Single option

1. The pH of 0.2 M NaHCO

3
solution at 25C is 9.2. A 22 mL. 2.0M solution of
2 3
H CO when treated
with 80 mL 0.5M NaOH results into formation of H
2
CO
3
-NaHCO
3
buffer with pH of 8.6. Hence
2
a
pK of H
2
CO
3
is
(A) 10.8 (B) 7.6
(C) 9.2 (D) 8.6
1. HCO3

ion is amphiprotic anion.

2
3 3
HCO H CO ;
+
+
2
a 2 3
K (H CO )

3 2 2 3
HCO H O H CO OH ;

+ +
1
w
a 2 3
k
K (H CO )

Na
+
ion is unhydrolysable. Hence pH of a solution of NaHCO3 is equal to
1 2
a a
1
[pK pK ]
2
+ , irrespective of the concentration of solution.
Thus,
1 2
a a
1
9.2 [pK pK ]
2
= +
The pH of H2CO3 - NaHCO3 buffer is given by the equation
pH =
1
a
[Salt]
pK log
[Acid]
+
From question
No. of m. mole of H2CO3 taken = 22 2 = 44
No. of m. mole of NaOH added = 80 0.5 = 40
No. of m. mole of NaHCO3 formed = 40
No. of m.mole of H2CO3 left out = 4
So 8.6 =
1
a
40
pK log
4
+

1 2
a a
pK 7.6 so pK 10.8 = =

2. An inorganic salt, when warmed with NaOH solution, gives off a gas that turns a filter paper
soaked with an alkaline solution of K
2
[HgI
4
] brown. After complete evolution of gas, the reaction
mixture when warmed with Al powder and NaOH solution a gas is evolved that gives white
fumes with a glass rod wet with HCl solution. The salt responds to the brown ring test when
acetic acid is used in place of conc. H
2
SO
4
. The cation and anion which may be present in the salt
are, respectively,
(A) NH
4
+
and NO
3

(B) NH
4
+
and NO
2

(C) Any cations and NO
3

(D) Any cation and NO

2

2. NH4
+
+ OH

H2O + NH3
NH3(g) turns Nesslers reagent brown
Al + 4OH

AlO2

+ 2H2O + 3e
NO3

+ 6H2O + 8e NH3 + 9OH

NO2

+ 5H2O + 6e NH3 + 7OH

NH3(g) gives white fumes of NH4Cl with HCl.
Ring test is responded with use of CH3COOH indicating thereby that it is NO2

ion rather
than NO3

. With conc. H2SO4, NO2

will get decomposed rapidly to give NO(g) which will

combine with atmospheric O2 to give brown fumes of NO2(g) thereby destroying the ring.
3.
24
12
Mg when bombarded with o-particle converts into a radioactive isotope of some element
with emission of neutron. The radioactive product so formed will disintegrate by
(A) |

- emission (B) |
+
- emission
(C) o - emission (D) neutronemission
3.
24 4 27 1
12 2 14 0
Mg Si n + o +

27 27 0
14 13 1
(stable)
Si Al e
+
+ i.e. |
+
4. The incorrect statement amongst the following is?
(A) Black phosphorous is thermodynamically most stable allotrope of phosphorous
(B) Fe(III) is thermodynamically more stable than Fe(II)
(C) Graphite is thermodynamically more stable than diamond
(D) White phosphorous is kinetically least stable allotrope of phosphorous and so is graphite in
comparison to diamond
(Note: All comparisons are in their respective standard states)
4. 2Fe
3+
+ Fe 3Fe
2+
, AG = ve
o
cell
E ve = +
More then one
1. The correct order of the properties as given in the parenthesis from among the following is
(are):
(A) Cl
2
> Br
2
> F
2
> I
2
(Bond energy)
(B) CH
3
Cl > CH
2
Cl
2
> CHCl
3
> CCl
4
(dipole moment)
(C) BeF
2
> NO
3

> I
3

> BrF
5
(s-character of hybrid orbital of central atom)
(D) BaCO
3
< SrCO
3
< CaCO
3
< MgCO
3
(thermal stability)
1. Thermal stability of metal carbonate decreases as ionic character decreases and
covalent character increases. So, D is incorrect. In Cl2 and Br2 there is pt - dt bonding
and hence their bond strength are greater than that of F2. The hybridization of the
central atom in BeF2, NO3

, I3

and BrF5 are sp, sp

2
, sp
3
d and sp
3
d
2
respectively.
2. Choose the correct statement(s) from among the following
(A) The corrected pressure P +
2
2
an
v
in vander waals equation (symbols have their usual
meanings) is the pressure which the gas would exert is it were ideal.
(B) Above their respective Boyles temperature, N
2
shows throughout positive deviation
(z > 1) while O
2
shows negative deviation (z < 1) followed by positive deviation
(z > 1).
(C) A gas shows negative deviation when long range attractive intermolecular forces are
dominating
(D) The intercept of PV vs. P isotherm of any gas at 27C is equal to 24.6 L atm mol
1
.
2. Choice (B) is incorrect as all the gases above their respective Boyles temperature
show throughout +ve deviation
Passage
A is a substance that converts into B, C and D by three first order parallel paths simultaneously
according to the following stoichiometry.
1/ 2
t 86.625 min. Path II
A 2C
=

Path III
D
Path I
B

The partial t
1/2
of A along path I and path II are 173.25 min and 346.5 min, respectively. The energies of
activation of the reaction along path I, path II and path III are 40 kJ mol
1
, 60 kJ mol
1
and 80 kJ mol
1

respectively.
64. The percent distribution of C in the product mixture B, C and D at any time is equal to
(A) 20 (B) 60
(C) 80 (D) 40
65. The initial rate of consumption of A and the sum of the initial rate of formation of B, C and D are
respectively, taking [A] = 0.25 M, equal to
(A) 2.0 10
3
mol L
1
min
1
and 2.5 10
3
mole L
1
min
1

(B) 2.0 10
3
mol L
1
min
1
and 2.0 10
3
mole L
1
min
1

(C) 2.5 10
3
mol L
1
min
1
and 3.0 10
3
mole L
1
min
1

(D) 4.0 10
3
mol L
1
min
1
and 2.0 10
3
mole L
1
min
1

66. The overall energy of activation of A along all the three parallel path is equal to
(A) 52 kJ mol
1
(B) 60 kJ mol
1

(C) 55 kJ mol
1
(D) 80 kJ mol
1
64. If k1, k2 and k3 be the rate constants of the reaction along path I, II and III respectively,
then overall rate constant of consumption of A will be k1 + k2 + k3. So
86.625 min. =
1 2 3
0.693
k k k + +

So, k1 + k2 + k3 =
3 1
0.693
8 10 min
86.625

=
k1 =
3 1
0.693
4 10 min
173.25

=
k2 =
3 1
0.693
2 10 min
346.5

=
Hence k3 = 8 10
3
2 10
3
= 2 10
3
min
1

% distribution of C =
3
2
3
1 2 3
2k 2 2 10
100 40
k 2k k 10 10

= =
+ +

65.
1 2 3
d[A]
(k k k )[A]
dt
= + +
= 8 10
3
0.25 = 2 10
3
mol L
1
min
1


1 2 3
d[B] d[C] d[D]
k [A] 2k [A] k [A]
dt dt dt
+ + + = + +
= (k1 + 2k2 + k3) [A]
= (4 10
3
+ 2 2 10
3
+ 2 10
3
) (0.25)
= 2.5 10
3
mole L
1
min
1

66.
3 1 2
a a a(2) a(3)
1 2 3 1 2 3 1 2 3
k k k
E E (1) E E
k k k k k k k k k
= + +
+ + + + + +

= 0.5 40 + 0.25 60 + 0.25 80
= 20 + 15 + 20
= 55 kJ mol
1


Single integer type

14)
16)
In alkaline medium
2 2 7
K Cr O reacts with 30%
2 2
H O and forms a red-brown complex
compound. The oxidation state of Cr is + n in that complex. Then n value is.



17) The presence of nitrate ion is detected by brown ring test. The number of unpaired
electrons present at the metal ion in that complex is.
Ans 3