R-Elft& rft::r eR:

I CfiEMISTRY
I Paper I
Time allowed: Three Hou ... s

cpl?.l7 JTFif CfiT Tr11 # 'R" "{!! f.i RfRf&rl cn7 t 41'19.,c/Cb r:rf :
.Hl(! w::r! it qT -q ?MJ ft.:ift :#/( crRl # EN ! I
rrftqmff -q:;1 3K7 Ww JJRl cfi "3fT( # # I
I A-BRL .. M-DIFA I
31f'Wi?f11 3W> : 250
Maximum Marks : 250
w::r 1 3tk 5 3#rqp;f # am fi # (ITTS T[Cn J1FI rtr.r w-ii "3fT( 1
w;r j'JlTIT 3/q; "f17"1Fr 7JT! # I
w-ii c1i 3m JHt 1Tf"ap:[ # fffli m-r:r57 # fWr; rmr :#/( q;r p:fQ(! 3ft&
J/R-8"$-Yf{( !j&-'[Od W 3ifiri?T f.rRoc W qpr 3f@Rslrl 31Fcrfi:m .3PT
Rf>dt if ff:r& Tff[ Yffr W citf 3fcn I
3lH&J Cf>7, >lR q;r Yffr # cfi ffrrf f4r! Tff[ # rft f?R7 I
aq; :r fiit?r ?f8/T :ti&<;IC/dJ -qr;rq; 31Pif # Jf!fffi # I
it "3V!Fh q;r ?f2!1
JJRl cfi :m<f ctft 1JURT $hllljSN eft \ifT(('{t I <iZ, CfiTCT it JiN Yffr eft 1JURT eft \ifT(('{t 3fT( 3iw?f: 7[qf
Qf I # &Tfft g:W 1flt <lT affl q;f Pm cnTCl iJfR7 I
Question Paper Specific Instructions
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

SECTION A
Ql. (a) S::044H m enur, L t 1 epur t
(x) Pll4iR1Rsln :
{2 . nnx
'fin (x) = sm L ; n = 1, 2, 3, ...
(i) n = 1, n = 2 3fu: n = 3 d{J ICf)<190Jl

P (x) = \jf* (x) \jf (x) cnT CRTI I
n n n
(iii) n = 1, n = 2 3fu: n = 3 31cff2IT3it CfiUT
\lfR ehl cor {@IR151 I
(iv) cnur Bim CRJT
(b) (i)
CiiD 25C 1R, mu BShAOt cor qftqJ.,
18961 kJ mol-
1
3fu: 4f\C4d"i 32552 J mol-
1
I 25C 1R
tzyrr ?dN tzyrr -CflT 6f{)4(il fiWr<ft
(c)
P= RT a
Vm- b - y2
m
(Pc, Vc,
Cf>T Htffiur 4)) Nl Q\, 3ltR A 1141'"4 I
A-BRL-M-DIFA 2
(d) PJqR1fuJ(i i;flif 3fu: tf>IR:<!it qf{cnfl"l :
(i) H20 (l) H20 (g)
(ii) CaC0
3
(s) CaO (s) + C02 (g)
(iii) 2H
2
(g) + 0
2
(g) H
2
0 (g)
(iv) H
2
0 (s) H20 (l) HzO (g)
(v) NH
4
Cl (s) NH
3
(g)+ HCl (g)
(e) 31Tcrul\il"l

