IA-BRL..

M-DIFA I
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7[qf

Question Paper Specific Instruction s

Please read each of the following instructions carefully before attempting questions :
There are EIGHT questions divided in two SECTIONS and printed both in HINDI and in ENGLISH.
Candidate has to attempt FIVE questions in all.
Questions no. 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 I 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 TrUJ,rks 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.
Attempts of questions shall be counted in chronological order. Unless struck off, attempt of a question shall be
counted even if attempted partly. Any page or portion of the page left blank in the answer book must be clearly
struck off.

A-BRL-M-DIFA

~A

SECTION A

Ql.

S::044H m cor~ enur, ~ L

(a)

'~'n (x)

~-~~it~~ 1epur

<i(JfCf)~H

Pll4iR1Rsln ~ :
'fin (x)

(i)

= 1,

{2 . nnx
= ~L sm L ;

= 1, 2, 3, ...

= 2 3fu: n = 3 ~ m~ ~~ ~ ~ d{J ICf)<190Jl ~ {~sll~?l

~I

Pn (x)
(iii)

(iv)

(b)

= \jf*n

n = 1, n = 2

(x) \jf (x) cnT CRTI ~ ~ I

n

= 3 ~ m~ 31cff2IT3it ~ ~' CfiUT ~ ~ ~ ~

3fu: n

~ \lfR

ehl

SII~Cfl<i l cor {@IR151 ~ I

~if

cnur COT~ Bim CRJT ~?

25C

1R,

(i)

CiiD

~q;r~c:

18961 kJ mol-1 ~

~:
(c)

tzyrr ~-m ~

mu

3fu: ~

BShAOt

cor

~~

qftqJ.,

4f\C4d"i 32552 J mol-1 ~ I 25C 1R

?dN if~~~~

tzyrr -CflT

6f{)4(il

fiWr<ft ~?

P=

RT

Vm- b -

y2
m

~~~' ~~~~ sniRtCflf?~ (Pc, Vc, Tc)~~&i\i!Chl

Cf>T

A-BRL-M-DIFA

Htffiur 4)) Nl Q\,

~~~

3ltR A 1141'"4
2

~~ I

(d)

PJqR1fuJ(i

i;flif ~' ~ ~ ~ 3fu: 'k!Ri~ tf>IR:<!it ~ qf{cnfl"l ~ :

~

(i)

H20 (l)

H20 (g)

(ii)

CaC03 (s) ~ CaO (s) + C02 (g)

(iii)

2H 2 (g) + 0 2 (g)

(iv)

H 20 (s)

(v)

NH4Cl (s)

H20 (l)

('l(ll~ui CfK1T ~' ~ 02

(a)

~ HzO (g)

NH3 (g)+ HCl (g)

31Tcrul\il"l cR1ff1~}31l ~ fcKq;r

(e)

H 2 0 (g)

cit

mm ~~<'"cfl

2465 kJ mol- 1 ~ I ~ ~
Rl<~11)(1 q:){ ~' ~ ~?

"*t

A particle of mass m is confined in a one-dimensional box of length L.

The wavefunctions \Ifn (x) of the particle are given by
\!In (x)

/2 sm
. L;
nrcx

= VL

= 1, 2, 3, .. .

n is the quantum number, and 0::;; x::;; Lis the distance along the length
of the box.
(i)

Sketch the wavefunctions for the states with n

= 1, n = 2 and

n= 3.

(b)

(ii)

Describe what is meant by the Born interpretation,

(iii)

Sketch the probability of finding the particle within the box for
the states with n = 1, n = 2 and n = 3.

(iv)

What is the average momentum of a particle in a box ?

(i)

How is entropy defined thermodynamically ?

(ii)

What role does ~S play in determining the direction of

spontaneous change ?

(iii)

At 25C, the enthalpy change of the graphite

1

transition is 18961 kJ mor

1

---7

10

diamond phase

and the entropy change is

32552 J mol- . Which is the spontaneous direction at 25C ?

Which direction is favoured by a rise in temperature?
10
A-BRL-M-DIFA

Determine expressions for the critical constants (Pc, Vc, Tc) of a

Van der Waals gas, defined by the expression

(c)

P=

RT
Vm- b -

vm2

where the symbols have their usual meanings.

Calculate the number of phases, components and degrees of freedom in

the following systems :
10

(d)

(e)

Q2.

10

(i)

H20 (l)

(ii)

CaC0 3 (s)

(iii)

2H2 (g) + 02 (g)

(iv)

H 2 0 (s)

(v)

NH4 Cl (s)

H20 (g)
~

CaO (s) + C02 (g)

~

H 20 (l)
~

H20 (g)
~

H 20 (g)

NH 3 (g) + HCl (g)

The molar enthalpy of formation of oxygen atoms is 2465 kJ mor1.

What is the longest wavelength photon which could dissociate 0 2 ?
10

(i)

(a)

(ii)

~;jil OF, OF- 3fR OF+ ~ ~ cf))Niq: 3fR ~ ~ ~ 311~~

Cf)~, ~cq ~, ~cq ~ci~,~lll, ~cq ~m ~ 31jj<!lenfCI lR
~ eh)N!q: I

Pt10001R=IRs!d ~ ~ ~ ~ ~ ~~ ~ ~ co1ur ~ ~

3fu: ~?

