1. PART-A
Select the correct alternative(s). (One or More than one is/are correct) [20 × 4 = 80]
There is NEGATIVE marking. 1 mark will be deducted for eachwrong answer.
Q.21 Thevapourpressureofanaqueoussolutionwhichshowelevationinboilingpoint(Tb)equalto1.04°C
is found to be 760 torr at 373 K. Find the atmospheric pressure in torr. Given Kb (H2O) = 0.52 K-kg
mol–1 [atNormalboilingpoint].
(A*) 787.36 (B) 761.23 (C) 759.08 (D) none of these
[Sol: 04
.
1
Tb 

Kb
= 0.52 K Kg mol–1
molality
K
T b
b 


1.04 = 0.52 × molality
molality 2
52
.
0
04
.
1




s
s
0
P
P
P
molality × M.Wsolvent
× 10–3
3
0
10
18
2
760
760
P 




3
0
10
36
760
760
P 



3
0
10
36
760
760
P 



 = 27.36
P0
= 760 + 27.36
P0
= 787.36 torr ]
Q.22
(I) (II) (III) (IV)
(V) (VI)
AandB are respectively.
(A) I and II (B*) II and IV (C) V and VI (D) I and III
XIII Paper-1

2. [Sol:
]
Q.23 Forwhich of the following dn configurationof octahedral complex (es), can not exist in both high spin
andlowspinforms.
(A*) d3 (B) d5 (C) d6 (D*) d8
Q.24 For the reaction
CO(g) +
2
1
O2 (g) CO2(g)
usingdatagivenintableat 298Kfindout incorrect statement(s)among thefollowing.
213
395
)
g
(
CO
205
0
)
g
(
O
197
110
)
g
(
CO
)
Kmole
/
J
(
S
)
mole
/
kJ
(
H
2
2
o
f







(A*) H° > U° for the reaction at 298K.
(B*) In standard state condition, the reaction CO(g) +
2
1
O2 (g) CO2(g)
attain equilibrium at verylow temperature.
(C*)
dT
)
H
(
d 

= CV
(D*) In a CO, O2 fuel cell electrical energy obtained by cell (at 298 K) > | o
combustion
H
 [CO (g) ]|
[Sol: )
g
(
)
g
( 2
2
)
g
( CO
O
2
1
CO 


R
P H
H
H 



= 







 2
2 O
CO
CO H
2
1
H
]
H
[
= (–395) – [–110]
= –395 + 110

3. = –285 kJ
R
P S
S
S 



= 






 2
2 O
CO
CO S
2
1
S
S
= 







 205
2
1
197
213
= 213 – 197 – 102.5
= –86.5 J
RT
n
U
H g





= RT
2
1
U 

U
RT
2
1
H 



 U
H 


forequilibrium S
T
H
G 




S
T
H
O 



5
.
86
10
285
S
H
T
3






 = 3294.79 K.
kJ
285
H C
of
.
comb O 


Electrical energyobtainedbycell at 


 G
K
298
=  





 S
T
H
= ]
5
.
86
298
10
285
[
kJ
10
5
.
86
298
kJ
285 3
3








 = –[–285+25.77]
= + 259.23 kJ
 Electrical energy< Hcomb.
]
Q.25 Whichofthefollowingwill givethreedifferentcompoundsonozonolysis
(A) (B*) (C*) (D)
[Sol: (B)  + O=CH–CH=O +
Three differenceproducts are

4. (1) (2) (3)
(C) Three difference products are
]
Q.26 Potassium chromatesolutionisadded toaqueoussolutionsofmetal nitrate.TheYellowprecipitate thus
obtainedareinsoluble in acetic acid. These are subjected toflame test, flame colourof individual ppt.
is/are
(A)Lilac (B*)Apple green (C) Crimson red (D*)Blue
Q.27 A compound 'A'transform bytwo parallelfirst order paths
A (g) 

 


)
(min
k 1
1 2B (g) k1 = 6.93 × 10–3 min–1
A (g) 

 


)
(min
k 1
2 C (g) k2 = 6.93 × 10–3 min–1
If reaction started with pure 'A' with conc. 0.1 mol/Lin a closed container with initial pressure 2 atm.
What is thepressure(inatm)developedin container after50 minutes from start ofexperiment.
(A) 1.25 (B) 0.75 (C*) 2.50 (D) none of these
Q.28 + 
2
PhN Cl–  ? 
 