fcKq;r "*t mm 2465 kJ mol-

1
I
CfK1T 02 cit q:){
(a) A particle of mass m is confined in a one-dimensional box of length L.
The wavefunctions \If n (x) of the particle are given by
/2 . nrcx
\!In (x) = VL sm L; n = 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.
(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 ?
(b) (i)
How is entropy defined thermodynamically ?
(ii) What role does play in determining the direction of
spontaneous change ?
(iii) At 25C, the enthalpy change of the graphite ---7 diamond phase
transition is 18961 kJ mor
1
and the entropy change is
32552 J mol-
1
. Which is the spontaneous direction at 25C ?
10
Which direction is favoured by a rise in temperature? 10
A-BRL-M-DIFA 3
(c)
(d)
(e)
Q2. (a)
Determine expressions for the critical constants (P c, Vc, Tc) of a
Van der Waals gas, defined by the expression
P= RT a
Vm- b - v
2
m
where the symbols have their usual meanings.
Calculate the number of phases, components and degrees of freedom in
10
the following systems : 10
(i) H20 (l) H20 (g)
(ii)
CaC0
3
(s) CaO (s) + C0
2
(g)
(iii)
2H2 (g) + 02 (g) H20 (g)
(iv)
H
2
0 (s) H
2
0 (l) H
2
0 (g)
(v)
NH
4
Cl (s) NH
3
(g) + HCl (g)
The molar enthalpy of formation of oxygen atoms is 2465 kJ mor
1
.
What is the longest wavelength photon which could dissociate 0
2
? 10
(i)
(ii)
OF, OF- 3fR OF+ cf))Niq: 3fR
31jj<!lenfCI lR
eh)N!q: I
Pt10001R=IRs!d co1ur 3iroT
3fu:
(1)

(2) SF2 3fR BeF2
(3)

BF4
(4)

(5)

4
f(v) = 4n M v2 e-Mv2/2 RT
(
J
3/2
2nRT
(i) -3fu: N2 f(v) I
(ii) fcfi f(v) t
00
J f(v) dv = 1
0
(c) 20C 11{ \iR1 cor (RlCf 7275 x 10-
3
Nm-
1
1 (flq 11{
3324 crr#t Cf>T y = 3324 x 10-
3
Nm-
1
1 "0f
p = 09614 x 10
3
kg m-
3
fctet""l"l 3fR 09982 x 10
3
kg m-
3
\iR1
-;rffi -q fct(1""l"'' Cf)l1 Wn?
(a) (i) Compare the molecules OF, OF- and OF+, discussing molecular
orbitals, bond orders, bond lengths, bond energies, and
paramagnetism.
(ii) Which of the following pairs is expected to have the larger bond
15
angle and why? 10
(1) H
2
0 andNHs
(2) SF2 and BeF2
(3)
BF3 and BF4
(4)
PH3 andNH3
(5) NH
3
andNF
3
A-BRL-M-DIFA 5
(b) The molecular speeds are distributed according to the Maxwell
distribution,
f(v) = 4n 1 v2 e- Mv2/2 RT
(
w J3/2
2n:RT
. (i) Sketch f( v) for He and for N 2
(ii) Show that f(v) is normalized, i.e.
=
J f(v) dv = 1
0
(iii) Show that the most probable molecular speed Vmp, is given by
Vmp =
(c) The surface tension of water at 20C is 7275 x lo-
3
Nm-
1
. A
3324 vol% solution of ethanol has y = 3324 x 10-
3
Nm-
1
at the same
temperature. Given p = 09614 x 10
3
kg m-
3
for the solution and
09982 x 10
3
kg m-
3
for water. How much less will alcohol solution rise
in the same capillary tube?
(i)
(ii)
A-BRL-M-DIFA
!-! c;T BAI;:ftd I me,
$c'ICf?T"i * ?
6
15
10 .
(iii) if> 3-l-1w
OfiT Jt ("'!! i 6h"'l Nl l!; :
00
f
?. d
< r > = \jf r \jl 4n r.... r
0
00
?Y=r J n - ar d n!
Q l<:t> r e r = --
an+l
0
Z 3fR a
0
= 4n
0
h
2
/mee
2
= 529 pm

(iv) (a
0
/Z) -a fiffl
(b) Cf>lfbd6hl a = 520 pm Clffi 3ld:
Thn&:Rid Wm I
(i) wr if> if> ?
(ii) f9hRd14 K mg cfiT fiHdl ?
KCf)T tm: = 391)
(c) Cd-Ni rnfi!INfJI *
CRIT

"ffi.;r Cd Ni "6hl Qffi ?
A-BRL-M-DIFA
7
'
(a) The basic Schrodinger equation for a hydrogenic (1-electron) atom is
h
2
2 ( Ze
2
J - - V \If - \If = E\lf
21-1 4rc e
0
r
(i) Explain what the terms in this equation mean.
5
(ii) ~ is the reduced mass of the electron-nucleus pair. For hydrogen,
how does it compare with me , the mass of t he electron ? 5
(iii) Evaluat e the average electron-nucleus separation for the ground
state of a hydrogenic atom :
00
< r > = f w* r \If 4n r
2
dr
0
given that
00
f rn e- ar dr =
0
n!
and the wavefunction is given by
where Z is the nuclear charge and a
0
= 4rt E
0
h
2
/me e
2
= 529 pm
is the Bohr radius.
10
(iv)
Why is this different from the most pr obable radius (a
0
/Z) ? 5
(b) Potassium crystallizes as a body centred cubic lattice having unit cell
length a = 520 pm.
5x3=15
(i)
What is the distance between nearest neighbours ?
(ii) What is the expected density of crystalline K metal ?
(Given : At. wt. of K = 391)
(iii) What is the ionic radius of K+ ?
(c) What are the electrode reactions for charging and discharging of the
Cd - Ni alkaline battery ?
What are the advantages of choosing Cd and Ni for the cell ?
A-BRL-M-DIFA
8
5
5
5
10
Q4. (a) N0
2
fro (ffq fTB I cit
ooc if t (Jf ilf?ci<:i1 trR "f<g t
-{1-r \ifRIT I
<D CfiT m (Oj4JCf1<Uf Rifulq:,
Cfi1 !
(ii) "fi 1:R 3"11tnfur, fcF; Cf(ff CITffi
I
(iii ) 298 K 1:R Cf)f
N02 PP<=i Rifulct
Cf)f !:?fdlOJ 1(1 :
(b) (i)
PN
02
= 46 mm Hg, . p = 23 mm Hg
WC'ill"'l CRIT m-ar ?
(ii) XA XB i"C4i?l4"'1 GHR fcf>
Pt8R1fulct :
(c) (i)
n = nA + nB A nA B nB
felC144 efiT lOJT;fl I
(ii) d(l llf>0'il it H
2
3"111 Cfi1 crof1 Cf>8
VB a{liCf>t=H Ptkiklruaa =
A-BRL-M-DIFA
(i) -ij \liT fc;r&r "ffi2l ch1Nio:
a1 "JB flcqun 1
9
(a) N0
2
gas is a paramagnetic brown gas at room temperature. When a
sample of the gas is cooled below ooc, its molecular weight increases,
(b)
(c)
and it loses its paramagnetism and colour. 5x3=15
(i) Using electron dot structur e, write an equation which accounts
for these observations. 5
(ii) Based on these observations, predict whether the reaction taking
place is endothermic or exothermic. 5
(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 :
(i)
pN
02
= 46 mm Hg, p (product) = 23 mm Hg
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 + nB is the total amount of solution resulting from
5
5
nA moles ofliquid A and nB moles ofliquid B. 10
(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
Compare with the wavefunction you wrote in (i) and comment on
5
the differences, if any. 15
A-BRL-M-DIFA 10

SECTIONB
Q5. (a) fcj) ft-a ,j&flJOluft;q >WoR -q

CP = 3=1 q Rs-tdT -zy;r 1:R Rl I
(b) 185C -B I (ffq
et>T q:m ?
(lTq * f9F>;q1fclrtr ?
(c) R'"'"IR1Rsid
H2 (g) + 02 (g) + H20 (l) 2H+ + 20Ir


I
Pt101R1fuld
_!_ 02 (g)+ H20 (l) + 2e- 20H-
2
E;
98
CfiT qf{Cfifl'"l eh)Niq: I
: 1 = 96,500 c)
(d) (Ifill! RCfi A B cfiT fh;q I Rl RT Cf)) R'"'"l R1ful d fffisrr \liT WRri

A* B
(i)
A-BRL-M-DIFA
11
(ii) A* (Of blCf>C!O'"i CfiT lfR CR [A] 3fu:
ii , B Wr
chlNt Q, I
(iii) fcR if; (1) 3fu (2) cnTF2: c6l
"\jf1'ffi ?
(e) iR=r m 3iCJ!tntl ol ?
4l'IN-IQ; fct> {fil!tflt\lul m AP
l+KP
I
(a) Show that in the adiabatic reversible expansion of a gas
where
ll cP = -(aH)
8P T
f..!= Joule - Thomson Coefficient
CP = Molar specific heat at constant pressure.
(b) Below 185C triethylamine is miscible with water in any proportion.
What is the temperature known as ?
What is the molecular mechanism for the existence of such a
temperature ?
(c)

is found to be - 778 kJ, for the following reaction
1
+ -
Hz (g) +
2
0
2
(g) + H
2
0 (l) 2H + 20H
Calculate E;
98
for the following half-reaction
10
10
(Given: 1 Faraday = 96,500 C)
10
A-BRL-M-DIFA
12
(d) The mechanism of a chemical reaction A -j B can be written as follows :
(i)
K
1
A+A A*+A
K_l
A* B
. . - d [A] d [A*]
Wnte expressiOns for and in terms of [A], [A*]
dt dt
and the rate constants.
(ii) Assuming a steady state approximation for A*, express the rate
constant for the formation of the product B in terms of [A] and
the rate constants.
(iii) Under what conditions does the reaction become (1) first order
and (2) second order?
10
(e) How many types of absorption are there on solid adsorbents?
Prove that, for chemisorption, 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.
Q6. (a) R
3
SiCl, R
2
SiCI
2
, RSiC1
3
, (R = col fBR1et>"i CSI)f1Chl cn1 -ij
\ifRIT I -ij '!(lf?t<i} cn1 chlWlll: I
(b) :
(i) [CuCl4]
2
- CfiT t [Cui4]
2
- COT q@ I
(ii) [Co(CN)6]4- [Co(CN)6]
3
- t
[Fe(CN)
6
]
3
- [Fe(CN)6]4- I
(iii) 'C:f@ HCN -ij f.:r7ftR Rn.1fi!d m \3ffift t
B(>"IOR{RCf> -ij Rlf1fild -;r@ I
(iv) [Cu(en)2]
2
+ CfiT [Cu(NH3)4]
2
+
1
(c) (i)
(ii)
A-BRL-M-DIFA
(en = NH
2
- CH
2
- CH
2
- NH
2
)
qf{Clf5"i Cf)f -srmq CRn ?
C mg Cf)f croR chlNlll: I
13
10
(a) R
3
SiCl, R
2
SiCl2, RSiCI
3
, (R = methyl) are used for making silicon
polymers. Explain the roles of these compounds in the synthesis.
10
(b) Explain why
(i) The complex [CuC1
4
]
2
- exists, but [Cul
4
]
2
- does not.
(ii) [Co(CN)
6
]
3
- is more stable than

whereas
[Fe(CN)
6
]
4
- is more stable than {Fe(CN)e]
3
-.
(iii) Copper metal dissolves in HCN with evolution of hydrogen gas,
but it does not dissolve in sulphuric acid.
(iv) The stability constant of [Cu(en)
2
]
2
+ is higher than that of
[Cu(NH3)4]
2
+
(en = NH
2
- CH
2
- CH2- NH2).
(c) (i) What is the co-operative effect of haemoglobin during oxygen
transport ?
(ii)
Describe the metal site of Cytochrome C and its function.
Q7. (a) m kf(1'!00f
3'1Cl!t0t5101 453 nm 3fu:

