[1]

XIII (VXY) PHYSICAL CHEMISTRY

ANSWER KEY
PART TEST-1
SITTING -1
Q.1 A Q.2 C Q.3 C Q.4 A Q.5 D Q.6 D Q.7 A
Q.8 D Q.9 B Q.10 B Q.11 C Q.12 B Q.13 A Q.14 D
Q.15 C Q.16 B Q.17 0.25 L Q.18 FeO = 19.15% , Fe
2
O
3
= 80.85%
Q.19 0.04 M Q.20 10.625% Q.21 1148 Q.22 12.50 mL
SITTING -2
Q.1 B Q.2 C Q.3 B Q.4 D Q.5 B Q.6 C Q.7 A
Q.8 B Q.9 D Q.10 B Q.11 B Q.12 C Q.13 A Q.14 B
Q.15 C Q.16 A Q.17 ABCD Q.18 (A) S (B) T (C) P,Q (D) R
Q.19 6225 Q.20 8 Q.21 0.70 atm Q.22 30 Q.23 4 Q.24 10
Q.25 3.4 Q.26 4856 Q.27 80 Q.28 400 Q.29 102
SITTING -3
Q.1 D Q.2 A Q.3 C Q.4 C Q.5 D Q.6 C Q.7 B
Q.8 A Q.9 A Q.10 D Q.11 A Q.12 A Q.13 D Q.14 D
Q.15 C Q.16 D Q.17 B Q.18 B Q.19 ABC Q.20 ABC
Q.21 (A) P, (B) P,Q,R (C) P,Q,R,S Q.22 130 kJ/mole
Q.23 AS
system
11.52 J/K, AS
surrounding
= 11 J/K Q.24 5
[2]
SOLUTION
SITTING -1
Q.1 Total moles of KI
166
8 . 49
= 0.3
AgNO
3
+ KI AgI + KNO
3
2KI + KIO
3
+ 6HCl 3ICl + 3KCl + 3H
2
O
10 ml of 0.1 M KIO
3
reacted with KI
no. of milli moles of KI in 20 ml = 10 0.1 2 = 2
No. of m. moles of KI present in 2000 ml solution 2
20
2000
200 or 0.2 mole
Moles of KI reacted with AgNO
3
= 0.3 0.2 = 0.1 mole
Molarity of AgNO
3
solution
5 . 0
1 . 0
0.2
Q.2 2.22 ml CaCl
2

2 mg CaCO
3
1.9 ml MgCl
2

2 mg CaCO
3
Total CaCO
3
= 4 mg
ppm =
6
3
3
10
10
10 4

= 4 ppm
Q.3 50 meq. KMnO
4
= 50 meq. O
2
(n = 2) = 25 m mole = 25 22.4 10
3
= 0.56 L
Q.5 C
8
H
18
+ 12.5 O
2
8CO
2
(g) + 9H
2
O (l)
M(C
8
H
8
) = 114
wt. in gm of octane = 1.425 10
3
0.8 = 1140 gm
number of moles of octane = 10
O
2
needed = 10 12.5 = 125 moles
Q.6 C
n
H
2n+2
+
|
.
|

\
| +
2
1 n 3
O
2
nCO
2
+ (n+1) H
2
O
P
|
.
|

\
| +
2
1 n 3
P nP (n+1) P
increase in pressure
= P (

|
.
|

\
| +
+
2
1 n 3
1 ) 1 n 2 (
=
|
.
|

\
|
2
1 n
P
546 K and 4.6 atm 273 and 2.3 atm
Increase in pressure = 0.3 atm
P =
V
nRT
=
M
6 . 11

|
.
|

\
|

4 . 22
273
273
4 . 22
|
.
|

\
|
2
1 n
) 2 n 14 (
6 . 11
+
= 0.3
[3]
|
.
|

\
|
+

2 n 14
1 n
=
6 . 11
6 . 0
=
58
3
58 n 58 = 42 n + 6
16 n = 64 n = 4 C
4
H
10
Ans.
Q.7 K
2
Cr
2
O
7
+ X
+n

+
3
5
O X + Cr
+3
n = 6 n = (5 n)
6 10
3
6 = (5 n) 9 10
3
n = 1
Q.8 Let the moles of NaHC
2
O
4
be a and that of KHC
2
O
4
H
2
C
2
O
4
be b and volumes of each consumed
be V litre.
when KMnO
4
used : 0.2 V = 2a + 4b ....(1)
when NaOH used : 0.12 V = a + 3b ....(2)
from (1) and (2) a = 0.06 V ; b = 0.02 V
b
a
=
1
3
Ans
Q.9 meq. of Na
2
S
2
O
3
= meq of I
2
= meq of Cu
2+
10 = meq of Cu
2+
= m moles of Cu
2+
(n = 1)
molarity =
100
10
= 0.1
Q.10 1.5 10
3
(102x) = 0.03 5
1000
40
x = 3
Q.11 +4 +5 +6 0
(a)
2
3
SeO +

3
BrO + H
+

2
4
SeO
+ Br
2
+ H
2
O
+5 +3 1 +5
(b)

3
BrO +

2
AsO
+ H
2
O Br +
3
4
AsO
+ H
+
In reaction (b)
gm eq. of

3
BrO = gm. eq. of

2
AsO
2 n 6 n
2 3
AsO BrO
=

=
2
25
1
1000
5 . 12

= 10
3
6
10
n
3
BrO
3

In reaction (a)
moles of

3
BrO consumed =
6
10
60
1
1000
70
3
= 10
3
gm eq. of
2
3
SeO = gm. eq. of

3
BrO
5 10 2 n
3
SeO
2
3
=

3
SeO
10 5 . 2 n
2
3

=
Ans.
Q.12 Fe
0.93
O
1.00
Let number of moles of Fe
+2
= x moles
and number of moles of Fe
+3
= (0.93 x) moles
2x + 3 (0.93 x) = +2
On solving , x = 0.79
% of Fe
+2
=
93 . 0
79 . 0
100 = 85 % Ans.
Q.13 C
2
H
2
+
2
5
O
2
2CO
2
+ H
2
O
2 mol 5 mol
C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O
1mol 3 mol
CH
4
+ 2O
2
CO
2
+ 2H
2
O
2 mol 4 mol
Total moles of O
2
required = 12 mol
& moles of N
2
= 12
20
80
= 48 mol
16 2 28 1 26 2
28 48 32 12
n hydrocarbo of Mass
air of Mass
+ +
+
=
112
1728
32 28 52
1344 384
=
+ +
+
Ans.
Q.14
x 18 254 24
055 . 1
+ +
x 18 = (1.055 0.695) x = 8 Ans.
[5]
Q.15 3 40 gm NaOH present in 1000 gm water
total wt. of solution = 1000 + 120 = 1120 gm
Volume of solution = 1120/1.1 = 1018.18 ml
Molarity =
litre lution in vol. of so
es of Neon no. of mol
= 1000
18 . 1018
3
= 2.94 M
Q.17 MnO
2
(s) + 4HCl (aq.) MnCl
2
(s) + Cl
2
(g) + H
2
O (l)
No. of moles of HCl = 0.1 0.4 = 0.04
No. of moles of Cl
2
produced =
4
04 . 0
71 0.71 g
Volume of Cl
2
produced
84 . 2
71 . 0
0.25 litre
Q.18 meq of FeO = meq of KMnO
4
= 0.25 100 5
mmol of FeO =
1
5 100 25 . 0
total meq of Fe
+2
= 1000 0.1 6
total mmol of Fe
+2
=
1
6 1 . 0 1000
(from FeO and Fe
2
O
3
after reaction with Zn dust)
mmol of Fe
+2
from Fe
2
O
3
=
1
6 1 . 0 1000

1
5 100 25 . 0
= 475
mmol of Fe
2
O
3
=
2
475
mmol of FeO = 125
wt of FeO =
1000
) 16 56 ( 125 +
gm = 9 gm
wt. of Fe
2
O
3
=
1000
160
2
475

= 38 gm
% FeO =
9 38
9
+
100 = 19.15%
% Fe
2
O
3
= 100 19.15 = 80.85%
Q.19 224 moles CO
2
at STP = 0.01 moles CO
2
(i) if NaOH is limiting Na
2
CO
3
+ NaHCO
3
= 0.01/L
(ii) if NaOH is in excess Na
2
CO
3
= 0.01 moles/L, NaOH = y moles
Volume of HCl used with ph as indicator = 30
m moles of HCl = 0.3 NaOH is present in excess
m eq of HCl = m eq of Na
2
CO
3
+ m eq of NaOH
0.3 = 0.1 + m eq of NaOH
M eq of NaOH = 0.2 m eq = 0.2 m mole
Na
2
CO
3
= 0.1 m mole 0.2 m mole NaOH used in reaction
3 2 2
CO Na CO NaOH 2 +
Total NaOH originally present = 0.4 m mole in 10 ml
0.04 M Ans.
[6]
Q.20 m moles of KBrO
3
= 1.25 m moles (limiting)
m moles of Br

=
119
2000
= 16.80 m mole (excess)
Total m moles of Br
2
produced = m moles of KBrO
3
3 = 3 1.25 = 3.75 m moles
m moles of Br
2
(unused) = m moles of I
2
=
2
hypo of eq m
=
2
5 . 2
= 1.25 m moles
m moles of Br
2
used with HOQL = 2.50
m moles of HOQL =
|
.
|

\
|
2
50 . 2
m moles
Now m moles of Al
3+
=
3
HOQL of moles m
=
3 2
50 . 2

m moles
m moles of Al
2
O
3
=
2 6
50 . 2

m moles =
3
10 102
12
50 . 2


gm
% = 100 10
2 . 0 12
102 50 . 2
3

)
`

= 10.625% Ans
Q.22 Normality of chromic acid = 0.5 3 = 1.5 N
Normality of KI = 1N (From third experiment)
Ist flask: meq of KI left = 10 1.5 = 15
meq of KI = H
2
O
2
= 20 15 = 5
Initial meq of H
2
O
2
= 20
6 . 5
8 . 2
= 10 k = ln
5
10
; k = 0.693
IInd flask: Let x meq of H
2
O
2
left undecomposed.
3k = ln
x
10
ln(2)
3
= ln
x
10
; x = 1.25 = meq of KI consumed
meq of KI reduced with chromic acid = 201.25 = 18.75
18.75 = 1.5 V
V = 12.50 mL
Vol. of chromic acid required = 12.50 mL
[7]
SITTING -2
Q.1
w
a
K
K
= 10
10
CH
3
COOH + OH CH
3
COO + H
2
O
Q.2 pH = pK
In
+ log
] HIn [
] In [
s
pH = pK
In
+ log
] HIn [
] In [
s
= 5.3 + (1.30) = 4 = 5.3 + 1.60 = 6.9
Q.3 [H
+
] =
a
cK
4 10
4
=
a
K 2 . 0
16 10
8
= 0.2 K
a
K
a
= 80 10
8
= 8 10
7

A
b
) K (
=
a
w
K
K
=
7
14
10 8
10

= 1.25 10
8
Q.4 Ag
2
CrO
4
2Ag
+
+ CrO
4
2
10 mmol 80 mmol
5 0 75
500
x
500
75
then |
.
|

\
|
|
.
|

\
|
500
75
500
x
2
= 15 10
12
500
x

= 10
5
x = 5 10
3
[Ag
+
] =
500
10 5
3

= 10
5
Ans.
Q.5 5 = pK
b
+ log
25 . 0
] NH [
4
+
[NH
4
+
] = 0.5
[NH
3
] = 0.25
m moles of KOH added = 50
NH
4
+
+ OH NH
3
+ H
2
O
100 50 50
[8]
50 0 100
pOH = pK
b
+ log
100
50
pOH = 4.7 0.3 4.4
pH = 9.6 Ans.
Q.6 AgA(s) Ag
+
(aq) + A (aq)
x xy
AgA(s) + H
2
O (l) HA(aq) + OH(aq)
xy y y
K
sp
= x (x y)
K
h
=
) y x (
y
K
K
2
a
w

=
) y x (
) 10 (
10
10
2 5
10
10

x y = 10
6
x

= 10
5
+ 10
6
x = 1.1 10
5
K
sp
= 1.1 10
5
10
6
K
sp
= 1.1 10
11
Ans.
Q.7 Glycinium hydrochloride is a dibasic acid
(
+
3
NH CH
3
COOH)
pH at first half equivalence point = pK
1
pH at 2
nd
half equivalence point = pK
2
pH at first equivalence point
pH =
2
pK pK
2 1
+
= pH of isoelectric point
=
2
60 . 9 34 . 2 +
= 5.97 Ans.
Q.8 pH =
2
a
pK
+ log
] HCO [
] CO [
3
2
3

(11 log 4) + log

|
.
|

\
|
2
1
10.1
Q.9 Ag
2
CrO
4
(s) 2Ag
+
(aq) +
2
4
CrO (aq)
2x + 2y x
Ag
2
C
2
O
4
(s) 2Ag
+
(aq) +
2
4 2
O C (aq)
2y + 2x y
2
1
sp
sp
K
K
=
y
x
=
11
12
10 2
10 2

y
x
= 0.1
2 10
11
= (2x + 2y)
2
.y
[9]
= (2.2y)
2
.y 2 10
11
= 4.84 y
3
y = 1.6 10
4
x = 0.16 10
14
Total (Ag
+
) = 2x + 2y = (2 0.16 + 2 1.6) 10
4
= 3.52 10
4
Ans.
Q.11 N
2
O
4
(g) 2NO
2
(g)
at P
1
(t=Eq) 10.4 2(0.4)
= 0.6 = 0.8
at P
2
(t=Eq) 10.5 2(0.5)
= 0.5 =1
temperature is same , K
P
is same
1
2
1
P
4 . 1
6 . 0
P
4 . 1
8 . 0
|
.
|

\
|
=
|
.
|

\
|
|
.
|

\
|
2
2
2
P
5 . 1
5 . 0
P
5 . 1
1
5 . 0 5 . 1 ) 8 . 0 (
6 . 0 4 . 1
P
P
2
2
1

=
=
4
7
Q.12
2
10
9
1

= K
C
[0.08 500]
2
2
10
9
1

= K
C
(40)
2
40 40
K
100 9
1
C

K
C
=
9
16
Q.14 Balamed chemical equation is
3I
2
(s) + 6 OH

(aq) 5I

(aq) + IO

3
(aq) + 3H
2
O(l)
AG = 5 ( 50) + ( 123.5) + 3 ( 233) 0 6 ( 150) = 172 . 5 kJ/ mol
Q.15 AG = 2.3 RT log k = 172.5 10
3
J/mol
2.3
3
25
300 log k = 172.5 10
3
log k = 30
k = 10
3
[10]
Q.16 k =
6
3
5
] OH [
] IO [ ] I [

= 10
3

6
5
] OH [
] 1 . 0 [ ] 1 . 0 [

= 10
30
[OH

] = 10
6
M pOH = 6 pH = 8
Q.19 AG = AG + RT ln Q
AG = RT ln K
eq
+ RT ln Q
AG = RT ln
eq
k
Q
... (1)
A + B
k
f
k
b
P
At time t
t t
t
] B [ ] A [
] P [
Q = ... (2)
Given 12
r
r
b
f
= ,
] P [ k
] B [ ] A [ k
b
f
= 12
b
f
t t
t
k 12
k
] B [ ] A [
] P [
=
Putting value of Q & K
eq
in equation (1)
Ag = RT ln
f
b
b
f
k
k
k 12
k

Ag = RT ln 12 = 6225
Q.20 Initial partial pressure of A
2
and B
2
1 atm each.
5 . 0 y 2 x 2 y
4
3
x
4
3
z 2 y 2 x 2 z y 1 z x 1 . eq At
z 2 y 2 x 2
z
y
z
x
Change
1 1 Initial
) g ( AB ) g ( B ) g ( A ) g ( B ) g ( A
2 2


+

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

2z = 0.5 z = 0.25 .....(2)
also
2 2
B A
2
AB
P ; P
P
= 2
|
.
|

\
|

|
.
|

\
|

|
.
|

\
|
y
4
3
x
4
3
2
1
2
= 2
(3 4x) (3 4y) = 2 .....(3)
[11]
Putting value of x from (1) in (3)
(4y) (3 4y) =2
12y 16y = 2
6y 8y
2
=1
)
`

=
4
1
,
2
1
y
y > x
y =
2
1
x =
4
1
;
5 . 0
) 5 . 0 (
) 5 . 0 (
) x 75 . 0 (
) x 2 (
P
P
K
2 2
A
2
A
P
2
1
= =

= =
4
25 . 0
1
) y 75 . 0 (
) y 2 (
P
P
K
2 2
B
2
B
P
2
2
= =

= =
5 . 0
4
K
K
1
2
P
P
=
8
Q.21 2AB(s) A
2
(g) + B
2
(g)
0.5 + x x
K
p
=
2 2
B A
P . P
0.06 = (0.5 + x) x
x
2
+ 0.5 x 0.06
x =
2
) 06 . 0 ( 4 ) 5 . 0 ( 5 . 0
2
+

2
7 . 0 5 . 0 +
0.1
P
total
=
2 2
B A
P P +
0.6 + 0.1
0.70 atm
Q.22 SO
3
(g) SO
2
(g) +
2
1
O
2
o =
) 1 n ( d
d D

3
2
=
|
.
|

\
|

1
2
3
d
d 40
d = 30
Q.23 Since mixture is in contact with liquid water, then at equilibrium the partial pressure of water vapour will
be equal to 380 torr.
1 atm 0.25 atm 1 atm 1 atm
4NO
2
(g) + 2H
2
O(g) + O
2
(g) 4HNO
3
(g)
(1x)atm
2
1
atm
|
.
|

\
|

4
x
1
atm (1 + x)atm
[12]
K
P
is very large, so reaction will occur almost completely in forward direction and very small amount
of limiting reagent (NO
2
) will be present at equilibrium. The maximum value of x can be 1
So, K
p
=
|
.
|

\
|

+
4
x
1 ) 5 . 0 ( ) x 1 (
) x 1 (
2 4
4
x ~ 1
So 1 x = very small number = A
So, K
P
=
12
4
8
2 2 4
4
10
3 A
2
) 75 . 0 ( ) 5 . 0 ( A
2
=

A
4
=
12
8
10 3
2

A =
4 / 1
3 2
3
10 2

= 4 atm Ans. ]
Q.24 o is neglible w.r.t 1
[H
+
] mainly from first step
[H
+
] =
C K
1
a


1 . 0 10
5

= 10
3

3
a
K
=
] HA [
] A ][ H [
2
3

+
10
13
=
] HA [
] A [ 10
2
3 3

X =
] HA [
] A [
2
3

= 10
10
pX = 10
Q.25 1 10
3
+ 2 10
4
= 3 [H
+
]
10
3
+ 0.2 10
3
= 3 [H
+
]
[H
+
] =
3
10 2 . 1
3

= 0.4 10
3
= 4 10
4
pH = log [H
+
] = 4 log 4 = 4 0.6 = 3.4
Q.26 Minimum ] CO [
2
3

needed for ppt. of MgCO

3
=
] Mg [
) MgCO ( K
2
3 sp
+
=
1 . 0
10 4
8

= 4 10
7
M
Now, H
2
CO
3
2H
+
+ CO
3
2
K
a
=
] CO H [
] CO [ ] H [
3 2
2
3
2 +
[13]
or , [H
+
]=
] CO [
] CO H .[ K
2
3
3 2 a
=
7
17
10 4
05 . 0 10 5

= 2.5 10
6
M
Hence, pH = log (2.5 10
6
) = 5.6
Hence, MgCO
3
will not ppt below pH = 5.6
Similarly, minimum [CO
3
2
] needed for ppt of SrCO
3
=
] Sr [
) SrCO ( K
2
3 sp
+
=
1 . 0
10 9
10

= 910
9
M
[H
+
] =
9
17
10 9
05 . 0 10 5

=
5
10
3
5

M
pH = log
|
.
|

\
|

5
10
3
5
= 4.8
Hence, SrCO
3
will not ppt below pH = 4.8
Hence, range of pH for only the ppt of SrCO
3
= 4.8 to 5.6 Ans. 4856
Q.27 pH = pK
a
= 5
9 = 7 +
2
1
5 +
2
1
log C = 0.l M
Let V ml of NaOH is used
1 . 0
60 V
V 25 . 0
=
+
V = 40 ml
weight of acid = 0.25
1000
40
82 = 0.82 gm
Q.28 At equivalence point [Ag
+
] = =
sp
K 10
5
10
10
[CrO
4
2
] = 4 10
12
[CrO
4
2
] = 4 10
2
= 0.04 M
Q.29 CH
3
COOH CH
3
COO + H
+
1 0 0
1o o o
K
a
=
) 1 (
2
o
o
o << 1
o =
a
K
[H
+
] =
a
K pH = log [H
+
] = log K
a
1/2
=
2
pK
a
[14]
Equimolar mixture of CH
3
COOH and CH
3
COONa

solution Buffer Acidic
pH = pK
a
+ log
] Acid [
] Salt [
pH = pK
a
+ log 1
pH = pK
a

) COONa CH COOH CH (
COOH CH
3 3
3
pH
pH
+
=
2
1
pK
2 / pK
a
a
=
[15]
SITTING -3
Q.1 AU = q + w
q = w
q
I
= ( nRT ln
1
2
V
V
) = nRT ln
1
2
V
V
= P
i
V
i
ln 10
= 2.303 10 1
q
II
= (w) = 13 -atm
II
I
q
q
=
13
10 303 . 2
=
13
03 . 23
Ans.
Q.4
|
|
.
|

\
|
2
1
V
V
=
1
1
1
2
T
T

|
|
.
|

\
|
= (3)
3/2
= 8

|
|
.
|

\
|
=
1
1
2
2
1
T
T
P
P
= 3 / 2
3 / 5
) 3 (
= (3)
5/2
=
32
1
Q.5 AE = q + w
= 100
18 . 4
209
= 100 50
50 cal
AE = nC
v,m
AT ; q = n C
m
AT
m , v
m
C
C
E
q
=
A
; C
m
= 2 C
v,m
5 R Ans
Q.6 AH
vaporisation
= 300 30 J/mol
AS
condensation
=
int po boiling
on vaporisati
T
H A

300
30 300
J/mol.K 30 J/mol.K Ans.
Q.7 For given reaction AU = q + w 500 350
AU = 150 kJ Ans.
Q.8 A
r
G = A
r
G + RT ln Q
p
A
r
G = A
r
H T A
r
S 2 90.5
1000
) 190 205 210 2 ( 300
= 173.5 kJ/mol
[16]
A
r
G = 173.5 +
1000
5750
log
) 10 )( 10 (
) 10 (
2 4
2 5

A
r
G = 150.5 kJ/mol Ans.
Q.9
0
200
G A =
0
200
H A T
0
200
S A
0
200
H A = 20 4 = 16 kJ/mole
0
400
H A =
0
200
H A +
1000
200 20
kJ/mole
= 16 + 4 = 20 kJ/mole
Q.10 C
v
(T
h
T) = C
v
(TT
c
) T =
2
T T
h c
+
; AS =
}
2
1
T
T
v
T
dt C
AS
c
= C
v
ln
c
T
T
& AS
h
= C
v
ln
h
T
T
Total AS = C
v
ln
( )
c
h c
T 2
T T +
+ C
v
ln
( )
h
h c
T 2
T T +
= C
v
ln
( )
h c
2
h c
T T 4
T T +
Q.14 NH
4
CN + H
2
O NH
4
OH + HCN
A
solution
H = A
Nent.
H
=
| |
) O H ( f ) HCN ( ion ) OH NH ( ion
2 4
H H H A + A + A
= [ 7 + 8 57.3]
= [ 42.3]
= + 42.3 kJ/mol.
Q.15 C +
2
1
O
2
CO ; 25 Kcal
C + O
2
CO
2
; 75 Kcal
(A) C +
2
1
O
2
CO
Initial moles 10 4.5
final moles 1 9
heat evolved = 9 25 = 225 Kcal
(B) C + O
2
CO
2
initially
12
24
= 2
32
64
= 2
heat evolved = 2 75 = 150 Kcal
(C) C +
2
1
O
2
CO
[17]
initially 4 2
finally 4
CO +
2
1
O
2
CO
2
Initial moles 4 1.5
final moles 1 3 ; moles of CO
2
produced = 3 and moles of CO produced = 1
heat evolved = 3 75 + 1 25 = 250 Kcal
(D) C + O
2
CO
2
initially 2.5 2.5
finally 2.5
heat evolved = 2.5 75 = 187.5 Kcal
Q.16 An
g
=
2
3

; AH = AU + An
g
RT
AU AH = An
g
RT =
|
.
|

\
|

2
3
2 300 0.9 Kcal Ans
Q.17 6C (s) + 3H
2
(g) C
6
H
6
(g)
AH
Th
= 6 AH
sub
+ 3E
HH
3E
C=C
3E
CC
6E
CH
= 216
AH
Actual
AH
Theo.
= R.E
R. E. = 358 + 216 = 142 kJ/mol
Q.18 No. of moles of H
2
O = No. of moles of CaO = No. of moles Ca(OH)
2
produced = 500/18
CaO + H
2
O Ca(OH)
2
Total heat released =
1000 2 . 65
18
500

J
Mass of Ca(OH)
2
produced =
74
18
500

gm

) 25 T ( 2 . 1 74
18
500

=
1000 2 . 65
18
500

88.8(T 25) = 65200 ; T = 734.23 + 25 759.23C
Q.20 HA(aq) + BOH(aq) BA(aq) + H
2
O
AH = 57.3 + AH
ion
HA
= 42.3 option (A) correct
HA(g) + BOH(g) BA(aq) + H
2
O
AH = AH
solution
HA + AH
solution
BOH 57.3 + 15
= 93 option (B) correct
HA(g) H
+
(aq) + A

(aq)
AH = AH
solution
+ AH
ions
= 55.7 kJ option (C) is correct
BOH is strong base AH
ion
= 0 B
+
(aq) + OH

(aq) BOH(aq) AH= 0

option (A), (B), (C)
[18]
Q.22 A
r
H = 635 394 (1207) = 178 kJ/mole
A
r
S = S(CaO) + S(CO
2
) S(CaCO
3
)
= 40 + 214 94 = 160 J/K
A
r
G = A
r
H T A
r
S = 178
1000
160 300
= 178 48 = 130 kJ/mole
Q.23 AS
system
= nRln
1
2
V
V
2 R ln 2

11.52 J/K
AS
surrounding
=
300
1000 3 . 3

11 J/K
[1]
PHYSICAL CHEMISTRY
ANSWER KEY
PART TEST-2
SITTING -1
Q.1 B Q.2 A Q.3 C Q.4 A Q.5 B Q.6 C Q.7 B
Q.8 C Q.9 B Q.10 C Q.11 A Q.12 B Q.13 C Q.14 B
Q.15 A Q.16 A Q.17 CD Q.18 AB Q.19 0032 Q.20 4300
SITTING -2
Q.1 A Q.2 B Q.3 D Q.4 B Q.5 A Q.6 D Q.7 A
Q.8 A Q.9 D Q.10 D Q.11 C Q.12 B Q.13 A Q.14 C
Q.15 D Q.16 B Q.17 B Q.18 ABCD Q.19 ABD Q.20 AC Q.21 AD
Q.22 AB Q.23 BD Q.24 1.45 Q.25 96 Q.26 75
SITTING -3
Q.1 A Q.2 B Q.3 C Q.4 D Q.5 A Q.6 B Q.7 D
Q.8 A Q.9 C Q.10 C Q.11 A Q.12 B Q.13 C Q.14 B
Q.15 C Q.16 C Q.17 B Q.18 B Q.19 AC Q.20 AC Q.21 AB
Q.22 ABC Q.23 (A) P,Q,R (B) P,Q,S (C) R (D) P,Q,R Q.24 1188 nm
Q.25 7256 Q.26 8
[2]
SOLUTION
SITTING -1
Q.1
o
Ag / AgI / I
E =
o
Ag / Ag
E
+ +
1
059 . 0
log K
sp
Q.2 K
sp
(Cd(OH)
2
) = [Cd
2+
] [OH

]
2
10
14
= [Cd
2+
] [10
4
]
2
[Cd
2+
] = 10
6
M
0
Cd | Cd Cd | Cd
2 2
E E
+ +
=

2
0591 . 0
log
)] aq ( Cd [
1
2+ 0.40
2
0591 . 0
log
6
10
1

= 0.5773 V Ans V Ans

Q.3
2
7 2
O Cr + 14 H
+
+ 6 e 2Cr
3+
+ 7H
2
O
Initial con
n
1 0.1 0
After reaction 0.5 0.1 M 1M
E
RP
=
o
RP
E

6
06 . 0
log
14 2
7 2
2 3
] H ][ O Cr [
] Cr [
+
+
E
RP
= 1.33
6
06 . 0
log 14
) 1 . 0 ( ) 5 . 0 (
1
= 1.33
6
06 . 0
log (2 10
14
)
= 1.187 V
Q.4 14H
+
+
2
7 2
O Cr + 6e 2Cr
3+
+ 7H
2
O
E = E
6
06 . 0
log
14
2 3
] H [
] Cr [
+
+
On changing pH from 0 14
[H
+
] changes from 1 10
14
Keeping all other concentrations constant.
E' = E
6
06 . 0
log [Cr
3+
]
2

6
06 . 0
log [H
+
]
14
E' = E + (14) 0.01 log [H
+
]
E' = E + (14) (0.01) (14)
1.96 volt Ans.
Q.5 for (A) and (D)
o
cell
E = ve AG = + ve
for (C)
o
cell
E = + 0.46
for (B)
o
cell
E = + 1.56
AG is most negative for (B)
[3]
Q.6 Anode reaction : H
2
(0.4 atm) 2H
+
(10
1
M) + 2e

Cathode reaction : 2H
+
(10
2
M) + 2e

H
2
(0.1 atm)

cell reaction H
2
(0.4 atm) + 2H
+
(10
2
M) 2H
+
(10
1
M) + H
2
(0.1 atm)
E = 0
2
059 . 0
log
) 10 )( 4 . 0 (
) 1 . 0 ( ) 10 (
4
2 1

= 0.041V
Q.7 2Cl

Cl
2
+ 2e

A
o
1
G = 2 F (1.36)
2OCl

+ 2H
2
O + 4e

2Cl

+ 4OH

A
o
2
G = 4 F (0.94)

2OCl

+ 2H
2
O + 2e

Cl
2
(g) + 4OH

A
o
3
G = 2 F
o
3
E
2 F
o
3
E = 2 F ( 1.36) 4F(0.94)
o
3
E = 1.36 + 2 0.94 = 0.52 V Ans.
Q.8
7 . 18 100
x 10
x
=
|
|
.
|

\
|
+
x = 2.3 or 0.1 mol
Na
+
+ e Na Hg
= 0.2 F ( q = 0.5)
Q.9 G* =
a
l
=
100
10
= 0.1 ; G = 0.0001 S ; V = 100 10 = 1000 cm
3
= 1 litre
k
= G G* = 0. 0.0001 = 10
5
^
m
=
M
100 k
=
5 . 0
1000 ) 0001 . 0 1 . 0 (
= 0.02 Scm
2
mol
1
Ans.
Q.10 HA H
+
+ A

C(1o) Co Co ; o =

.
.
eq
eq
10/200 = 0.05
[H
+
] = 0.1 0.05 0.005
pH = 3 log5 2.3
Q.11 Molar conductance of HCl will be maximum and CH
3
COOH will be minimum
because (i) [H
+
] have exceptional ionic mobility
(ii) CH
3
COOH is a weak electrolyte
[4]
Q.12 k =
1000
M .
m
.
=
1000
04 . 0 200
= 8 10
3
Scm
1
k = G
|
.
|

\
|
A
l
8 10
3
= G
|
.
|

\
|
4
8
G = 4 10
3
V = IR =
G
I
I = V G = 10 4 10
3
A 0.04 A Ans.
Q.13 w = Z n q
Z =
96500 2 9 . 0
5 . 96

= 5.55 10
4
Q.14 AG = nFE
cell
or 2 ( 237.39 10
3
) = 4 96500 E
cell
E
cell
= 1.23 V Ans.
Q.15 Mole of H
2
needed for 237.39 kJ of useful work = 1
Mole of H
2
needed for 23.739 kJ of useful work = 0.1

P
nRT
V
2
H
=
=
1
298 083 . 0 1 . 0
= 2.47 l Ans.
Q.16 Theoretical Efficiency of cell
% 100
H
G

A
A
=
% 100
8 . 285
39 . 237

= 83.06% Ans.
Q.19
2
1
H
2
(g) H
+
(aq) + e

Ag
+
(aq) + e

Ag (s)
-----------------------------------------
2
1
H
2
(g) + Ag
+
(aq) H
+
(aq) + Ag(s)
------------------------------------------
E
cell
=
2 / 1
H
o
cell
) P ]( Ag [
] H [
log
1
06 . 0
E
2
+
+

= 0.8 0.06 log

9
10 2
2 . 0

= 0.8 0.06 log 10

8
= 0.32
[5]
Q.20 0.6 =
o
Cell
E 0.06 log [H
+
]
0.6 =
o
Cell
E + 0.06 pH
1
0.75 =
o
Cell
E + 0.06 pH
2
0.15 = 0.06 (6.8pH)
2.5 = 6.8pH
pH = 6.8 2.5
= 4.3 Ans.
[6]
SITTING -2
Q.1 for octahedral void
R = 0.414
2 2
362
Q.2 Edge not covered by atom = a 2r
& in BCC unit cell ; r =
2 2
a
Therefore, edge not covered = a 2
2 2
a
0.293 a
Fraction of edge is not covered = 0.293 Ans.
Q.3 Nearest neighbour located at distance
2
a
= 0.70 a,
Total number = 12
Alternative
Na
+
make fcc lattice in NaCl structure. There are 12 next nearest neighbours at distance
2
a
Q.4 Let volume of fcc unit cell = V
d
A
=
V . N
M 4
A
A

d
B
=
V . N
M 8
A
B

B
A
d
d
=
B
A
M 2
M
=
50 2
30

= 0.3
d
B
= 3.33 g/cc
Total density = d
A
+ d
B
= 4.33 gm/cc Ans
Q.5 2r =
4
a 3
or r =
8
a 3
=
8
356 732 . 1
= 77.07 pm
Q.8 The formation of micelle only above certain temperature called Kraft temperature suggests positive AS
of micelle formation which even overcome effect of positive AH of micelle formation. Besides kinetic
effect also become important at high temperature.
[7]
Q.12 Cu
1.92
S Cu
192
S
100
Cu + Cu
2+ +
x (192x)
Hence 2 x + 1 (192x) = 200
x = 8
Hence
23
1
184
8
Cu
Cu
2
= =
+
+
Ans. (B)
Q.15 (P.E.)
OV
= 3
3 3
a
) r 414 . 0 (
3
4
4 r
3
4
4 t + t
(P.E.)
TV
=
3
3 3
a
) r 225 . 0 (
3
4
8 r
3
4
4 t + t
Now, 4
3
4
t(0.414 r)
3
> 8
3
4
t (0.225 r)
3
0.378 t r
3
> 0.1215 t r
3
Q.18 (A) d
FCC
= 3
A
a N
M 4
=
3
A
2
r 4
N
M 4
|
.
|

\
|
d
hcp
= 3
A
r 2 24 N
M 6
Both are same.
Q.20 XY (aq) X
+
(aq) + Y(aq)
X
+
(aq) + H
2
O(l) XOH (aq) + H
+
(aq)
At equation
C(1 o) Co Co
[H
+
] = Co =
C
K
K
b
w

; (10
5
)
2
=
5
14
10 4
10

M
80

2
1
M = 100 gm/mol ; o =
C
K
h
100 2.5 10
3
[8]
a for XY : 3 a = 2 (r
+
+ r)
1.732 a = 2 (1.6 + 1.864)
a = 4 = 4 10
8
cm
Effective formula unit of XY = 1
d =
A
3
N a
M . Z

= 23 3 8
10 6 ) 10 4 (
100 1


=
384
1000 1
= 2.6 gm/cc
Q.24 d =
3
A
a N
M Z
d
dia
=
3
A
a N
mole / gm 12 8

...(1)
4
3 a
= 2r = 1.50 ; a = (1.50 )
|
.
|

\
|
3
4
d
si
=
) 3 / 4 ( ) 25 . 2 ( N
mole / gm 28 8
A

...(2)
si
dia
d
d
=
28 8
)] 3 / 4 )( 25 . 2 [( N
)] 3 / 4 )( 50 . 1 [( N
12 8
3
A
3
A

=
|
.
|

\
|
28
12
3
5 . 1
25 . 2
|
.
|

\
|
=
8
27
28
12

= 1.45
Q.25 Theoretical density = 3
A
a . N
M . Z

3 10 23
3
) 10 4 ( 10 6
10 24 4



Theoretical density d = 3
A
a . N
M . Z
2.5 10
3
kg/m
3
% occupancy =
density Ideal
density Observed
100

3
3
10 5 . 2
10 4 . 2

100 = 96 % Ans.
[9]
Q.26
x
r
x = r \2
45
2r
x
h
Sphere of 2 layer
nd
Spheres of 1 layer
st
(2r)
2
= h
2
+ x
2
h
2
= 2r
2
height =
r 2
,
area = 4r
2
Volume = area height
= 4r
2
r 2
3
r 2 4
,
Z = 1,
)
`

|
.
|

\
|
+ = 5 . 0 4
8
1
Z layer 2 in shared is
2
1
& layer 1 in shared is th
8
1
nd st
P.F. =
2 3 r 2 4
r 3 / 4 1
3
3
t
=
t
= 0.75 75 %
OR
As this packing also give rise to FCC lattice it can be directly commented that P.F. = 0.75
[10]
SITTING -3
Q.4 Probability of finding electron between distance r and r + dr = dr r 4
2 2
t =
dr e ) r 4 (
a
Z
0
a / Zr 2
2
3
0
3

t
|
|
.
|

\
|
t
For maximum f(r) =
0
a / Zr 2
2
3
0
3
e ) r 4 (
a
Z

t
|
|
.
|

\
|
t
must be maximum
setting
dr
) r ( df
= 0 2r =
|
|
.
|

\
|
0
2
a
Z 2
r
r =
Z
a
0
for He
+
ion =
2
9 . 52
= 26.45 pm is the most probable distance of electron in He
+
ion
Q.5 Hint: v o
n
Z
; r o
z
n
2
; frequency of revolution =
n
n
r 2
v
t
; Coulombic force of attraction = 2
0
2
r ) 4 (
Ze
e t
Q.7 Probability of finding electron between distance r and r + dr = dr r 4
2 2
t =
dr e ) r 4 (
a
Z
0
a / Zr 2
2
3
0
3

t
|
|
.
|

\
|
t
For maximum f(r) =
0
a / Zr 2
2
3
0
3
e ) r 4 (
a
Z

t
|
|
.
|

\
|
t
must be maximum
setting
dr
) r ( df
= 0 2r =
|
|
.
|

\
|
0
2
a
Z 2
r
r =
Z
a
0
for He
+
ion =
2
9 . 52
= 26.45 pm is the most probable distance of electron in He
+
ion
Q.8 K.E. of particle = qV
=
mv
h
=
mKE 2
h
=
mqV 2
h
option (A)
Q.9 +
(angular)
= constant
s-orbital
Also two radial nodes n01 = 2
n =3
3s orbital
option (C)
[11]
Q.10 l = 0 and n = 4
4s
no. of radial nodes = (nl1) = (4 0 1) = 3
Q.11 Potential energy =
r
) e ( ) Ze (
4
1
0

e t

|
|
.
|

\
|

e t

r
e 3
4
1
2
0
Ans.
Q.12 r
n
=
2 2
2 2
me 4 z
h n
t
=
z
n
2
(constant)
x =
1
3
2
(constant)
and r
4
=
3
4
2
(constant)

4
r
x
= 3
4
3
2
2
=
16
27
r
4
=
27
16
x Ans.
Q.14 Given 3 Ax = AP , Ax . AP >
t 4
h

t
>
A
4
h
3
) P (
2
t
> A
4
h
) v ( m
2 2
2 / 1
2
m
1

4
h 3
v
|
.
|

\
|
t
> A
;
t
> A
h 3
m 2
1
v
Q.15 E = IE
1
+ IE
2
= 24.6 + 13.6 (2)
2
79 eV
Q.20 At radial nodes
(r) = 0
(o1) = 0 : (o
2
8o + 12) = 0
o = 1 ; o = 6,2
[12]
Q.21 Since n photons are absorbed & exactly n photons are emitted transition must have taken place from
1 to 2.
Energy of photon = 10.2 z
2
where z = 1, 2, 3, 4
Q.22 13.6
6 . 13
) 4 (
z
2
2
=
z = 4
Q.24 AH =
2
1
500 150 = 100 kJ /mol
AH =
A
N
hc

100 =

23 8 34
10 6 10 3 10 6 . 6
Q.25 First letter (R) : n l 1 = 5
l = 1
n = 7 Ans.
1
7 n
=
l
Second letter (O) : PE =
r
KZe
2

, TE =
r 2
KZe
2

2
TE
PE
=
Ans.
Third letter (C):
max
) KE ( 04 . 0
12400
1240
+ =
(KE)
max
= 0.06 eV
=
06 . 0
150
= 50 = 5 nm Ans.
Fourth letter (K): Number of radiations =

) n n (
1 2
=

= + + = = 6 1 2 3 3 ) 2 5 ( Ans.
Q.26 We have AE =
4
3
0.85 eV
as energy = 0.6375 eV the photon will belong to brackett series
(as for brackett series 0.306 s E s 0.85 )
So
4
3
0.85 = 13.6 (

2 2
n
1

4
1
n = 8 ; Hence x = 8
[1]
PHYSICAL CHEMISTRY
ANSWER KEY
PART TEST-3
SITTING -1
Q.1 A Q.2 B Q.3 A Q.4 B Q.5 A Q.6 C Q.7 D
Q.8 C Q.9 B Q.10 A Q.11 B Q.12 C Q.13 C Q.14 C
Q.15 C Q.16 B Q.17 C Q.18 D Q.19 ABD Q.20 ABD Q.21 AB
Q.22 (A) P, Q (B) R, P Q.23 0.025 mole/L Q.24 437.5 mg
Q.25 5.11 10
5
s
1
Q.26 4.5 10
04
Q.27 0050.00 Q.28 7500
Q.29 5 Q.30 2
SITTING -2
Q.1 B Q.2 B Q.3 A Q.4 B Q.5 C Q.6 D Q.7 D
Q.8 B Q.9 AB Q.10 C Q.11 D Q.12 A Q.13 D
Q.14 ABCD Q.15 (A) P (B) Q,R,S (C) T (D) P,Q,R,S,T Q.16 180 Q.17 248
SITTING -3
Q.1 B Q.2 C Q.3 C Q.4 D Q.5 D Q.6 A Q.7 C
Q.8 A Q.9 A Q.10 A Q.11 A Q.12 B Q.13 D Q.14 A
Q.15 B Q.16 ABD Q.17 BD Q.18 ABD Q.19 AC
Q.20 (A) P,R,S (B) P,Q,S (C) P,Q,S (D) P,R,S Q.21 600 Q.22 6568 Q.23 96
Q.24 75
[2]
SOLUTION
SITTING -1
Q.3 E
I

~
E
II
~
E
V

~
E
VI
E
III

~
E
IV
E
III
> E
II
(due to loss of resonance energy)
II III (is slowest step)
III IV (is fast step)
Q.4 A + B C + D
t = 0 1 1
t 1-x 1-x x x
rate = k[A] [B]

dt
A d ] [
= k(1x)

(1x)

( )
dt
x d 1
= k(1 x)
dt
dx
= k(1 x)
}

x
x
dx
0
1
= k }
t
dt
0
[ln (1x)]
0
x
= kt ln(1x) = kt
ln(1x) = kt t =
|
.
|

\
|
x k 1
1
ln
1
When [A] = 0.25
x = 0.75
t = 4 ln
31 . 2
10
25 . 0
1
ln
10 31 . 2
1
3
3
=

=
31 . 2
693 . 0 10 2
3

=
31 . 2
693 . 0 10 2
3

= 600 Sec.
Q.5 E
net
=
2 1
a 1
k k
) E ( k
1
+
+
2 1
a 2
k k
) E ( k
2
+
=
2 2
2 2
10 4 10
100 10 4 80 10


+
+
=
2
10 5
4 8 . 0

+
= 96 kJ/mole
Q.6 From 1
st
and 2
nd
data order of reaction w.r.t. ICl is 1, from 1
st
and 3
rd
data order of reaction w.r.t. H
2
is
1, so overall order of reaction is 2.
Q.9 k
1 (300K)
=
20
693 . 0
; k
2 (320)
=
5
693 . 0
; ln
) 300 ( 1
) 320 ( 2
k
k
=
(
(

2 1
a
T
1
T
1
R
E
E
a
=
1
2
1 2
2 1
k
k
log
) T T (
T T R 303 . 2

=
1000 20
314 . 8 303 . 2

300 320 log 4 55.14 kJ/mol

Q.11 Rate = k . [Acetone]
x
. [Br
2
]
y
. [H]
z
6 10
4
= k . (0.15)
x
(0.025)
y
(0.025)
z
... (i)
6 10
4
= k . (0.15)
x
(0.050)
y
(0.025)
z
... (ii)
12 10
4
= k . (0.15)
x
(0.025)
y
(0.050)
z
... (iii)
8 10
4
= k . (0.20)
x
(0.025)
y
(0.025)
z
... (iv)
(i)

(ii), 1 =
y
050 . 0
025 . 0
|
.
|

\
|
[3]
y = 0, hence rate does not depend upon the concentration of Br
2
.
(i)

(iii),
12
6
=
z
050 . 0
025 . 0
|
.
|

\
|
;
2
1
=
z
2
1
|
.
|

\
|
z = 1
(i)

(iv),
4
3
=
x
4
3
|
.
|

\
|
x = 1
Q.13 Rate law =
dt
dp
= K
2
[R] [C]
at steady state
0
dt
] R [ d
=
=
dt
] R [ d
K
1
[A] K
2
[R] [B] K
2
[R] [C] = 0
K
1
[A] = {K
2
[B] + K
2
[C]} [R]
[R] =
]} C [ ] B {[ K
] A [ K
2
1
+
Rate = K
2

] C [
] C [ ] B [
] A [
K
K
2
1

+
=
1
] C [
] B [
] A [ K
1
+
where C is very high
Rate = K
1
[A]
order of reaction = 1Ans.
Q.14 ln K =
T
2500
10
+ 3 ln T
dT
) K n ( d l
=
2
T
2500 +
+
T
3
=
2
T
T 3 2500+
E
a
= (2500 + 3T) R
Q.15
2
r
1
r
3 2
SO O
=