A~BRL-M-DIFA

(1)

H20~NH3

(2)

SF2 3fR BeF2

(3)

BF3 ~ BF4

(4)

PH3 ~NH3

(5)

NH3 ~NF3

3iroT ~

f(v)

3/2

= 4n (

2nRT

N2 ~ ~' f(v) ~ ~JSitft=!-;~ ~ I

(i)

He~~

(ii)

~ fcfi f(v) Sl~tiilr41C[Ict

-3fu:

v2 e-Mv2/2 RT

~~

J
00

f(v) dv = 1

(c)

20C
3324

cor ~ (RlCf 7275 x

~-stfd~ta crr#t fctet<:~"'' Cf>T

11{

\iR1

= 09614 x

103 kg m-3 fctet""l"l

~ I~ Ch~l6fll -;rffi

(a)

(i)

-q

10-3 Nm-1 ~ 1 ~

= 3324 x
~ ~ 3fR 09982
y

~~~Tcl fct(1""l"'' -~

Cf)l1

(flq 11{

-..;~ ~

10-3 Nm-1 ~ . 1 "0f

x 103 kg m-3 \iR1 ~

Wn?

Compare the molecules OF, OF- and OF+, discussing molecular

orbitals, bond orders, bond lengths, bond energies, and
15

paramagnetism.
(ii)

A-BRL-M-DIFA

Which of the following pairs is expected to have the larger bond

10
angle and why?

(1)

H 20 andNHs

(2)

SF2 and BeF2

(3)

BF3 and BF4

(4)

PH3 andNH3

(5)

NH3 andNF3
5

(b)

The molecul ar speeds are distribu ted accordin g to the Maxwel l

distribu tion,
f(v)

. (i)
(ii)

= 4n

w1 J3/2 v2 e- Mv2/2 RT
(2n:RT

Sketch f( v) for He and for N 2

Show that f(v) is normali zed, i.e.

J
=

f(v) dv

(iii)

Show that the most probable molecul ar speed Vmp, is given by

Vmp

(c)

= ~2~T

15

The surface tension of water at

20C

3324 vol% solution of ethanol has y

tempera ture. Given p

is

= 3324

7275 x lo- 3 Nm-1.

x 10- 3 Nm- 1 at the same

09614 x 103 kg m- 3 for the solution and

09982 x 103 kg m- 3 for water. How much less will alcohol solution rise

in the same capillary tube?

10 .

(i)

(ii)

!-! ~JI<'fS'T'"i-~ ~ c;T BAI;:ftd $:0~AI"i ~ I t:; l~~l\J1'1 ~ ~' ~ me,

$c'ICf?T"i ~ $:0~~1'1,

A-BRL-M-DIFA

* m~ fern~~~~ ?
6

(iii)

~1$~\Jl;:ft<!l ~ ~ ~ 3-~
OfiT

Jt("'!! i6h"'l

if>

3-l-1w

~clef?l'"i-~ ~21%{01

~I Nl l!; :
00

= f \jf~ r \jl 4n r....?. dr

<r >

J
00

?Y=r

~~

~" Q l<:t>

r n e - ar dr

n!=an+l

~ Z ~ ~~
~~I
(iv)

= 4n

h 2 /me e 2

= 520

pm

(ii)

f9hRd14 K mg cfiT Slflll~ld fiHdl ~ ~ ?

R6hcCIRf~1

if> ~ ~ ~ ~ ?

tm: = 391 )

Cd- Ni ~ ~ ~ ~ ~ rnfi!INfJI
~?

~ $clct~ls ~ CRIT ~

"ffi.;r ~ ~ Cd ~ Ni "6hl ~ ~ ~ ~ Qffi ~ ?

A-BRL-M-DIFA

'

529 pm ~

Clffi ~ 3ld: ~ ~ ~ ~

~ wr

if>

-a fiffl ~ ?

(i)

(~ : KCf)T ~

(c)

a0

~ ~ ~ ~ ~~ ~ ~ (a /Z)
0

ci)~~l<!l~ ~ Cf>lfbd6hl ~ a
~it Thn&:Rid Wm ~ I

(b)

3fR

(a )

The basic Schroding er equation for a hydrogen ic (1-electro n) atom is

2

- -h V 2 \If - ( Ze
\If
21-1
4rc e0 r

= E\lf

(i)

Explain wh at the terms in this equation mean.

(ii)

~L is the reduced mass of the electron-n ucleus pair. For hydrogen ,

how does it compare with me , the mass of t he electron ?

(iii)

Evaluat e the average electron-nucleus separation for the ground

state of a hydrogen ic atom :
00

<r >

= f w* r \If 4n r 2 dr
0

00

given that

rn e- ar dr =

n!

and the wavefunc tion is given by

where Z is the nuclear charge and a 0

is the Bohr radius.
(iv)
(b)

Why is this different from the most pr obable radius (a 0 /Z) ?

10
5

Potassium crystallize s as a body centred cubic lattice having unit cell

length a = 520 pm.
5x3=15
(i)
What is the distance between nearest neighbou rs ?
5
(ii)

(iii)
(c)

= 4rt E0 h 2 /me e2 = 529 pm

What is the expected density of crystallin e K metal ?

(Given : At. wt. of K = 391)

What is the ionic radius of K+ ?

What are the electrode reactions for charging and dischargi ng of the
Cd - Ni alkaline battery ?
What are the advantage s of choosing Cd and Ni for the cell ?

A-BRL-M-DIFA

10

Q4.

(a)

fro ~&f (ffq ~ ~ 3"1j:iciic1~ ~ fTB ~ I ~ ~ ~ ~ ~ ~ cit

ooc if ~ ~ ~ ~ t (Jf ~ ilf?ci<:i1 trR "f<g ~ t ~ ~

N02

3'1j~cii6fl'~ 31~ -{1-r ~ \ifRIT ~ I

<D

~~~~'"! ~ ~ CfiT ~:RiJOft('"l

~, ~ ~ (Oj4JCf1<Uf

Rifulq:,

~~

"St~ Cfi1 fY~et>{Of ~ ~ !

