C.S.E.

Chemistry (MAIN)~ 2005

169

C.S.E. (MAIN)

CHEMISTRY

2005

PAPER- I
Time Allowed: Tltree Hours

M11ximum .~1arks :.300

C.S.E. Chemistry {MAIN)- 2005

wh(~l't' following kinetic

Initial concn. (mol

data were obtained:

Initial reaction rate
(mol dm3 s1)

dm- 3)

(;N-(aq)

o.sn

n-so

1-on x w-~

Hlo

o-so

4-0I

wl

l-()()

1-00

7-96

1() 4

\ d!t u!<1!<' OVl'r<lll ord<r of n<~rlion ,md lls rdt<' constcwt

J.

,:) ~ .. ~tifv th,~l S-Oi'\:>i\(1[$ (\!'~ I\OI)Qin:ctiona! Wh<'rt'aS

~
,u1d <.l-orbitals !Hve dircr;tion;~l character. D<rivl' wa~
ft<!Kiion!i of spl hyhridiz.<~d orbitals.
20
b) ~~il;lt ;He seven crystal sys~~~n_,_s and ~.'1 l!r<lV<li/t:)411'S.
t.hs,uss t!w structures of C. sCI <1nd 7.r6.r ~ 20
:.) W!.H:!t ;:.''~ _th<~ fac!(~TS, that de; ide thi? ~i ionir
, h.. r.-ltlu 111 pol<H co!.lpounds: ~
20

st,,hiliratio,~~c~FSE) Wh<ll
!actors wh lt"'t its magnitude?

1. (.-\j h.;plclin nplcll lie!ds

Me lhc vill"ious

CFSt~ <1iKi

ma

m 1cnts

(f.l,. 11 } in ta.ses
of h~U,. bl tp <tnd K :,~ 'N),.
25
(l') Derive C!ausius-U< c
1uation lor !he variation
of vapour press ,_,
,~rltpNatun~. Calculate the
PCjtrilibriurn p
. r tiw conversion of graphltt~ to

C1kul<ll1.

diamond ;~~
~ ssurning thc~ir densities to bl~ 2-23
and 3-5i g
' nd ;\G" "' 2900 J mol 1
25
[c) 1\:pla tlw r of metal ions in biological systems and
th
'i1tlon tr<msport across tb(~ rellmembrane. 10

SECTION-ll
5.

any three of the foitmving

iO

3 =60

suit<tble t~xamp!e for t~ach.

(b) Explain tht~ intense blu(' colota of aqueous
permanganate soluti.on. What happens to it when the
snlution is ldt in sunlight for t1 day?

C.S.E. Chemistry (MAIN)- 2005

(c)

Hemt~

acts as carrier of 0 2 in the system whereas toxic

dfL><:ts of CO can be explained by replacenHmi reClction.
Explain.
(d) Draw the nature of a typical polarogram and explain
diffusion current, limiting curr<;?nt and residu;~l current.
Show that F,,, is indepc:nden t of mnct~ntration.

6. (a} Nanw all the lilnthanidts and show how its common
l)xidation state is 3 though sonw of thes(~ (!Xhibit other

oxidation stat(~$ as wdl. Explain why ionic radii

decreases from Lr3' to l..u 3 ' even though illornic nunv.
iner<~ases bv H
30
(h) Explain the nature of mclaJ.carbony! hond m r<Hbon)' .
[)raw tlw structures of h~~(C0),1, F(.(C0) 3 ,.~:(.! 0

and Ni(CO),. In what respects t(~rminG.a

~p is

different than bridging CO in such co Jiex s ,

20
(c) Disruss the role \)f photosyntl~ .rrodoxin
molecule and describe its stru~t!.Vres
1U

7. (<l} ~Vhill <~re mct<dlorcnes <md

feillurf.!~ 7 Di~UlSS the s

'-.~.<Kk~ristic strudural
Jf\! f fl~rrO(\!mJ with MO
di<~gram.
20
(b) Explain 'trilns efft~ (US~ its theories. Describe
substitution in
compkxes with suliable
examples.
20
(c) Describe
truction and ftm(tioning of lithium

01

uavanar

8. ~m!k~" 1::,;:,::::~ ;:~::~:.:":::::,:::~:~

0

nee. Show that heat capacity <)f an ideal

!. R

~1as

20

2
( ) Derive an expression for th(? entropy of mixing of two

tdl!al gases at the same temperature and pres:;ure. 20

(c) Explain homogenous and

hcterogeneou~

<:atalysis with

a suitabl~ example for each. Derive and expression for

' of a surface catalyzed reaction.
the rate
20

C.S.E. Chemistry (MAIN )- 2005

PAPER - II - 2005
Time A IT owed : Three Ho"rs
Maxim um Marks ; 300
CatJdida tes should attemp t Questi ons 1 and S w hich are
compu lsory, aud auy THREE of the remai11i11g que:;ti<ms
selet"tiug at least ONE questiou from each SectiQtl.
Tile numba of rna rks cam'e-d by each questi011 is i11dic a ted at

the end of the question.

20><3=v

l. Ans_we r any three of the followi ng . .

. ,
(a) fhe stcruoc hemtstr y of nud(.'6philll: ~ubsntution by
Sw) m ec hanism ts al mos t al way.~ racemi zatio

However the stereoc hemistry of substit utior\

thiophe noxidc ion is depend ent upon the con

on
of nucleop hik. When it is low, the pro
ost
rac\lmk but wht:n it is high, the
o etained
sterevchem is try. Explain .
(b) Ex p l;tin the mentio ned pK~Of t
follow ing

prl
o tS

C<)mpo unds:

"'

C)
(i)
p Ka 1058
(c)

I'>""

i)

(iii)
5-06

'(J 779

th followi ng observ ations with respec t ot

Nl

--4

15

[>--N ,-N

N '
-4

[>-N ,
3 '-~

[>- N,
ij:.

.
.

1>- N -N> N
15
97%

1>-- N 77%

N N

15

C.S.E. Chemistry (MA1N)- 2005

(d) Halide A solvolyzes ten tim~ faster than halide B. Both
give C as the product of solvolysis in aqueous ethanol.

Eplin.cb x
A

d:t HOili
B X

2. (a) (i) Expla in why the following 4 + 2 cycloaddition

reaction does not occur to produce cantharidin

Co

H3cy \ --}
H3C~(
0

Hz! Pd

H C CH 0
'3
3

tn

,,

'(J

din

e foUowing to solvolysis
s in the same as they are
S+l0 =15

the

(ii) Bromine react5 about 165 times faster with

PhCH = CHPh than with PhCH "' CHBr.
(iii)The following rea c tion proceed s 35 time s less
rapidly when R = CH, than when R "' H :

OzN --9-Br

~ Ho-702N-P-{~)

r.

(c)

lnt!tcatc~ the stt>ps by rm~ans of which you wtll df~ct

the following convt!rsions in good yields:
(D

O,cocH, -----> O,cocH. Cll cu,

COCH3

tii)

6-+
6
R'-. ~
weJ

OH

20

0
CJ

(iii}

(i,)

R'-.
/H
H/c = c"- a

The~\ re~gents available are m-chloroperbenzonic

~triphenyl

0~'

fj

phosphine.

zaldehyde on reaction with alcoholic CN6 gives

zoin but acetaldehyde under the same conditions
does not give acetion. Why ? If you were to get acetoin,
how will you proceed to synthesize it ?
10

.~

3. (a) In the following rea.;:tions (i) and (ii), the major product

of the reaction is A with very little amount nf B.

Rationalize the observations:
15

Elr

(i)

~ .eas~

o0-...

Ether

~I
B

(ii)

(iii)

(iv)

th~

:::declivity shown in the tollowii\S

15
(i}

Base

Oil H ~
>

(d} On heating A in toluene in the presence of SbFs and

Hf, one gets over 95% yieids of pnitro toluene. Explain
the mechanism of the reaction.
10

N02

)
4. (a) liow will you prov:that Beckmann rearrangement is
an intermolecular rcarrang!)ment ? Take suitable
examples to illustrate your enswcr.
10
(b) Give t~1C medumis~ oi the reaction that explainsCJ

l.

lol!owu"lg observiltiO:ns;

Heat in a sealed
tube at 120C

29%

71%

(c)

CH ~COOCH~CH
. ~co

c
Ph001 2GI 2CO;
D

-~

~'

(d) (i) How do you e'<plain the concept<; of aromMitity,

anti-aromatidty und homo-aromaticity ?
(ii} Which of the following compounds ar~~ ar<.lmatic
and why ?
10 + 15 = 25

)1"

u
~'

(1)) Normal 0 - H stretch com

Is the red uced mass for

reduced mass when
rn
dou bled in tum; i. ,
and 5 - H ? In f t
t

at about 250
(b) Indicate
~

--- 0.

1 ) .

out 3600cm 1. WJu1l

hat happct's to the

mass of each ntom is

H is

conv(~rt(ld

to 0 - D

. () ;md S l I stretch \.Orne

y?
ectrum can be used to distinguish :

CH, ""d

v\_

CH,

(c) Indicate how NMR can be used to distinguish

Cll:1
(i)

~CI

CH3

CHa

~ Gland

.. )
(.11

6.

fro m the inspection of mass

20
spectrum of the com pound that it contains
(ii) one (h.lorine atoms
(i) one JUtr<JgNI atom

(i.ii) two chlorine atoms

(iv) one bromine atom
(c) Outline the synthesis of 100% cispoly(isoprene).
Discuss reasons for the choice of reagents or catalysts
and the mechan.i:;m of polymerization.
20
7. (a) The natural product bullatcnone was isolated in th<1
1950s and assigned the structure A. When ~:ompo~o~nd
A was synthesized, it was not identical with the natural
sample. Predict the expected 11! NMI~ spectrum of A.
Civen the full spectroscopic data available MWadays,
hut not in 1950s, say why A was wrong and suggest a
b~tt~n structure for bulla~none.

Ph

0
CJ

tv1ass spectrum :

(b) (i) Sketcl~

resolution H NMR spenrum of ethyl

aceto~

{ii) I

.....
~

ica te main stretch frequenc:io:s for functional

pt present in acetyl acetone. What would
a en to the spectrum if a small amount of organic
5e is added to it 1
10 x 2"' 20
ustrate Woodward-Fieser Rules to calculate thr:
xpected ''m.- of enones in the uv-spectrum.
10

~, (a) Give the steps involved in the synthesis of the following

compounds from indicated materials:

15
(i) Phenolphthalein form phenol, phthalic al'lhydride
and sulphuric add.
(ii) (X-methyl cinnamic acid from benzaldehyde, base
<H1d propanoic <H\hydride.
(b) Using chemical and/ or spectral methods (as indicated),
show how !he following can lw. differ(>n!iated :
15
( i)

(ii)

(c)

o possible products from Favorskii

thal occur. when A reads with sodium
. What are the products and which will be

in larger amount ?
0

Cl

II

Ph CH 1 C - C - (CII l )2
A

15