:?kfl'lf""l 508 nm 1:R 1 s!lf!{lf8 cfiT 40% I

Cf)T Slrn;{)rn ?
(b) t!CfliW'i 3"1Cl!?flt5f01 '(OqCf?lOf
"ffia:uT 4ilN!Q\ I
(c) 3fu CR-Tf-ep;rr ? \iR1 cfiT I
-a, I
(d) 25C 1R N
2
0
5
cr 3fu: 10
4
s 3"14t4Ra Cfil qf{CflfH chlNlQ\,

k= 693 x 10-
5

1
(a) A solution of a dye has its maximum wavelength light absorption at
453 nm and maximum fluorescence emission at 508 nm. The quantum
efficiency of fluorescence is 40%. What percentage of absorbed light is
20
20
emitted as fluorescence?
15
(b) The absorption spectra of lanthanide ions are sharper than those of ions
of the first transition series. Explain.
10
(c) What are the differences between the triple point and boiling point ?
Illustrate with the help of the phase diagram ofwater.
10
(d) Calculate the half-life ofN
2
0
5
at 25C and the fraction decomposed after
10
4
s, given that the rate constant of its decomposition is
k = 693 x lo-
5
s-
1
.
15
A-BRL-M-DIFA
14
.,.
QS. (a) (i) [Co(NH
3
)
4
Cl
2
]+ it> ? ""@, W
3fR B"'IC!l!cHil >ref>R cfiT

(ii) {mil!R<:fl (IUPAC) -;m:r Rifu!Q\ I
(iii) <FIT B"'ICI4Cil :JUTt'Jlf {lf!ll!H<:fl

(b) ooc 36 g enr, ooc .jci)qon;q
lJRt Cf>T I 0C 1WR efa :JH 335 Jg-
1


(c) % <FIT CfiROT t fcF; A 3fu im B fR fe1(14"'1 ll(1"'1$tliRtet>
I
(d)
Hg
2
CI
2
+ CI
2
--7 2Hg
2
+ + 4Cr
1lHeti fcn:rcr E
0
CfiT I
: R'4 k1 f@ (1 3'1 q ;:j '!H fcrtrer :
Eo (Hg
2
Clz /Hg) = 027 V
Eo (Hg
2
+ J = 092 V
Eo (Hg /Hg
2
+) = 079 V
Eo (Clz/CC) = 136 V
fu'Q:
A-BRL-M-DIFA
NA = 6022 x 10
23
mol-
1
h = 6626 x lo-
34
Js
KB = 138 x lo-
23
JK-
1
c = 30 x 108 ms-1
R = 8314 JK-
1
mor
1
F = 96,500 C
15
(a) (i) Does the complex [Co(NH
3
)
4
Cl
2
]+ have isomeric forms ? If so,
draw their structures and identify the type(s) of isomerization.
(ii) 'Write the chemical (IUPAC) name of the complexes.
(iii) Do the isomers have identical physical properties and chemical
reactivities ?
(b) Calculate the values of D.G, L'iS and L'iH for the reversible condensation of
36 g of water at ooc to ice at 0C. The latent heat of melting of ice at
15
0C is equal to 335 Jg-
1
.
15
(c) Explain why the eutectic point of a solution between solid A and solid B
is invariant.
(d) Calculate the standard potential Eo of the reaction
Hg
2
Cl2 + Cl2 --7 2Hg
2
+ + 4Cl-
Given the following reduction potentials :
Given : Constants for use
NA = 6022 x 10
23
mol-l
h = 6626 x 1o-
34
Js
KB = 138 x Io-
23
JK-
1
c = 30 x 10
8
ms-
1
R = 8314 JK-
1
mol-
1
F = 96,500 C
A-BRL-M-DIFA
16
10
10
f/1T[{ : rfB r:tt
Time Allowed : Three Hours
'({11 i '1 f4 #11 '1

CHEMISTRY
Paper-11
'3"m "tt frli='1R:!R"'a 1
I A-BRL-M-DIFB I
3fcF: 250
Maximum Marks : 250
cwr 3lTO (8) -GT -if -aqr ern- -if Wl" 1
qiT \f!1;:j'f I
1 5 I if Cfilf Cfilf \f!1'1" cfR \f!1;:j'f

\f!1'1" 3tcP \f!1'1" 3lCf if I
m -'l?f if lfftl:f11 -if ffficr;:rr -aqr -if
\ifTW 'T{ cpm 3WIVWF I liTUf11 3lffiC.IT 3RT liTUf11 if fc1@ 1]if 3fcF ffi

\ifif-"Cfllff m, (1liPCIC1 (Diagram) "lf!1-;:fiw fqpr 'T{ N I
3RT21T '1" "i?)-;f 'T{ SlllilfUICfi i?fiT I
3fCR if, 3liCI!1l1Cfi wffi, 3TTUR-'ffiinft ffi tG1Z Cfit I
if fTR I ffi CfllZ CfiT f1i-:Rft if ffrtrr 1Rffit
if -m 1 if m 'f'1T -rrr Lp<=j"T 3l"n 3TlT{ tG1Z
cprc I
QUESTION PAPER SPECIFIC INSTRUCTIONS
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.
Question 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/ 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 medium other than the authorized one.
Coordinate diagrams, wherever required, shall be drawn in the space provided for answering the question
iteself.
Unless otherwise indicated, symbols and notations have their usual standard meanings.
Assume suitable data, ifconsidered 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-DJFB

SECTION-A
Q. 1. (a) if,
1f\
tnT
-c;cF
cF

>rGr-1

cFr
ait\
cF.
cF ffnz
f41Scl<fi'(UI
Addition of bromine to ethylene in methanol gives bromomethyl methyl ether as one of
the products. Formulate the reaction and give mechanistic explanation for the formation
of this product.
10
(b) -cF -cF ale. KOH if, 3A"91 tiif cr't
3!1'HllCildl ihfi
t-Buo-K+/DMSO if, (iiJildOJ Cfi11 -q-{ 1J:Cfi fii-:rc
"B" Cf1l1 if (i.il IR:id \5fT
I :gWT ffnz "C!1T{UT
I
The dehydrobromination of isopropylbromide requires several hours of refluxing in
ale. KOH, whereas, in t-Buo- K+/DMSO, dehydrobromination can be carried out in less
than a minute at room temperature. Give reason for this observation.
10 (c) (i)
fct; fcRr "Ci1T{UT "B"

(C6Hsh CHCl + p- liq.
cr't
cr't -cF m Utt-rlrt \Jffifi 1
(ii)
Explain why the rate of the reaction :
liq. so
3 (C
6
H
5
)
2
CHCl + r
gradually decreases with the progress of reaction.
3lh: fct<iR., m <F ffnz,
quf<=f
5
1J:Cfi {I (i I il f.1 Ci1 tnT
Describe a simple chemical test to distinguish between aniline and benzylamine.
5
(d)
if, cr't
if, tnT
HBr
-cF

Isobutene is treated with cone. HBr in the presence of dibenzoyl peroxide in acetonitrile
solution. Formulate the reaction and give explanation for the formation of the product.
(e) f.1HR1fid if
(X) 3ih: (Y)
:
Write the products (X) and (Y) in the following reactions :
(X)
CH = CH
A- BRL- M-DIFB
(Y)
2

10
10
Q. 2. fcl1 fcR:r "CfiRUT (M + 1) 3Wf'1" \5fTdT
fcl1 3!14 i1Cfi(OI it fcR:r * 3ffilT it tr'BTCAl"
iKlT 3Th: <m1T '4T :
Explain why (M + 1) ion peak is observed in mass spectrometry. Indicate, which electron
is most likely to be lost in the ionization of following compounds and write the radical
cation formed :
(i) CH
2
= 0
(ii) CH
2
= CH
2
(iii) C
6
H
5
CH
2
CH
3
(iv) CH
3
Cl.
(b) l-<te1l {) Jfl til sf'fq \ifC1 <R
cnT fuQ:
1-chloromethyl cyclopropane on hydrolysis chiefly gives three products. Write a mechanism
to show their formation.
15
(X), aq. H0
8
m21 "Cfi"&r
An or:ganic compound (X) reacts with aq. H0
8
.
CH
3

