P A PER - 2 ( CH E MI ST R Y )

PART-B
MATCH THE COLUMN [6 × 10 = 60]
INSTRUCTIONS:
Column-I and column-II contains four entries each. Entries of column-I are to be matched with some
entries of column-II. One or more than one entries of column-I may have the matching with the same entry
of column-II and one entry of column-I may have one or more than one matching with entries of column-I

Q.3 Column I Column II

LiAlH 4 NaNO
(A) HCN
 (A)    (B)  
2  (C) (P) Formation of six member ring takes
traces of KOH HCl
place


NH OH H
(B)  (A)  (B)  (C) (Q) Final product is Ketone
LAH
 2


O O
|| || HO 
(C) CH 3  C  CH 2  CH 2  CH 2  C  H  (A) (R) Final product formed will give

positive Tollen's test

(D) H
 (A) (S) Final product formed will react with

2,4 DNP.

[Sol. (A) + HCN + KOH 

 LiA
 / H4


Cyanobydrin (H) NaNO2  HCl

(A)

(C) ring expansion. [Ans.  A  P,Q,S]

 

(B) NH 2OH H

/D

 
  H 2O
(A) ring
(oxime) expansion

(C) Piperidine Cyclic amide (B) [Ans. B  P]

(C) CH3 – – CH2 – CH2 – CH2 – – H OH /D

 
e.g. of intramolecular aldo/condensation i.e., Dieckmann Condensation reaction.

(A) [Ans. C  P,Q,S]

(D) e.g. of Pinacot-Pinacolone rearrangement :-

[Ans. D  P,Q,S]
Q.4 Column I Column II
(A) ZnCl2 + H2S (P) Pale green colouration
(B) CuSO4 + Excess KI (Q) Brown ppt. / appearance
(C) Pb3O4 + conc. HNO3 (R) White turbidity
(D) FeCl3 + H2S (S) No change is observed
[Ans. (A) S; (B) Q, (C) Q; (D) P, R]
[Sol: (A) ZnCl2 + H2S  ZnS  + 2HCl
white

Cu 2 I 2
(B) CuSO4 + KI  + I2 + K2SO4
brown

PbO 2
(C) Pb3O4 + HNO3  Pb(NO3)2 + + H 2O
brown

S
(D) FeCl3 + H2S  white + FeCl2 + HCl]
turbidity

PART-C
SUBJECTIVE:

Q.4 100 ml of 0.05 M CuSO4 (aq) solution was electrolyzed using inert electrodes by passing current till the
pH of the resulting solution was 2. The solution after electrolysis was neutralized and then treated with
excess KI and formed I2 titrated with 0.04 M Na2S2O3. Calculate the required volume (in ml) of
Na2S2O3. [5]

[Sol. pH = 2

[H+] = 10–2
meq of Cu+2 discharged = meq of H+ produced.
= 10–2 × 1 × 100
=1
Cu+2 + KI–1  I20 + Cu+
meq of Cu+2 left after electrolysis = meq of KI used
= meq of I2 liberated
= meq of Na2S2O3 used
meq of Cu taken initially – meq of Cu+2 discharged = 0.04 × 1 × V
+2

0.05 × 2 × 100 – 1 = 0.04 V

10–1 = 0.04 V
9 = 0.04 V
9
V= = 225 ml Ans. ]
0.04
Q.5 A white coloured inorganic salt (A) gives the following reactions.
(i) It is soluble in water. The solutions turns black in presence of H2S.
(ii) The solution gives a white ppt. with dil. HCl which is soluble in hot water.
(iii) The salt when heated gives acetone and a yellow coloured residue.
Identify the salt (A) and calculate molecular mass of salt (A) [5]
Pb(CH 3COO) 2 H S PbS 
[Sol: ( A )LeadSugar 
2
 Black

Mol. wt of (A) Pb(CH3COO)2 = 207 + 59 x 2 = 325 Ans]

Q.6 Reaction 1— 5 HIO

 4 

Reaction 2— 5 HIO
 4 

Ratio of moles of formaldehyde obtained in the reaction (1) and reaction (2) [5]

[Sol. Reaction (1) 5 HIO formaldehyde only 2 mole.

 4 

Reaction (2) 5 HIO for maldehyde only 1 mole.