(ii)

"fi ~&fUTI 1:R 3"11tnfur, '{~ljA H ~~II~Q\ fcF;

Cf(ff

CITffi

~Q:J~~j)tl) ~ ~ ~ ~~ ~ I
(iii )

298 K 1:R ~ ~ ~ BIS:41Cf~ ~

Cf)f

qf{Ch~H ~ ~ ~'

B IRll~~ ~ N02 ~ ~ ~ ~ ~ ~ ~
Cf)f

= 46 mm Hg, . p (~) = 23 mm Hg

(i)

~ WC'ill"'l CRIT m-ar ~ ?

(ii)

Ullf~ ~

XA

XB

~ -m~-ur ~ ~ ~

n = nA + nB

~~

GHR ~ ~' ~ fcf> ~ ~

Pt8R1fulct ~ ~ :
i"C4i?l4"'1

~~ A ~

Ulll~3if ~ q f{Uj jlOJ ~ \4 ~ felC144

(c)

nA

~~~ ~ ~ B ~

nB

efiT ~ lOJT;fl ~ I

(i)

(ii)

~~~~l\JH-~ d(l llf>0'il ~ ~

it

H 2 3"111 Cfi1

crof1 Cf>8 ~ ~'

~ ~ ~ ~ ~ ~l'#llOJI~~n VB a{liCf>t=H Ptkiklruaa ~

~ (i) -ij \liT (1{41Cf>~~ fc;r&r ~ ~ "ffi2l ~ ~

~ ~ ~,

A-BRL-M-DIFA

!:?fdlOJ 1(1 c:h1~iQ; :

PN
02

(b )

PP<=i Rifulct

a1 "JB ~ flcqun
9

chl~q: 1

Ql~l0{

ch1Nio: ~'

(a)

N02 gas is a paramagnetic brown gas at room temperature. When a

sample of the gas is cooled below ooc, its molecular weight increases,
and it loses its paramagnetism and colour.
5x3=15
(i)

Using electron dot structur e, write an equation which accounts

for these observations.

(ii)

Based on these observations, predict whether the reaction taking

place is endothermic or exothermic.

(iii)

Use the following data for the pressures of N0 2 and its product
at equilibrium to calculate t he equilibrium constant for the
reaction at 298 K :
pN
02

(b)

p (product)

= 23 mm Hg

(i)

What is an ideal solution?

(ii)

Show that the entropy of mixing of two liquids to form an ideal

solution of mole fractions xA and xB is

where n
nA

(c)

= 46 mm Hg,

=nA + nB is the total amount of solution resulting from

moles ofliquid A and nB moles ofliquid B.

(iii)

What mole fractions give the maximum entropy of mixing ?

(i)

Construct a trial LCAO - MO wavefunction for the H 2 molecule.

(ii)

The trial VB wavefunction used by Heitler and London to

describe the H 2 molecule m terms of hydrogen-like
wavefunctions is

10
5

Compare with the wavefunction you wrote in (i) and comment on

the differences, if any.

A-BRL-M-DIFA

15

10

~B

SECTIONB
Q5.

~ fcj) ~:81

(a)

ft-a ~ ~ ,j&flJOluft;q >WoR -q

J.l=~-~~
CP

(b)

185C

= 3=1 q Rs-tdT -zy;r 1:R "!Ifli~ Rl ~1\SC ~

-B ~ ~-"QJ'2lf!Q:l:i11

~ ~ ffi~ ~ ~ ~ ~ ilf~ ~ I ~

(ffq

et>T q:m ej-,~J ~ ~ ?

(lTq

~ d'lffdrc~

R'"'"IR1Rsid

(c)

~ ~-m 3'11~Cf; f9F>;q1fclrtr ~ ?

H2 (g) +

02 (g) + H20 (l)

~ 2H+ + 20Ir

~~ ~G2 98 'Cf>l-778kJ~~~ I

Pt101R1fuld

3=rd-~
_!_

02 (g)+ H20 (l) + 2e- ~ 20H-

~ ~ E; 98 CfiT qf{Cfifl'"l

(~ : 1 ~
(d)

eh)Niq: I

=96,500 c)

(Ifill! RCfi ~ A ~ B

cfiT fh;q IRl RT Cf)) R'"'"l R1ful d ~

~:

A*

(i)

A-BRL-M-DIFA

11

fffisrr \liT WRri

A* ~ ~ ~141 ~~ (OfblCf>C!O'"i

(ii)

f?~ ~ ~
chlNtQ, I

ii,

(1)

"\jf1'ffi ~ ?
(e)

iR=r

~~n15Jcfi]1:f{ ~ m

4l'IN-IQ; fct> {fil!tflt\lul

lfR CR ~ ~' [A]

~ B ~ ~ ~ ~

fcR ~3-1-l if; ~' ~

(iii)

CfiT

>f~ ~

Wr

3fu:

~ ~

3fu (2) ~ cnTF2: c6l ~

~ 3iCJ!tntl ol ~ ~ ?

~ ~' 3iC!~O~d ~ m ~ ~

AP ~ ~
l+KP
t~P~~~~~~tA~K~~~~~ I

(a)

Show that in the adiabati c reversib le expansio n of a gas

ll cP

-(a8PH)

where
f..!= Joule - Thomso n Coefficient

CP = Molar specific heat at constan t pressure.

(b)

10

Below 185C triethyla mine is miscible with water in any proporti on.
What is the tempera ture known as ?
What is the molecul ar mechan ism for the existenc e of such a
tempera ture ?

10

~G2 98 is found to be - 778 kJ, for the following reaction

(c)

Hz (g) + 1 0 2 (g) + H 20 (l) ~ 2H+ + 20H2

Calcula te E; 98 for the following half-rea ction

(Given: 1 Faraday = 96,500 C)

A-BRL-M-DIFA

10
12

(d)

The mechanism of a chemical reaction A - j B can be written as follows :

K1

A+A

A*+A

K_l
B

A*
(i)

(ii)

(iii)

.
.
- d [A]
d [A*]
Wnte expressiOns for
and
in terms of [A], [A*]
dt
dt
and the rate constants.
Assuming a steady state approximati on for A*, express the rate
constant for the formation of the product B in terms of [A] and
the rate constants.
Under what conditions does the reaction become (1) first order
and (2 ) second order?
10

How many types of absorption are there on solid adsorbents?

(e)

Prove that, for chemisorpti on, the amount of the adsorbed phase m is
equal to AP where P is equal to the pressure of the adsorbent, A
l+KP
and K are some constants of the system.
10
Q6.

R3SiCl, R2SiCI2 , RSiC13 , (R = .qf~)

(a)

~ \ifRIT ~-

col fBR1et>"i CSI)f1Chl cn1 ~ -ij

I ~}(~tiOI -ij ~ '!(lf?t<i} ~ ~m cn1 ~ chlWlll: I

~'fdlllf1

~ll$il~ll: ~ :

(b)

(i)

~ [CuCl4] 2- CfiT ~~fCI

(ii)

[Co(CN)6]4- ~

~~
3
[Fe(CN)6] - ~ :!ChiCSI~ [Fe(CN)6]4- ~ "f~ ~ I

(iii)

~ 'C:f@ HCN -ij ~~~'$l\JI"i ~ ~

:!Cf>l1~

~ [Cui4] 2- COT q@ I

[Co(CN)6] 3-

f.:r7ftR ~ m~

Rn.1fi!d

m\3ffift t

~ B(>"IOR{RCf> ~ -ij Rlf1fild -;r@ ~ I

(iv)

[Cu(en)2] 2+ CfiT ~ "fi'~ [Cu(NH3)4] 2+ ~ "f~ ~ ~

~men~ 1

(en = NH2 - CH2 - CH2 - NH2 )

(c)

(i)

~Tc:ffii\Ji"i qf{Clf5"i ~ ~' ~~1J~If~"i

(ii)

~1$ll~l4 C ~

A-BRL-M-DIFA

mg ~

Cf)f

~~~
13

~~et>ltl -srmq CRn ~ ~ ?

Cf)f

croR chlNlll: I

(a)

R 3SiC l, R2SiCl2, RSiCI , (R = met hyl

) are use d for ma kin g silicon
3
polymer s. Exp lain the role s of the se com
pou nds in the syn the sis.
10
Exp lain why
(i)
The com plex [CuC1 ] 2- exis ts, but [Cu 2
l4 ] - doe s not .
4
(ii)
[Co(CN)6 ] 3 - is mo re stab le tha n
[Co(CN) 6 ] 4 ~, whe rea s
4
[Fe (CN)6 ] - is mo re stab le tha n {Fe(CN 3
)e] -.
(iii)
Copper me tal diss olve s in HC N wit h
evo luti on of hyd rog en gas ,
but it doe s not diss olve in sulp hur ic acid
.
(iv)
The stab ility con stan t of [Cu(en) ] 2
2 + is hig her tha n tha t of
[Cu(NH3)4] 2 +

(b)

(en =NH2 - CH2 - CH 2- NH2).

(c)

(i)

Wh at is the co- ope rati ve effect of hae

mo glo bin during oxygen
tran spo rt ?

(ii)

Q7.

(b)

(b)
(c)
(d)

~~

(c)

(a)

Des crib e the me tal site of Cyt och rom e

C and its fun ctio n.

20

~ kf(1'!00f ~ ~ ('f{ll~4 ~
3'1Cl!t0t5101 453 nm ~ 3fu:
~ Slfa~rn :?kfl'lf""l 508 nm 1:R ~ 1
s!lf!{lf8 cfiT ~ ~~ 40% ~ I
~C!:{n~ct ~ ~ ~ SIRI~I<'idl Cf)T Slrn
;{)rn ~ ~ ~ 3("(1J~ ~ ~ ?
"Sf~ ~Sf)lOJUI ~ ~ ~ ~ t!CfliW'i ~
~ ~ ~ 3"1Cl!?flt5f01 '(OqCf?lOf ~
"ffia:uT ~ ~ I~ 4ilN!Q\ I

(a)

(d)

20

3fu CfCf~ ~ ~ CR-Tf-ep;rr

-a, 3C:I~{Ui ~ ~ ~ ~ I

~ ~ ~ ? \iR1 ~ ~ ~

cfiT fl~l4d I

25C 1R N 20 5 cr ~-~ 3fu: 104 s ~

~ 3"14t4Ra ~ Cfil qf{CflfH chlNlQ\,
~t~~ ~ er>r~~ ' k=
693 x 10-5 s- 1 ~ 1
A solu tion of a dye has its max imu m
wav elen gth ligh t abs orp tion at
453 nm and max imu m fluo resc enc e emi
ssio n at 508 nm . The qua ntu m
efficiency of fluo resc enc e is 40%. Wh
at per cen tag e of abs orb ed ligh t is
em itte d as fluo resc enc e?
15
The abs orp tion spe ctra of lan tha nid e ion
s are sha rpe r tha n tho se of ion s
of the firs t tran siti on seri es. Exp lain .
10
Wh at are the diff eren ces bet wee n the
trip le poi nt and boi ling poi nt ?
Illu stra te wit h the hel p of the pha se dia
gra m ofw ate r.
10
Cal cul ate the half -life ofN 0 at 25C
and the frac tion dec omp ose d afte r
2 5
10 4 s, giv en tha t the rate con stan
t of its dec omp osit ion is
k = 693 x lo-5 s-1.
15

A-BRL-M-DIFA

14

.,.

QS.

(a)

~ ~ [Co(NH3 )4 Cl2]+ it> ~P''IIC!l!cfl ~ ~ ? ~ ""@, W ~

~311 ~ {@1~51 ~ 3fR B"'IC!l!cHil ~ >ref>R (~ ~) cfiT ~

(i)

~I
(ii)

~ ~ {mil!R<:fl (IUPAC) -;m:r

(iii)

<FIT B"'ICI4Cil ~ ~ ~

Rifu!Q\

:JUTt'Jlf

~~?

~-'1\ {lf!ll!H<:fl ~f5t>llt~ftMdl~

ooc ~ ~ ~ 36 g enr, ooc ~~it .jci)qon;q ~ ~ ~ ~G,

(b)

lJRt Cf>T

qf~:ct'>M4 ~ I 0C ~ ~ ~ 1WR

~s ~ ~H

efa :JH ~ 335

Jg- 1 ~

~~I
~ ~~ % <FIT CfiROT

(c)

fcF; ~ A 3fu im B ~ fR fe1(14"'1 ~ ll(1"'1 $tliRtet>

~fuw~~ I
~

(d)

Hg2 CI2 + CI 2 --7 2Hg2+ + 4Cr

~ 1lHeti fcn:rcr E 0 CfiT qf(Ch~H chl~Q\ I
~

: R'4 k1 f@ (1

3'1 q;:j '!H

fcrtrer :

Eo (Hg2Clz /Hg) = 027 V

Eo (Hg2+JHg~+)

= 092 V

Eo (Hg /Hg2+) = 079 V

Eo (Clz/CC) =136 V

~ : ~fd"'I M ~

fu'Q: ~

NA = 6022 x 1023 mol-1

= 6626 x lo-34 Js
KB = 138 x lo- 23 JK-1
c = 30 x 108 ms-1
R = 8314 JK- 1 mor 1
h

F = 96,500 C
A-BRL-M-DIFA

15

(a)

(b)

(i)

Does the comp lex [Co(NH3 ) 4 Cl ]+ have isome ric forms ? If so,
2
draw their struc tures and identi fy the type(s ) of isome rizati on.

(ii)

'Write the chem ical (IUPA C) name of the complexes.

(iii)

Do the isome rs have identi cal physi cal prope rties and chem ical
reacti vities ?

Calcu late the value s of D.G, L'iS and L'iH for the revers ible conde nsatio
n of
36 g of water at
to ice at 0C. The laten t heat of melti ng of ice at
0C is equ al to 335 Jg-1.

15

ooc

(c)

(d)

Expla in why the eutec tic point of a soluti on betwe en solid A and
solid B
is invar iant.

15

10

Calcu late the stand ard poten tial Eo of the reacti on

Hg2 Cl2 + Cl2 --7 2Hg2+ + 4ClGiven the following reduc tion poten tials :

10
Given : Cons tants for use
NA

= 6 022 x 1023 mol-l

= 6626 x 1o-34 Js

KB

= 138 x Io- 23 JK- 1

c = 30 x 108 ms- 1
R = 8 314 JK- 1 mol- 1

F = 96,50 0 C
A-BRL-M-DIFA

16

IA-B RL- M-D IFB I

'({11 i '1

f4 #11 '1

~-~-11

CHE MIS TRY

Pape r-11
f/1T[{ :

rfB r:tt

~ 3fcF: 250

Time Allow ed : Three Hour s

Maximum Mark s : 250

~ ~ '3"m ~ "tt -~ frli='1R:!R"'a ~ ~

~l<i'J_ct<fl ~ 1
3lTO (8) ~ -GT ~ -if ~ ~ ~ -aqr ern~ ~ ~ ~;:j'f ~* -if Wl" ~ ~ 1
-qft~~ qiT ~ ~ \f!1;:j'f ~ ~ ~-;f ~ I
~ ~ 1 ~ 5 ~ ~ I ~ ~ if ~ ~
~ - ~ Cfilf ~ Cfilf ~ \f!1'1" ~ ~ cfR \f!1;:j'f
~
~~I

cwr

~ \f!1'1" /~ ~ 3tcP \f!1'1" ~ 3lCf if ~ ~ I

if ~ lfftl:f11 -if ~ ffficr;:rr ~ ~ -aqr ~ ~ (Questi
on-cum-Answer) ~ -if ~
\ifTW 'T{ ~ cpm 3WIVWF ~ I ~ liTUf11
~ 3lffiC.IT 3RT liTUf11 if fc1@ 1]if ~ ~ 3fcF ffi ~
~I

m -'l?f

\ifif-"Cfllff

m,

(1liPCIC1 ~

(Diag ram) "lf!1-;:fiw ~ ~ fqpr 'T{ N ~ I

ldi~fd<fl ~ ~ SlllilfUICfi ~ 3T~ i?fiT I
3fCR ~ ~ B'1~'1" if, ~ 3liCI!1l1Cfi wffi, 3TTUR-'ffiinft ffi ~
tG1Z ~ ~ ~ Cfit I
~ ~ ~ ~ ~ if fTR ~Tr I ffi CfllZ
~ ~ ~ ~ CfiT ~ f1i-:Rft if ffrtrr ~ 1Rffit
~
~ ~ ~ if ~ ~ -m 1 ~-~ if
'f'1T -rrr Lp<=j"T ~ 3l"n 3TlT{ ~ ~ -a~ ~ ~~
tG1Z
~ ~ cprc ~<i"T ~ ~ I
3RT21T ~ '1"

"i?)-;f

'T{

QUES TION PAPE R SPEC IFIC INST RUCT IONS

Pleas e read each of the follow ing instru ction s caref

ully befor e attem pting quest ions.
There are EIGH T quest ions divided in Two Secti ons
and printed both in HIND I and in ENG LISH .
Candidate has to attem pt FIVE quest ions in all.
Quest ion no. 1 and 5 are comp ulsor y and out of the
remaining, THR EE are to be attempted choos ing
at least ONE from each section.
The number of marks carrie d by a quest ion/p art is indica
ted again st it.
Answers must be written in the mediu m autho rized in
the Admi ssion certif icate wh ich must be stated clearl y
on the cover of this Ques tion-c um-A nswer (QCA ) bookl
et in the space provided. No marks will be given
for answe rs written in mediu m other than the autho rized
one.
Coordinate diagr ams, where ver requi red, shall be drawn
in the space provi ded for answ ering the quest ion
iteself.
Unless other wise indica ted, symb ols and notations have
their usual stand ard meanings.
Assume suitab le data, if consi dered neces sary, and indica
te the same clearl y.
Attem pts of quest ions shall be count ed in chron ological
order. Un less struck off, attem pt of a quest ion shall
be count ed even if attem pted partly. Any page or portio
n of the page left blank in the answe r book must
be clearl y struck off.
A-BRL -M-DJ FB

SE CT IO N- A
Q. 1. (a) it~ if, ~
1f\ ~ tnT ~ -c;cF
~ cF ~if ~
~ ~ZR >rGr-1
~ ~I ~ cFr ~ ~
ait\ ~ ~ cF. ~ cF ffnz ~
f41Scl<fi'(UI ~I
Addition of bromine to ethyle
ne in methanol gives bromome
thyl methyl ether as one of
the products. Formulate the rea
ction and give mechanistic exp
lanation for the formation
of this product.
10
(b) 3!1~~:i'nl'l41~fl~ilii~>S -cF s"ml
~~i'Pf1f1Cil{UI -cF ~~ ale
. KO H if, 4~il clliH ~ 3A"91
tii f cr't
3!1'HllCildl ihfi ~~ ~ t-B
uo -K +/D MS O if, slt?l~~i!sfH
"ICfl{OI (iiJildOJ Cfi11 -q-{ 1J:Cf
"B" Cf1l1 if (i.il IR:id ~ \5fT
i fii-:rc
~
~ I ~

:gWT

ffnz

"C!1T{UT

~I

The dehydrobromination of
isopropylbromide requires sev
eral hours of reflux ing in
ale. KOH, whereas, in t-B uo
- K+/DMSO, deh yd rob rom ina
tio n can be carried out in les
tha n a mi nu te at room temper
s
ature. Give reason for this ob
servation.
10
(c) (i) ~ ~ fct; fcR
r "Ci1T{UT "B" ~
(C6Hsh CHCl

cr't

~ ~

cr't

+ p~

liq.

so3~

-cF m

Utt-rlrt

Explain why the rate of the

rea cti on :

\Jffifi

liq. so3
(C6 H 5) CH Cl + r -~
2
gradually decreases with the
progress of reaction.

(ii) ~-;fu;!T;r 3lh: ~\Jll~fiO\l"i"l'i ~

~
quf<=f ~I

fct<iR.,

<F ffnz,

1J:Cfi ~

{I (i Iil f.1

Ci1 W~ tnT

