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Time Allowed: 3 hours

Maximum Marks : 300

PA,I!R "' U
SEC110NA

Answer any three of the follo1Mng

~
(a)
(i)
State and explam Heisenberg's uncertamtypnnc1ple Why 1s
ot phcable to large
part1cles

(10)
(ii)
When an electron was accelerated through a ..E2'
fference of I. 00 0.0 I
kilovolt, what is the uncertainty of position of '7e"'cle~-~ong its line ofproj ection?
(I 0)
of
a
chem1cal
bond?
(b)
How does the pnnaple of 'max1mum overla~
e
Enumerate the essential cond1tton
(20)
j e atom1c packmg factor m s1mple cubic
What 1s atonuc rad1us of a cub1c Ia
(c)
system, body- centered cub1c syste
cub1c system

ra

ce

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om

Can eli dates should attempt Question Nos. I and 5 which are compulsory, and any three of the remaining
questions selecting at least one question from each Section. Assume suitable data if considered necessary
and mcli cate the same clearly
~

am

4_:
~tered

(d)
(a)

(b)

.e
x

2.

3.

(b)

(c)
4.

(a)

(20)
What are semi conductors ? Explain n - type and p-typ e semiconductors. Discuss the effect of
temperature on semiconductors.
(20)
(i)
Derive the Kelvin equation for the vapour pressure of droplets and bubbles.
(I 0)
(ii) What are nucleation centres? Indicate their importance.
(I 0)
Explain the criteria of equilibrium and spontaneity in terms of U, S, A and G.
(20)
"The third law of thermodynamics states an impossibility." Justify this statement.
(i)
(I 0)

................................................................................................................................................................................................................................................................................................................................................:.~1

Explain why the molar entropy of ice crystals approaches 335 JIC 1mor1, as the
temperature approaches zero kelvin.
(I 0)
Define chemical potential. Explain its significance. Deduce equations for the variation of
chemical potential with temperature and pressure.
(20)

(ii)

(c)

(i)

What is the maximum number of phases that can be in equilibrium at constant

pressure and temperature in two- and three- component systems?

(u)

For the reaction N2 (g)+ JH2 (g) I~ 2NH3 (g)

Kp = I 64 x 10' at 670 K Calculate ll.G0

.c
om

(b)

(I 0)

5.

Denve an equation to relate temperature on rate o~~

activation
~

(c)

(1)

"Tetrahedral complexes of 3d
statement

(u)

Calculate the crystal field s

[V(H20)6f

(a)

(20)
d cal cui ate the energy of

ra

tran~
1 O:,..._~e always of high spm" Justify(~~
-~

am

1h

(1)

(I 0)
nergy and spm-only magnetic moment of
(I 0)
formation than lanthanides " Just! fy the

(b)

.e
x

6.

coe~and mdicate how

(b)

(d)

i~n ~Iutton

0.

Define activity, activity coefficient and mean activity coefficient of

Denve and use the Debye-Huckel hm1t1ng law for mean activity
it can be extended to more concentrated solution.

ce

(a)

(10 + 10 = 20)
d explain the law of photochemical equivalence. How are the discrepancies of this
explained?
(20)
What are heterogeneous catalysts ? Discuss the characteristics and mechanism of reaction on
heterogeneous catalysts.

7.

(b)

(20)

(i)

(ii)

Identify one significant role m biological processes for each of the following
elements:
Fe, Mg, K, Zn, I
(I 0)
How is iron stored and transported in mammals? What is the oxidation state of iron
for storage and transfer?
(I 0)

(c)

(i)
(ii)

(a)

(i)

.c
om

"The complex [NiCI.t is paramagnetic whereas [Ni(CN).t is diamagnetic." Justify

the observations.
(I 0)
Explain the origin of pale pink colour of [Mn(H20)6] 2.
(I 0)
Explain the possible isomerism in the following complexes:
[Co(NH3 )5 Br] SO
[Co(Nfu)sN02] 2
[Co(en)2Cl2]

(b)

(20)

(c)

.e
x

am

ra

ce

(20)

..

!!'i!'r~\;~.~.\:~~\~~~~~.;~.\~;~.~::~\.;:~~~:~.:\~~~\~~;~~\~;~m~,l----------------------------~r.;
;{

(i)

(c)

(2 xI 0 = 20)

.e
x

(ii)

am

(ii)

(b)

ce

>

(i)

ra

(a)

Maximum Marks : 300

.c
om

Time Allowed: 3 hours

~;

;~

A~.

2.

(a)

(b)

e~J

,.:a 8llld E, _..D

~;

Ozonolysis of ~ C:...-a
B;c
(Where B & D are stronger electron donor than A and E) pro duces four ozonides. Explain
mechanistically.
(20)
Butadiene on reaction with Br-F (mole ratio= I: I) produces two products. Explain.
(I 0)

C:...O

J~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Jl

L ..................................................................................................................................................................................................................

N~

(c)

C6 H5 -Cl on reaction with NaOH in an autoclave produces phenol (major), diphenyl ether and
p -phenyl phenol. Explain the mechanism of formation.

(d)

Why p-nitro benzaldehyde does not follow benzoin condensation? Explain.

(e)

C6 H5 CHO is refluxed in the presence of NaOH and excess HCHO. Write the major aromatic
product.

(20)
(5)
(5)
3.

Identify the intermediates and pro ducts:

II

(a) (i) C6Hs - CHO + CH3C - CH3 base

Acid
CHz(0t)z B ltydrolylfis ) C

llaae

frl) L 3--butadi.ene (excess) + ~benzoquinone

atSO"C

heateri
5
\rilhSe

Zn+add

AlCl,
Room temp.

.e
x

or,

(c)

am

ra

---"--+A

ce

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om

4.

Identify the products in the following reactions:

~?

(:H,-CB,-C -Oi:t

C!l2-t::lr_-1-0I't

(a)

(.,!

J-..

,_;'

u;"l

CliO

J:~l"
<,;li~J -----

to

CN"

!\tf\

<.:~toil),~

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om

.,..,,_..,CHO

(bl

(il Z:~ HCI

. OCN,

----->-A

-----;>lJ

(ii) TINO, riC

WiJ(C~

am

ra

ce

(Hj) i:J.ojJo,:od kl

.e
x

ONB

following in their electronic j~

(c)

(i)
(ii)

(d)

(i)

(2 x I 0 = 20)
Explain the appearance of m/z = 44 peak in the mass spectrum of CH3 CH2 CH2 CHO.
The dehydration of I, 2-dimethyl cyclohexanol (cis or trans) gives three alkenes. How
can you distinguish them on the basis of their IR spectra?
(2 x I 0 = 20)
The geometric isomers of stilbene show ~ at 278 and 2 94 nm. Assign each value to
appropriate isomer and sketch them.

i;

j~
i<
~{
i<

j~

j~
i<
~{
i<

,,,,,,,,,,,,,,,,,,,,,,,,~~~>,,,,,,,,~:-~~-~~-~~-~~-~~~--~~-:-~-~-~~~~-~:::.~-~~=~:~. -~~---Jl

h>

UH OH

(2 x I 0 = 20)
Identify A-D in the following
(a)

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om

6.

(b)

How adipic acid can be produced from phenol (only two steps)?

(d)

2, 3-dimethyl-2-chlorobutane on E2 dehydrohalogenation gives ho

they be distinguished by IR spectroscopy ? Justify your ans~
Explain the mechanism o Hollowing transformation:

d:i.=0Y'

-(b)

() Whuhy!:sr.N

.e
x

(c)

(ii)

Mechanical.streng

(iii)

Why

(I 0)
y products? Can
(20)

'(j

am

...----

CJ

ce

(a)

(I 0)

ra

7.

(c)

20)

NA'

(15)
(15)

(I 0)

ylon is better than polyester. Explain.

doe~ollow anti-Markovnikovs addition to

(I 0)

8.

"'it 1

(c)

(d)

(I 0)

oscopy ? Give method for chemical separation of the two compounds.

(20)

w is azelaic acid obtained from oleic acid?

Azelaic acid HOOC(CH2) 1 COOH
Oleic acid= CH3 (CH2) 1 -CHCH(CH2) 1 COOH.

(I 0)
A cyclonitrile can be polymerized by base catalyzed reaction but not by acid catalyzed
reaction. Explain.
In the mass spectrum of CH3 CH2 C-OCH3 the peaks <J. m/z = 57, 59, 8 8 appear. Explain.

II
0

(15)