 4 

[Ans. Therefore, ratio  2 : 1 i.e., 2/1]

(1) Ac O , AcONa, 
Q.14 Reaction 1—  2    (A)

( 2 ) H 3O , 
 O
|| Al( OCHMe 2 )3
Reaction 2— Ph – CH  CH – C  CH 3      (B)
CH 3  CH  OH
|
CH 3

OH
| (1) NaOI
Reaction 3— Ph – CH  CH  CH  CH 3    (C)

( 2) H
Degree of unsaturation present in compound (A + B + C) is? [8]
[Sol. Reaction (1) is an example of perkin cendensation

 
AC
2O / ACO Na
 
Ph– –H H 3O

/D

Degree of unsaturation in (A) is  6

Reaction (2) is an examples of M.P.V. reduction

Al 
(OCl M2 )3
 Ph – CH = CH –
 – CH3
Degree of unsaturation in (B) is  5 (B)
Reaction (3) is an example of halo from reaction

Ph–CH = CH – – CH3

NaOI
Ph–CH = CH – – CH3 
 Ph – CH = CH – – OH + CHI3
H
(C)
Degree of unsaturation in compound 'C' is  6
[Ans. : Degree of unsaturation present in compound A+B+C  6+6+5  17] [Ans. 17]

Q.15 The specific conductivity of a 0.5 M aq. solution of monobasic acid HA at 27°C is 0.006 Scm –1. It's
molar conductivity at infinite dilution is 200 S cm2 mol–1.
Calculate osmotic pressure (in atm) of 0.5 M HA (aq) solution at 27°C.
atm L
Given R = 0.08 . [8]
mol K
[Sol. K = 0.006 –1 cm–1
C = 0.5 M HA T = 27°C
   200  1cm 2 mol 1
    (Since nf = 1 for HA)

1000
Kv 
 C
 = v 
 
 1000
0.006 
 0.5  12  0.06
200 200
HA H+ + A–
C(1–) C C
C(1  )  C  C
i=  (1   ) = 1 + 0.06 = 1.06
C
 = CST × i
= 0.5 × .08 × 300 × 1.06
= 12.72 atm. Ans. ]

Q.16 21.4 g XCl salt is dissolved in water and formed 2 litre of solution. The pH of the resultant solution was
found to be 5. Calculate the density (in g/cc) of solid salt XCl, if XCl forms NaCl type crystal having
–
r (radius of X  ) = 0.8 Å & rCl – (radius of Cl ) = 1.7 Å.
X

Given : Kb (XOH) = 2 × 10–5; NA = 6 × 1023 Use 10–0.7 = 0.20, log2 = 0.3 [8]

[Sol. Kb = 2 × 10–5
×OH

XCl  Salt of weak base and strong acid.

1
pH = – [log Kw + log C – log Kb]
2
1
6=– [log 10–14 + log C – log (2 × 10–5)]
2
1
=– [–14 + log C – log 2 – log 10–5]
2
1
=– [–14 + log C – 0.3 + 5]
2
1
5=– [–14.3 + 5 + log C]
2
10 = 14.3 – 5 – log C
log C = 14.3 – 5 – 10
log C = – 0.7
C = 10–0.7
= 0.2
C = 0.2
21.4 / M
 0 .2
2
21.4
M=  53.5
2  0 .2
a = 2r+ + 2r–
= 2(r+ + r–) = 2 × (0.8 × 1.7)
 = 2 × 2.5
a  5Å ]

n  mol. wt

NA  a3
4  53.5

6  10  (5  10 8 )3
23

4  53.5
=
6 1023 125 1024
= 2.853
= 2.85 gm/cm3 Ans. ]

Q.17 Calculate the EMF (in V) of the cell

Pt | H2(g) | BOH (aq) || HA (aq) | H2 (g) | Pt
0.5 bar 0.1 M 0.01 M 1 bar
RT
Given: Ka(HA) = 4 × 10–6, Kb (BOH) = 10–5, 2.303 = 0.06, log 2 = 0.3 [8]
F
[Sol. Pt. H2 | BOH aq || HAaq || H2 Pt
(g)
0.5bar 0.1M 0.01M 1 bar
H2 2H+ + 2e–
P1 =0.5 C1
+
2H + 2e – H2
C2 P2=1
H2 + 2H+ 2H+ + H2 Cell A
P1= 0.5 C2 C1 P2=1
In anode [OH–] = K b.c

= 105  0.1 = 10–3 M

1014
C1 = [H+] = 3
 1011 M
10
In cathode [H+] = K a .c

= 4 106  0.01
C2 = 2 × 10–4 M
.06 C12  P2
Ecell = E0 log
cell – 2 P1  C 22

0.06 (10 11 ) 2  1

= 0.0 –  log
2 (0.5)  (2  10  4 ) 2

0.06 1022 10 14

= log = 0.03 log  0.03[14  0.3]  0.03  14.3 = – 0.429 V ]
2 4  0.5 108 2