ~ I

ttf%a eel~ <iiiM~ 1

'3'1 cfl "1'11 <R

9>"11

fclfu
. 15

(~) ~ ik-2-~ ~ Os04 ~ NaHS03 liRT llli'ffl"l'!'d

f<hlll "'ldr ~d'Gf H+"'l~Ria if~m(A lllll<ir B)
"'ij d I ~ ? '{-1 4; A 'ito! ~ 9il!l fclfu ~ e-llS<!
<iiiM~ I
10
CH2CH3

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)

Identify the compound susceptible for

oxidation and justify
(i)

CH3

I
l

CHNH,

I .

CH,OH

(ii)

(e)

Write the reagents required for the following

conversions.
10
. (i)

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;)
~

H""'1MR1d Gia<:un .it

<it iii d l'<ll

~ ~<i<f; ~
.

10

(i)

(ii) .

CH3

CHO

Cl:f,

C-DTN-K-DIB

CHO

17

(Contd.)

..

8. (a)

An organic compound with molecular formula

C 9 H 10 gives following spectral characteristics.
. Electronic : Amax at 235 nm
spectrum
.

Infrared
spectrum

3035; 3000, 2925, 1640, 990,

915,"740 and 615 cm-1

NMR
spectrum.

8 at 31(2H), 48(IH), 51(1H),

58(1H), 71(5H)

Mass
spectrum

m/e at 117

Suggest a- possible structure with probable

justification for each spectral feature.
30
(b)

What characteristic bands. will be observed in

the ir spectrum of J,phenylethanone?
10

(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)

How would you determine molecular wt of

acetone on the ,basis of its mass spectrum ?
Suggest possible fragmentation pattern.
10

C-DTN-K-DIB

18

(ar) <:% qo;t"ff.i~ <ilfi'lqo; fiileqo;l 3llf04qo; ~ C 9 H 10 ~

.. -. ,.!.f.i"'1PiR'I<~ fG'I~>l1-~ ~ ~:

s.

3l q'('ffi

'

3035, 3000, 2925, 1640. 990,

915, :740 ~ 615 <:m- 1

fG~'l

o ~ 31(2H), 48(1H),

51(1H),

58(1H), 71(5H).
m/e~l17

l::ciq'il"'
~'IC:'i

~ <3<""1'11

li!'fl lt,ll CMT !ii<llqo;

;>flf'i<:q <it m iilctl~i'l 1

9114'*'

~~'il

("1") 1-\hl'il~<'i~<'hl'i ~ ir ~~" if ~

<~)

~ 4~'ll R<at{

Q:ruc:I"<'IG:+il"-1'1
- ef?lqo;c: f.lJW: 8
~ I '3'1

f.lJW:
<~>

~.

lMr?

10

q,~:r ctT'f ~~am: ~~'"l <tt

= 197 ~ 214 ppm~ K<..'lldl
if; 1(01

f4 Q

Yffi ~ I

cfil M C{ I

3fi'1:f

if
10 .

~::oq., ..... ~'~~" if; '3ffiTR

~mer qo;"{>) ? ~ 14<..~6'1 Slru'll'i

q;r 3llfikl'*' "1R,

3{1'1

<it !i!'fi 1\\ll

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

'J'ff-'[f' 'R <H"fi?na Ptue ~ 'R

Cif/'1/
"''tffl~ 1 N:(T-'T'f r.rr oafii:lfilm +m.Gfif it> <HRtf<m
3RT t<t>m 1TTVPT if fi'riit ~ ~ r.rr cirf aiCf>
rrif fili'Ji'J I
!nif ti~, I
9('l}q;

wu:s

aik 5 <Hf.i<m[ ~I

iillcnl !n-;if

if it

Cfi1'f- it- Cfi1'f ~ !nif '!'1 '1Cfi < mril

citrr !n-;ff it> ~ <fl fit ({ I

zrfif ~'F'fl iff <it d4~ffi "'l<ti"$1" i'f>T "'14'1 1/Jt~
<F<r d'"l<til Ptfle cnJNt({ I
9('i}q; !nrr it>~ Pt4d aiCf> !nif it> :>Rr if M;
~~I
9dJ<ti)/i'l&'1-fiRt4 1"

~ if ~ 1f"4T

i'f>T

iff I

tlfl{l'"4

aN~.

'Jfiif

act>

'

Note : English version of the Instructions is printed on

the front cover of this question pape1: