PART-A

Select the correct alternative. (More than one are correct) [3 × 5 = 15]

Q.4 Which of the following is/are wrong:

(A*) MeCO – NH2 gives bad smelling substance with CHCl3 KOH
(B*) Phenol reacts with CCl4 in presence of NaOH to give salicylic acid, carbene is the intermediate
formed during this reaction
(C*) Carbene is the real attacking intermediate in Simmon Smith reaction
(D*) Ethylmethanoate reacts with excess of methyl magnesium bromide, followed by hydrolysis
to produce a 3° alcohol.

Q.5 Which is correct statement(s)?

(A*) [Ag(NH3)2]+ is linear with sp hybridised Ag+ ion
(B*) NiCl 24 , VO34 and MnO 4 have tetrahedral geometry
(C*) [Cu(NH3)4]2+ , [Pt(NH3)4]2+ & [Ni(CN)4]2– have dsp2 hybridisation of the metal ion
(D*) Fe(CO)5 has trigonal bipyramidal structure with d 2 sp3 hybridised iron.
z

Q.6 Which of the following will decolourise bromine water

(A*) CH2 = CH2 (B*) HC  CH (C) (D)

 PART-B
MATCH THE COLUMN [2 × 8 = 16]
There is NEGATIVE marking. 0.5 mark will be deducted for each wrong match within a question.
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 entries of column-II and one entry of column-I may have one or more than one matching
with entries of column-II.

Q.3 Column I Column II

(Pair of complexes) (Property which is similar in given pair)
(A) [Fe(CN)6]3– & [Co(NH3)6]2+ (P) Magnetic moment
(B) [Fe(H2O)6]2+ & [Fe(CN)6]4– (Q) Geometry
(C) [Ni(CN)4]4– & [Ni(CO)4] (R) Hybridisation
(D) [Ni(H2O)6]2+ & [NiCl4]2– (S) Number of d-electrons
[Ans. (A) P, Q, R (B) Q, S (C) P, Q, R, S (D) P, S ]

Q.4 Column-I (Carbanions) Column -II (Half lives)

(a) (P) 4.3 × 10–8 s

(b) (Q) 2.5 × 10–5 s

(c) (R) 8.7 × 10–7 s

(d) (S) 1.4 × 10–4 s

[Ans. (A) R, (B) S, (C) Q, (D) P ]

 PART-C
Q.6 The vapour pressure of water at 310 K is 25 torr. If the standard state pressure is defined as 1 bar
(750 torr) estimate the G° [in kJ/mol] for the process.
H2O (l)  H2O (g) at 310 K
(Neglect variation of H and S with pressure for liquid)
ln X
Use [R = 8.3 JK–1 mol–1 ; log X = 2.3, log 3 = 0.48] [6]

[Ans. 8.76]
[Sol. G=0
H2O (l) 310  H2O (g) ; 310 K
25 torr  25 torr

(310 K ; 750 torr) H2O (l) 310 K H2O(g) (310 K ; 750 torr)
 25 
G° = – TS = – T R ln  
 750 
 1 
= – 310 × 8.3 × 2.3 × log  
 30 
= 310 × 8.3 × 2.3 {1.48}
= 8.76 K Joule Ans. ]

Q.7 The ratio of activities of two radionuclides X and Y in a mixture at time t = 0 was found to be
8 : 1. After two hour's, the ratio of activities become 1 : 1. If the t 1/2 of radionuclide X is 20 min.
find the t1/2 [in minutes] of radionuclide Y. [6]
[Ans. 40]
A XO 8
[Sol. =
A YO 1

AX = A XO e   x t
 y t
AY = A YOe

AX 1 ( X X ) t
AY = = 8e y x
1
1 ( X X ) t
=e y x
8
1
ln   = (y – x) t
8

 ln 2 
3 ln 2 =    120
 20 

1  1 1 
=  20  t 
40  1/ 2 

 t1 / 2  20 1
20 t1 / 2 =
40
2t1/2 – 40 = t1/2
(t1/2)y = 40 ]

Q.8 Equimolar mixture of two gases A2 and B2 is taken in a container of volume 'V' at temperature
300 K. At constant temperature the gases reacts according to given equations:
A 2 (g) l 2A (g) kp = ?
B2 (g) l 2B (g) kp = ?
A2 (g) + B2 (g) l 2AB kp = 2 atm
If the initial pressure in the container was 2 atm and final pressure developed at equilibrium is
2.75 atm in which equilibrium partial pressure of gas AB was 0.5 atm, find equilibrium constant
kp for the reaction.
AB (g) l A (g) + B (g)
(Temperature & Volume of container remain constant throughout the experiment). [8]
[Ans.1]
[Sol. Initial partial pressure of A2 and B2 1 atm each.