Describe a simple chemical

tes t to distinguish bet we en ani
line and benzylamine.
(d) ~'il~?,l~fl ~ if,
5
>SI~~~lJ>fl 1":1\3!1Cf(ii~>S cr't ~
if, 3!1~Bl~ffi tnT ~ HBr
-cF mq~fctim\ifRIT~I ~
tn
r~~ 3lh:~<F ~
~ ~~

~I

Isobutene is treated with con

e. HBr in the presence of dib
enzoy l peroxide in acetonitri
solution. Formulate the reacti
le
on and give explanation for
the formation of the product.
(e) f.1HR1fid ~arr if
10
~ (X) 3ih: (Y) ~
:
Write the products (X) and
(Y) in the following reaction
s :
10
(X )

CH

A- BRL- M- DIFB

=CH
(Y)
2

Q. 2. (a)~ ~ fcl1 fcR:r "CfiRUT ~d0ls:JI'1 ~~it (M + 1) 3Wf'1" fum~

\5fTdT ~I ~
fcl1 PI~'1R1Rctd ~ ~ 3!14 i1Cfi(OI it fcR:r ~T~ 3ffilT it ~ Chi~ ~ tr'BTCAl"
iKlT ~ 3Th: ~ ~it <m1T ~ ~zr:r;:r '4T -~ :
Explain why (M + 1) ion peak is observe d in mass spectrometry. Indicate, which electron
is most likely to be lost in the ionizati on of following compou nds and write the radical
cation formed :

(i)

CH 2

(ii) CH 2 = CH2
(iii) C6H 5CH 2 CH 3
(iv) CH 3 Cl.
(b) l-<te1l {) Jfl ~ til ~Cfe1'1 sf'fq ~ \ifC1 ~1 <R

cnT

~it ~

fuQ:

~ 4i~<fl!;CI ~I

1-chloromethyl cyclopropane on hydrolysis chiefly gives three products. Write a mechan

ism
to show their formation.
15

(c)~ Cf)I~P\Cf) ~ (X), aq. H08 ~ m21 ~ "Cfi"&r ~I

An or:ganic compou nd (X) reacts with aq. H08 .

CH3

25/

C H -C-C l (X)

C6Hs
Pi~., Fc1Rcta ~

(i)

~ (X) ~T ~~

Cii) ~ oH- Chi ~

(iii) ~ ~

fuQ:

ciT ~ Chi ~Cf)I~ICf) tif#>4dl 'R ftaluft ~I

cn1 WT Cfl{ ~ \JlW, err ~ Chi ~ fcRr WFR

~ ~ 7

~ \4llfil~fl ~ . ~I

(iv) ~
(v)

cfi 4i~Cf) M cnT ~I

~ (X) it C2 H 3ih: C H ~ ~2.Wf
5
6 5
'R fZu:ruft ~ I

'R H -ncr ~

\ilW,

m~ ct\1

~Cf)I~ICf) tifsl:>4C11

Write the followin g :

(i)

If (X) is dextro, commen t on the optical activity of the product.

(ii) If concent ration of OH- is doubled, how rate of the reaction will change ?
(iii) Draw energy profile diagram for the reaction.
(iv) Write the mechan ism of the reaction.
(v) If C2 H 5 and C 6 H 5 in (X) are replaced by H, commen t on the optical activity of
the
product .
15
A-BRl-M -DIFB

Q. 3. (a)~ C H BrC l (ft-;

f fP11Cll:lC1l ~~:'iHI~ ~
2 2
<fiTcfT ~I
~

~ ~ ~~ ~: 1 - 1.5
, 9
~if~cp)JW4
"~~1

cD

3ih' 14 Hz I

mi l1 NM R ~,

~ ~lOJICll:l<1l,

t! l0llct4Fcl4r ~ ~{iFll~ ~
~

Th e com pou nd C H BrCI exh

ibits three isomeric structures
2 2
. Th e thr ee isomers in pro ton
NM R exh ibi t two dou ble ts eac
h having J - 1.5, 9 and 14
Hz respectively. Write the
structures of iso me rs and ass
ign J values to eac h one of the
m.
20
(b) \3q9,<te1 ~ ~
Cf)T ~talOJIC1 ~ ~~
rts:'iR1R9d ~qicn:orr cp1 '9ll: (f 'Cfl
ct ~

Gmm

'Q!n

fcttU

CfiT

crrrf1

De scr ibe usi ng app rop ria te rea

gents and conditions a me tho
d to ach iev e the following
transformations :

~-OCI-l3

(c) ~s:'iR11"01d ~m

cF

20
~ ~ ~ \3q9,'tt1
<:Jif?l<tl\Cl ~ :

Write the pro duc ts of the follow

ing reactions and giv e the sui
tab le me cha nis m :
hv

(i)

NS-1

hv

(ii)

NS-II

10

Q. 4. (a) rts:'ifctR9d ~m
if [X] 3fR [Y] ~ ~ ~I
ncF ~ cp) ~ ~I
Identify [X] and [Y] in the fol
lowing reactions. Ex pla in the
ir formation.

(i)

0=(Ph

~hv

Ph

A- BR L-M -DIF B

y[X]
~ [Y]

26
D

(ii)

(iii)

~ [X]

[Y]

~[X]
~ Wli (Low temp.)

[Y]

t.
~

20

crrq

(High temp.)

(b)~~ CfiT ~~1111:1

~ ~

~ CfiT

3fR

~~

3W1

~ ~

fC: I"&14

rn

? ~

i:!iGICfl, ct ~ ~ I

How will you prepare styrene .using Wittig reaction ? Write the name of reactants and
20
explain the mechanism of the reaction.
(c) f.'tl=1Fflfuid ~qjCj(OI <f; fffQ: ~ i:!iGICfl\Cl ~:

a -ftr;:fT;:r

ci(I
--~ cir

t?l~'9}te1l (1~'5 --~

Write a mechanism for the following conversion :

a-pinene hydrochloride

10

Cl

SECTION-B
Q. 5. (a) fm:r-

~-2- q;)11~<1-l <"ll~<fC1l~Cffifrflct

~ ~ CfiT

cruf"1"

err

H 3P0 4 cF m21 ~