C H -C-Cl (X)
2 5/
C6Hs
Fc1Rcta :
(i) (X) ciT Chi tif#>4dl 'R ftaluft
Cii) oH- Chi cn1 WT Cfl{ \JlW, err Chi fcRr WFR 7
(iii) fuQ:
(iv) cfi cnT
(v) (X) it C
2
H
5
3ih: C
6
H
5
'R H -ncr \ilW, m ct\1 tifsl:>4C11
'R fZu:ruft I
Write the following :
(i) If (X) is dextro, comment on the optical activity of the product.
(ii) If concentration of OH- is doubled, how rate of the reaction will change ?
(iii) Draw energy profile diagram for the reaction.
(iv) Write the mechanism of the reaction.
(v) If C
2
H
5
and C
6
H
5
in (X) are replaced by H, comment on the optical activity of the
A-BRl-M-DIFB
product.
15
3

Q. 3. C
2
H
2
BrCl (ft-;f fP11Cll:lC1l
<fiTcfT mil1 NMR
cD 1 - 1.5, 9 3ih' 14Hz I t! l0llct4Fcl4r


The compound C
2
H
2
BrCI exhibits three isomeric structures. The three isomers in proton
NMR exhibit two doublets each having J - 1.5, 9 and 14 Hz respectively. Write the
structures of isomers and assign J values to each one of them.
20
(b) \3q9,<te1
Gmm Cf)T rts:'iR1R9d cp1 '9ll:(f 'Cflct
'Q!n fcttU CfiT crrrf1
:
Describe using appropriate reagents and conditions a method to achieve the following
transformations :
a

0
20
(c) cF

\3q9,'tt1 <:Jif?l<tl\Cl
:
Write the products of the following reactions and give the suitable mechanism :
(i)
hv
NS-1
(ii)
hv
10
NS-II
Q. 4. (a) rts:'ifctR9d if [X] 3fR [Y]
ncF
cp)
Identify [X] and [Y] in the following reactions. Explain their formation.
(i)
0=(Ph
Ph
A- BRL-M-DIFB
y[X
]

[Y]
4

(ii)
26


[Y]
D

Wli (Low temp.)
20
t. [Y]
(iii)
crrq
(High temp.)
CfiT m 3W1 fC: I"&14 rn ? *
3fR CfiT i:!iGICfl , ct
How will you prepare styrene .using Wittig reaction ? Write the name of reactants and
explain the mechanism of the reaction.
20
(c) f.'tl=1Fflfuid <f; fffQ: i:!iGI Cfl \Cl
a-ftr;:fT;:r ci(I
Write a mechanism for the following conversion :
a-pinene hydrochloride cir Cl
SECTION-B
10
Q. 5. (a) fm:r- m err H
3
P0
4
cF m21 m cF IDU
CfiT cruf"1" I
Describe the products obtained by the treatment of cis- and trans-2-phenyl- 1-cyclohexanol
with H
3
P0
4
.
(b) f.1 s:1 R1Rcta it CfiT cp:rr ?
CXH
H
(i) 3iT\ (ii)
(i) (CH
3
)
3
COO- OH/H0
8
(ii) OsO it-BuOH
<fi i:!iGICfl,Cl
A- BRL- M- DIFB 5

What is the major product of each of the following reactions ?
CXH

H
(i) and (ii)

(i) (CH
3
)
3
COO- OH/H0
8
and (ii) OsOit-BuOH
Give the mechanisms of the reactions.
Identify [X] and [Y] in the following :


