Paper-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 each wrong answer.

Q.21 The vapour pressure of an aqueous solution which show elevation in boiling point (Tb) equal to 1.04°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 [at Normal boiling point].
(A*) 787.36 (B) 761.23 (C) 759.08 (D) none of these
[Sol: Tb  1.04
Kb = 0.52 K Kg mol–1
Tb  K b  molality
1.04 = 0.52 × molality
1.04
molality  2
0.52
P 0  Ps
 molality × M.W × 10–3
Ps solvent

P 0  760
 2  18  10 3
760
P 0  760
 36  10 3
760
P 0  760  760  36  10 3 = 27.36
P0 = 760 + 27.36
P0 = 787.36 torr ]

Q.22

(I) (II) (III) (IV)

(V) (VI)

A and B are respectively.

(A) I and II (B*) II and IV (C) V and VI (D) I and III
[Sol:

Q.23 For which of the following dn configuration of octahedral complex (es), can not exist in both high spin
and low spin forms.
(A*) d3 (B) d5 (C) d6 (D*) d8

Q.24 For the reaction

1
CO(g) + O (g) CO2(g)
2 2
using data given in table at 298 K find out incorrect statement(s) among the following.

H of (kJ / mole) S(J / Kmole)

CO(g)  110  197
O 2 (g ) 0  205
CO 2 (g)  395  213

(A*) H° > U° for the reaction at 298K.

1
(B*) In standard state condition, the reaction CO(g) + O (g) CO2(g)
2 2
attain equilibrium at very low temperature.
d (H )
(C*) = CV
dT
(D*) In a CO, O2 fuel cell electrical energy obtained by cell (at 298 K) > | H ocombustion [CO (g) ]|
1
[Sol: CO ( g )  O 2( g ) 
 CO 2( g )
2
H  H P  H R
 1 
= [H CO 2 ]  H CO  H O 2 
 2 
= (–395) – [–110]
= –395 + 110
 = –285 kJ
S  SP  SR
 1 
= SCO 2  SCO  SO 2 
 2 
 1 
= 213  197   205
 2 
= 213 – 197 – 102.5
= –86.5 J
H  U  n g RT
1
= U  RT
2
1
H  RT  U
2
 H  U
for equilibrium G  H  T S
O  H  T S
H 285  103
T  = 3294.79 K.
S  86.5
H comb.of CO  285 kJ
Electrical energy obtained by cell at 298K  G
= H  T S
298  86.5
= 285 kJ  3
kJ  [285  103  298  86.5] = –[–285+25.77]
10
= + 259.23 kJ
 Electrical energy < Hcomb. ]

Q.25 Which of the following will give three different compounds on ozonolysis

(A) (B*) (C*) (D)

[Sol: (B)  + O=CH–CH=O +

Three difference products are

 (1) (2) (3)
(C) Three difference products are

Q.26 Potassium chromate solution is added to aqueous solutions of metal nitrate. The Yellow precipitate thus
obtained are insoluble in acetic acid. These are subjected to flame test, flame colour of individual ppt.
is/are
(A) Lilac (B*) Apple green (C) Crimson red (D*) Blue
Q.27 A compound 'A' transform by two parallel first order paths
1
A (g) k
1 (min )
 2B (g) k1 = 6.93 × 10–3 min–1
1
A (g) k 2 (min )
  C (g) k2 = 6.93 × 10–3 min–1
If reaction started with pure 'A' with conc. 0.1 mol/L in a closed container with initial pressure 2 atm.
What is the pressure (in atm) developed in container after 50 minutes from start of experiment.
(A) 1.25 (B) 0.75 (C*) 2.50 (D) none of these


Q.28 + PhN 2 Cl–  ? H3O

Final product is a mixture containing:

(A*) (B*) (C*) (D*)

[Sol: e.g. of N–N coupling

 
+ Ph  N  N 

Q.29 Which of the following aqueous solution of cation(s) give(s) white ppt with NaOH and NH4OH solution
and formed ppt. is/are further completely dissolved in one of the excess reagent.
(A*) Cd2+ (B) Cr3+ (C*) Sn2+ (D) Bi3+

Q.30 True statements regarding SN1 reaction is/are

(A) Perfect racemisation is observed
(B) Only Walden inversion is observed
(C) Total retention of configuartion is observed
(D*) None of these

Q.31 CO 32 and HCO 3 can be distinguished by

(A*) Phenolphthalein (B*) MgCl2 solution (C*) HgCl2 solution (D) KCl solution

SOCl
Q.32 2  (A)

Major product (A) is:

(A*) (B) (C) H2C = CH2 (D)

[Sol: SOCl
2 
S
Ni

R– R–
In S N i mechanism retention of configuration takes place ]
Q.33

Which of the following options is/are correct regarding ‘P’ among the following
(A*) O3 (B*) excess Cl2 water (C*) conc. HNO3 (D) HCl

Q.34 Which of the following is the chain termination step during photochlorination of ethane:
 
(A*) CH 3  CH 2  Cl  CH3–CH2–Cl
 
(B*) CH 3  CH 2  CH 3  CH 2  CH3CH2CH2CH3

 
(C*) Cl Cl  Cl2
 
(D) Cl H HCl
[Sol: In chain terminating step two free radical reacts. H0 is highly unstable. ]

Q.35 Which of the following properties show a similar trend on moving from Li to Cs within the group
(A*) Ionic mobility (B*) Reactivity towards water
(C) Solubility of Bromide salt (D*) Thermal stability of Carbonate salt

Q.36 Which of the following statements is / are true :

(A*) Major part of energy needed for the heterolysis of C–X bond in S N1 reaction mechanism is
obtained by the solvation of X– by the polar protic solvent.
(B) Greater solvation of attacking nucleophile & poor solvation of transition state promotes the reaction
by SN2 mechanism.
(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 they are primary halides which do not give SN1
reaction.
Q.37 Which of the following statement is incorrect.
(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 In the given reaction

C7H12 (A) HBr



(A) is:

(A*) (B*)

(C*) (D)
[Sol: (A) H
 
HBr

(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 of the following will give same product with HBr in presence & absence of peroxide
(A*) ethene (B) 1-butene (C*) 2-butene (D) isobutene
[Sol: Symmetrical alkane provide same product with HBr in presence & absence of peroxide.
Mechanism is free radical addition ]