cF

IDU ~it~

~I

Describe the products obtained by the treatment of cis- and trans-2-phenyl- 1-cyclohexanol
with H 3P04 .
(b) f.1 s:1 R1Rcta ~3IT

it

~ ~ CfiT ~ ~ cp:rr ~ ?

CXH

(i) 3iT\ (ii)

H
(i) (CH 3) 3 COO- OH/H08 ~ (ii) OsOit-BuOH
~3IT
A- BRL- M- DIFB

<fi i:!iGICfl,Cl

~I
5

What is the major product of each of

the following reactions ?

CXH

(i) and (ii)

---~

(i) (CH 3) 3 COO- OH/H08 and (ii) OsO

it-B uOH
Give the mechanisms of the reactions.

Identify [X] and [Y] in the following

:

#~"

[X]

2-Pentyne

~ "'qoz
~./, <$'_,...,
%<
P
7

[Y]

(d) 3Wf

# ~ NMR~ ~

31TW

~ ? ~ ~

How man y NM R signals do you exp

ect in :

Explain thei r nature.

A- BRL -M- DIFB

<fi

~ ~~

(e) ~ :

Formulate the reaction :

- - -4

OH
CflT ~ ~ ~ ~ <fi fciTq;:r

CfiT

WlSZ

ro cF

~ ~ J if?i<f)(;q ~ I

and give a mech anism to expla in the formation of the produ

ct.

1Ox5

Q. 6. (a) ~ Cfi i<S1'T01 Cfi m-f1lcp C H 0, IR ~11 if 1710

cm- 1 1R 1ZCfi" ~ 3Jqf1f1tslol ~-g ~ ~ 1
4 8
m"if~ NMR if, W o 1.1 (fWF>) , 2.1 (~)3th" 2.3 ('il
~~ rid ~ ~ I ~ .eft
~~ ~- <:il11 ~

3th-

o "l=fR

f1<m

~I

An organic compound C H 0 gives a strong absorption band

at 1710 cm- 1 in IR spectrum.
4 8
In proto n NMR, it gives signat ' at o 1.1 (triplet), 2.1 (singl et)
and 2.3 (quartet). Write the
likely struct ure of the comp ound and assign the o values.
20
(b) 4-~li J"il4\C: I1(1 <fi 4-fJi2f'lCf<Al <~:~c!-'f(1 if ~q j(l(O I if ~
~ ~I
Write the steps involved in the conversion of 4-bromobutanal
to 4-m ethoxybutanal. 15
(c) w:fA't 3lTc1 frr"'til~~-::r cF "ffi21 ~ ffl 1R 1fru
-;:fu;rr "Df ~ ~ I ~ ~ CflT "Cfm
"Cf'>RUT ~

Amino acids on treatment with ninhy drin give intense blue colou
r. What is this colouration
due to ?
15
Q. 7. (a) f.1J:1fflftciC1 fl {'il11 ~ 1ZCfi" ~ CflT "1111
(i) tfucp ~ {'il1 1

(ii)

\jf](1

3th-

~- <:=tHI ~

~-{il11

(iii) ~-f?Pfu:r ~;i:Z'il1 1 I

H+ eft "\3'Tft~ if ~ ~ ~tfR<% 1 ~:S

cF

ci1 )f1Cfi1

cF

~ l:l if3iCfi, q ~ 1

Write the name and structure of one polym er having :

(i) Linear struct ure

{ii) Netw ork struct ure

(iii) Three dimen siona l structure.
Write the mech anism for the polymerizat ion of phenol and
forma ldehyde in the presence
of H+.
20
A- BRL- M - DIFB

(b) fPi~l<til!;

3-~z-rtT1

fctl ctm' 1,

cF

~ ~ lii)fFt>1

~~ffi~ l

iJ", GT

~ ~

cfi, ~ ~Cfii~Lj'f

Explai n why free radical polymerization of 1, 3-butad iene leads to macrom

olecule s having
two different types of monom er units.
15
(c) DNA it fCt<ilJOJH GT ~ ~ . q1~D~lH <t;Cfi l<t;ll'i cf; "1111 ~ ti{'il1 1 ~
I m?.T 1ft ftTlZ
~ fctl CftiT 91RUT ~ f.:l1 ~ 3lT1~ ~m it DNA
~ "1 f.:l1 RNA I

mar

Write the name and structu re of two purine and pyrimi dine units presen
t in DNA. Also
explain why most of the genetic materia ls contain DNA and not RNA.
15

(i)

~CHO
(ii)

~NO

0
(iii)

(iv)

-tPn:-~

(v)

IH2CO OC2H5 .
~~

(CH2)2

I
CH COOC
2

(vi)

2H 5

~OCOCH3

~ 'fiT 3, "1 Fcfrlll/;1

OCOC H3
(vii)

~frl;;_tl{l ~

A-BRL- M-DIFB

8
++++

(viii) IOOC2H5 +
COO C2 H 5

(ix)

Cl

cfic?1 n<Fl

1l'1Fcf~ttm

------~~~-----~

UC ONH2
(x)
N

Writ e the prod ucts of the follo wing nam e reac

tions :

ctro

(i)

Baey er-Villiger

----'-----=--~

~CHO

(ii)

Perki n react ion

~NO2
0
(iii)

Refo rmats ky

8=:J

(iv)

reactio~

Reimer-Ti eman n

(v)

CH2COO C 2H
5

Dieck mann react ion

(CH2)2

CH 2COO C H
2 5

&_ OC OCH3
(vi)

Frie' s rearra ngem ent

OCO CH

A-BR L-M-D IFB

(vii)

Cannizaro reaction

(viii) COOC2 H5

I
COOC H
2

(ix)

ex

A
+U

Claisen conden sation

----------------~

Cl
Favorskii rearrangement

----------~~-~

(x)

UI
::--..

CONH 2
Hoffmann rearrangement

-----------=---~

(b) f1Trl~ if (X)

3fR (Y) tt>i

10x4

~ ~

Identify (X) and (Y) in the following :

A-BRL- M-DIFB

o3 > (X)

NaBH4 ~ (Y)

10

10