[X]
2-Pentyne
z
"'qoz
<$'_,...,
%<P
7
[Y]
(d) 3Wf
# 31TW m <fi
How many NMR signals do you expect in :
Explain their nature.
A- BRL-M- DIFB
6


Formulate the reaction :
---4
OH
CflT <fi fciTq;:r CfiT WlSZ ro cF J if?i<f)(;q I
and give a mechanism to explain the formation of the product.
1 Ox5
Q. 6. Cfi i<S1 'T01 Cfi m-f1lcp C
4
H
8
0, IR if 1710 cm-
1
1R 1ZCfi" 3J qf1f1tslol 1
NMR if, W o 1.1 (fWF>) , 2.1 2.3 rid
<: il11 3th- o "l=fR f1<m I
An organic compound C
4
H
8
0 gives a strong absorption band at 1710 cm-
1
in IR spectrum.
In proton NMR, it gives signat' at o 1.1 (triplet), 2.1 (singlet) and 2. 3 (quartet). Write the
likely structure of the compound and assign the o values.
20
(b) <fi if if
Write the st eps involved in the conversion of 4-bromobutanal to 4-methoxybutanal. 15
(c) w:fA't 3lTc1 cF "ffi21 ffl 1R 1fru -;:fu;rr "Df I CflT "Cfm
"Cf'>RUT ?
Amino acids on treatment with ninhydrin give intense blue colour. What is this colouration
due to ?
Q. 7. (a) f.1J:1fflftciC1 fl {'il11 1ZCfi" CflT "1111 3th-
(i) tfucp {'il1 1
(ii) \jf](1
(iii) I
H+ eft if cF ci1 )f1Cfi1 cF l:l if3iCfi , q 1
Write the name and structure of one polymer having :
(i) Linear structure
{ii) Network structure
(iii) Three dimensional structure.
15
Write the mechanism for the polymerization of phenol and formaldehyde in the presence
of H+.
20
A- BRL- M- DIFB
7

I
(b) fctl ctm' 1, cF lii)fFt>1 iJ", GT cfi,

Explain why free radical polymerization of 1, 3-butadiene leads to macromolecules having
two different types of monomer units.
15
(c) DNA it fCt<ilJOJH GT <t;Cfi l<t;ll'i cf; "1111 ti{'il1 1 m?.T 1ft ftTlZ
fctl CftiT 91RUT f.:l1 it DNA mar "1 f.:l1 RNA I
.
Write the name and structure of two purine and pyrimidine units present in DNA. Also
explain why most of the genetic materials contain DNA and not RNA.
15
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
A-BRL-M-DIFB


2
0
w

H
IH2COOC2H5 .
(CH2)2
I
CH
2
COOC
2
H
5


OCOCH
3
0
0




'fiT 3, "1 Fcf rlll/;1


8
++++
(viii) IOOC2H5 + 6
COOC
2
H
5
Cl
cfic?1 n<Fl
(ix) a
0

UCONH2
N
(x)
Write the products of the following name reactions :
(i)
(ii)
(iii)
(iv)
(v)
(vi)
A-BRL-M-DIFB
ctro
Baeyer-Villiger



2
0
8=:J
H
CH
2
COOC
2
H
5
I
(CH2)2
I
CH
2
COOC
2
H
5
Perkin reaction
Reformatsky
Reimer-Tiemann

Dieckmann reaction
Frie's rearrangement
&_OCOCH
3
OCOCH
3
9


(vii) 0
0
(viii) COOC
2
H
5
A
I +U
COOC
2
H
5
Cl
(ix) ex
0
Cannizaro reaction

Claisen condensation

Favorskii rearrangement

U
CONH
2
(x) I
::--..
Hoffmann rearrangement

N
(b) if (X) 3fR (Y) tt>i
Identify (X) and (Y) in the following :
0
A-BRL- M-DIFB
o3 > (X) NaBH
4
(Y)
10

10x4
10