O
H3
Finalproductisamixturecontaining:
(A*) (B*) (C*) (D*)
[Sol: e.g. ofN–N coupling

5. +


 N
N
Ph 
Q.29 Whichofthefollowingaqueoussolutionofcation(s)give(s)whitepptwithNaOHandNH4OHsolution
and formedppt. is/arefurther completelydissolved in one ofthe excess reagent.
(A*) Cd2+ (B) Cr3+ (C*) Sn2+ (D)Bi3+
Q.30 Truestatements regardingSN1reaction is/are
(A)Perfectracemisationis observed
(B) OnlyWaldeninversion is observed
(C)Total retentionof configuartion is observed
(D*) None of these
Q.31 
2
3
CO and 
3
HCO canbe distinguished by
(A*)Phenolphthalein (B*)MgCl2 solution (C*)HgCl2 solution (D)KCl solution
Q.32 
 
 2
SOCl
(A)
Major product (A) is:
(A*) (B) (C) H2C = CH2 (D)
[Sol:
i
N
2
S
SOCl

 

R– R–
In i
N
S mechanism retentionofconfiguration takes place ]

6. Q.33
Which ofthefollowingoptionsis/arecorrectregarding‘P’amongthefollowing
(A*) O3 (B*) excess Cl2 water (C*) conc. HNO3 (D) HCl
Q.34 Whichofthefollowingisthechainterminationstepduringphotochlorinationofethane:
(A*)



 Cl
CH
CH 2
3  CH3–CH2–Cl
(B*)




 2
3
2
3 CH
CH
CH
CH  CH3CH2CH2CH3
(C*)


 Cl
Cl  Cl2
(D)


 H
Cl HCl
[Sol: Inchainterminatingsteptwofreeradical reacts. H0 ishighlyunstable. ]
Q.35 Whichofthefollowingproperties showasimilartrendonmovingfrom Li to Cswithin thegroup
(A*)Ionicmobility (B*) Reactivitytowards water
(C)SolubilityofBromidesalt (D*)Thermal stabilityofCarbonatesalt
Q.36 Whichofthe followingstatements is / are true:
(A*) Major part of energy needed for the heterolysis of C–X bond in SN1 reaction mechanism is
obtainedbythe solvation of X– bythe polar protic solvent.
(B)Greatersolvationofattackingnucleophile&poorsolvationoftransition statepromotesthereaction
bySN2mechanism.
(C*) Increase in the no. of phenyl ring at C of C–X causes a shift in mechanism from SN2 to SN1.
(D)Allyl & benzyl halides undergo SN2 reactions as theyare primaryhalides which do not give SN1
reaction.
Q.37 Whichofthefollowingstatementisincorrect.
(A*) O2 is paramagnetic, O3 is also paramagnetic
(B) O2 is paramagnetic, O3 is diamagnetic
(C*) B2 is paramagnetic, C2 is also paramagnetic
(D*) Different observation is found in their bond length when NO NO+ and CO  CO+
Q.38 Inthegivenreaction
C7H12 (A) 
 
HBr
(A)is:
(A*) (B*)
(C*) (D)

7. [Sol: (A)  


 
 
HBr
H
(B) 
 
H
(C) 
 
H ]
Q.39 Choose the correct statement.
(A*) BaCl2 +AcOH + K2CrO4  yellow ppt
(B) BaCO3 (s) + K2CrO4  yellow ppt
(C) BaCO3 (s) + K2CrO4 + AcOH  No ppt.
(D*) SrCO3(s) + K2CrO4 + AcOH  No ppt.
Q.40 Which ofthe followingwill givesameproduct withHBrin presence& absenceofperoxide
(A*)ethene (B) 1-butene (C*) 2-butene (D)isobutene
[Sol: Symmetrical alkaneprovide same product withHBr in presence & absence of peroxide.
Mechanismisfreeradicaladdition ]