A 2 (g ) B2 (g) A(g) B(g) AB(g)

Initial 1 1
Change  x  y 2x 2y  2z
z z
At eq. 1  x  z 1  y  z 2x 2y 2z
3 3
x y 2x 2y 0.5
4 4

1+ 1 + x + y = 2.75  x + y = 0.75 .....(1)

2z = 0.5  z = 0.25 .....(2)
2
1
 
2
PAB 2
also =2  3  3  =2
PA ; PB   x   y
2 2
4  4 
(3 – 4x) (3 – 4y) = 2 .....(3)
Putting value of x from (1) in (3)
(4y) (3–4y) =2
12y – 16y = 2
6y – 8y2 =1
 1 1
y  , 
 2 4
1 1
taking y = x=
2 4

1
  (1)
2
Kp = = 1 atm Ans. ]
1
2
Q.9 A cylindrical container of volume 4.48 litres is containing equal no. of moles of a monoatomic
gas in two sections A and B separated by an adiabatic frictionless piston as shown in figure. The
initial temperature and pressure of gases was 273 K and 1 atm. Now gas in section 'A' is slowly
heated till the volume of section B becomes 1/ 2 2 of initial volume. Find total change in H for
section A and B. (in cal/mole) [Cv of monoatomic gas = 3/2 R,  = 5/3 ]

[Use R = 2 cal/mol & 2 = 1.4] [8]

[Ans. 753.48]
[Sol. Initial volume of sec. A = sec. B = 2.24 litres
 2.24 
Final volume of sec. B =   litres
2 2 
The gas in sec.'B' compressed reversibly and adiabatically
r 1
 V1 
 T1V1 1 = T2 V2 1  T2 = T1  
 V2 
 
 T2 = T 1 2 2
2/3
= 2T1

5
{For monoatom gas  = }
3
The final pressure in sec. 'B'
P1V1 T2  T2   V1 
Pf = T , V = P 1 ×   . 
 T   V  P1 ×2× 2 2 = 4 2 atm
1 2  1  2

 Pressure in sec. 'A' = 4 2 atm

 P2   V2 
 Final temperature in sec. A T2 =  P   V  T1
 1  1 

 V1 
 P2   V1  V1  2 2 
T2 =  P    T1
 1 V1 
 

 1 
4 2 2  T
 2 2 1

 ( 4 2  1) ( 4 2 ) 
=   T1
 2 2 
( 4 2  1) 2T1
 
[8 2 T1  2T1  T1 ] = 4 2 T1  3T1 
HA = (0.1)
3
2

R 8 2 3 
3
HB = (0.1) R {273}
2
2( 4 2  1)
3
HT = (0.1) R (273) {2} ( 4 2  1) = 753.48 Ans.]
2
Q.10 For the reaction,
Cl2O (g) + H2O (g) l 2HOCl (g) : Kp = 0.1 at 300 K
º
The value of equilibrium constant is 0.1. From the given data, find H f [HOCl (g ) (in kJ/mol).
(All data given at 300 K)
H of [Cl2O(g)] = + 77 kJ/mol

H of [H2O(g)] = –242 kJ/mol

 r So = 15.91 J/K mole

ln X
Take [R = 8.3 JK–1 mol–1 ; log X = 2.3] [8]

[Ans. 77.25 kJ / mole]

[Sol. G° = – RT ln Kp
= 8.3 × 300 × 2.3 [log 0.1]
G° = + 8.3 × 300 × 2.3 = H° – TS°
H° = {8.3 × 2.3 + 15.91} × 300
= 35 × 300
H° = 10.500 kJ
H f (Cl 2 O)  H f [H 2 O(g)]  10.500
H fº [HOCl (g ) = | |
2
77  242  10.5
=| |
2
= 77.25 kJ /mole ]
 PART-D

Q.1 A gaseous compound 'A' reacts by three independent first order

processes (as shown in figure) with rate constant 2 × 10 –3, 3 × 10–3
and 1.93 × 10–3 sec–1 respectively for products B, C and D respectively.
If initially pure 'A' was taken in a closed container with P = 2 atm, find
the partial pressure of 'B' (in atm) after 100 sec from start of experiment. [6]
[Ans. 2.88 × 10–1]
[Sol. Overall rate constant = k = k1 + k2 + k3 = 6.93 × 10–3
0.693
t1/2 = = 100 sec
6.93 103
After one t1/2 PB + PC + PD = 1 atm
PB k1 200
PB  PC  PD = k k k =
1 2 3 693
200
PB = 1 × = 2.88 × 10–1 ]
693
k
Q.2 The kinetic data for the given reaction A (aq) + 2B (aq) 
 C is provided in the following table
for three experiments at 300 K

Ex. No. [A / M ] [B / M ] Initial rate (M sec 1 )

1 0.01 0.01 6.930 10 6
2 0.02 0.01 1.386  10 5
3 0.02 0.02 1.386  10 5
In another experiment starting with initial concentration of 0.5 and 1 mole respectively for A & B
at 300 K, find the rate of reaction after 16.667 minutes from start of experiment in (M/sec).
[8]
[Ans. 1.73 × 10–4]
[Sol. a b
r1 = k [0.01] [0.01] = 6.93 × 10 6 .....(1)
a b
r2 = k [0.02] [0.01] = 1.386 ×10 –6 .....(2)
r3 = k [0.02]a [0.02]b = 1.386 × 10–6 .....(3)
(0.02)a = 2  a = 1
(0.02)b =1  b = 0
 k = 6.93 × 10–4 sec–1
A + 2B  P
0.5 1  overall order = 1
3 Ao
6.93 × 10–4 = ln A
50  60 t

Ao Ao
0.693 = ln A  A = 2  At = 0.25
t t

1
 rate = 6.93 × 10–4 ×  
4
rate = 1.73 × 10–4 M sec–1 Ans. ]