3
SO
r
= 2
2
O
r
= 2
32
8
mol/sec. =
2
1
mol/sec.
=
80
2
1

= 40 gm/sec.
[4]
Q.16
x
) x 2 x 2 ( 4 x 7 +
=
1
4 28
= 24
Q.17 X
88
35

+
|
Y
88
34

o
Z
84
32
Y
88
34
&
Z
84
32

are isodiaphers
(A2Z) is same for both.
Q.18 Specific activity is different as molar mass of
238
UF
6
and
238
U is different.
Q.20 (A) AH = [2(1263) ] [(2238) + (285)] = 3 kJ
(B) C
12
H
22
O
11
+ 12O
2
12 CO
2
+ 11 H
2
O
C
6
H
12
O
6
+ 6O
2
6CO
2
+ 6H
2
O 2
C
12
H
22
O
11
+ H
2
O 2C
6
H
12
O
6
; AH = 3
Hence, A
C

11 22 12
O H C
H is greater than 2 A
C

6 12 6
O H C
H
(C) Hydrolysis is exothermic T | h +
(D) Concentration becomes one-forth is each equal time internal Hence, 1
st
order
Q.21 (A) Sucrose + H
2
O Glucose + Fructose K = (

t
0
r r
r r
log
t
303 . 2
;
K =
(

20 15
30 15
log
30
303 . 2
K =
(

35
45
log
30
303 . 2
K = 9.212 10
3
t
1/2
=
K
2 log 303 . 2
=
3
10 212 . 9
3 . 0 303 . 2

= 75 min
Q.22 Option (A) When concentration of B is maximum.
t
max
=
|
|
.
|

\
|

1
2
1 2
k
k
n
) k k (
1
l
Option (B)
When t = t
1/2
of A =
1
k
2 n l
and k
2
= 2k
1
[B]
t
=
1 2
0 1
k k
] A [ k

( )
t k t k
2 1
e e


= [A
0
] (e
ln2
e
2 ln2
) = [A
0
]
|
.
|

\
|

4
1
2
1
=
4
] A [
0
[C]
t
= [A
0
] [A] [B]
[5]
= [A
0
]
2
] A [
0

4
] A [
0
=
4
] A [
0
[B]
t
= [C]
t
Q.23 Since t
1/2
= 0.693/k t
1/2
= 500 sec.
Since volume is changing therefore half life does not mean that concentration will be reduced to half
rather half of initial moles of A will be reacted, therfore moles ( if initially 1 lit is assumed) remaining of A
= .05.
A 2B + C
1x 2x x
= n
f
= 1 + 2x x = 0.5
1+ 2x = 2
Also final volume of the container will be V
f
= 1 litre n
f
/n
i
2 litre
final

concentration of A will be 0.025M
Q.24 Let wt. of A is x and B is y
x + y = 10 ...(1)
wt. of A remaining after 6 hours =
3
2
x
=
8
x
wt. of B remaining after 6 hours =
2
2
y
=
4
y

8
x
+
4
y
= 2 ...(2)
From eqs. (1) and (2)
x + 2y = 16
x + y = 10
-----------
y = 6 so, x = 4
wt. of A remaining after 12 hours =
6
2
4
= 0.0625 gm = 62.5 mg
wt. of B remaining after 12 hours =
4
2
6
= 0.375 gm = 375 mg
Total wt. of mixture remaining in mixture = 437.5 mg
Q.25 Volume of thiosulphate o moles of I
2
o moles or reactant.
k =
t
3 . 2
log
t
0
] A [
] A [
=
t
3 . 2
log
|
|
.
|

\
|
t
0
V
V
The given data suggests first order kinetics
k =
60 30
3 . 2

log
(

45
50
sec
1
=
60 30
3 . 2

[log 10 log 9]
[6]
60 30
3 . 2

{12(.48)}
=
60 30
) 04 . 0 ( 3 . 2

= 5.11 10
5
sec
1
Q.26 k
eff
= k [H
+
]
1
=
t 0
0 0
V V
V V
n
t
1

l
k
eff
= k [H
+
] =
4
5
n
10
1
l
min
1
] H [
] Ester [
V
V V
0
0
0 0
+
=

=
] H [
3 . 0
5
3
25
15
+
= =
[H
+
] =
3
5 3 . 0
= 0.5 mole/L
4
5
n
10
1
l
= (0.5) k
k =
(

4
5
n
5
1
l
rate =
|
.
|

\
|
4
5
n
5
1
l
(0.1) (0.1)
4.5 10
05
Ans.
Q.27 Since B is in large excess, rate law will become
Rate = k'[A]
2

where k' = k[B]
t
] A [
1

0
] A [
1
= k't
2 / 1
0
t
' k ] A [
1
=
t
1/2
=
3 5
10 2 10 5 2 . 0
1


= 50 minutes
Q.28 t = 5 min << t
1/2
Hence, no change in activity of H
3
, let the total volume of water in body is V ml.
then,
1.08 10
11
= V 3.0 10
4
60
V = 60000 ml
weight of water in body = 60000 1 = 60000 gm = 60 kg
weight percent of water =
100
80
60

= 75 %
[7]
Q.29 2NH
3
N
2
+ 3H
2
Pressure at t = 0 3 atm 0 0
Pressure at t = 10 (32x)atm x atm 3x atm
rate of reaction =
2
1

dt
) NH ( d
3
= 0.1
dt
) NH ( d
3

= 0.2
For zero order, C
A
= C
A0
Kt
or (32x) = 3 0.2 10
or x = 1
P
total
= 3 2x + x + 3x = 3 + 2x = 5 atm
Q.30 SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)
10 mmole
10x x x
SO
2
+ Hypo = I
2
x 2 + 1 10 = 1 25
x = 7.5
[8]
SITTING -2
Q.1
0
A
0
B
0
A
A
0
A
0
B
A
P
P P
x
1
P
P
y
1
+ =
y
A
=
7
2
y
B
=
7
5
Q.4
700 P X P X
o
B B
o
A A
= +
.....(i)
600 P 70 . 0 P 30 . 0 P X P X
o
B
o
A
o
B
' '
B
o
A
' '
A
= + = +
if moles of A & B initially are x & y then
x = 0.75
3
2
(x + y) + 0.3
3
1
(x + y)
& x
A
=
y x
x
+
or x
B
=
y x
y
+
Solving gives
x
A
= 0.6
3
2500
P
o
A
=
torr
x
B
= 0.4
500 P
o
B
=
torr
Q.5 Moles of Benzene =
78
1560
= 20
Moles of Chlorobenzene =
5 . 112
5 . 112
=10
Mole fraction of Benzene =
30
20
=
3
2
Mole fraction of Chlorobenzene =
3
1
Total pressure at 100 C =
3
2
1350 +
3
1
300
(P
1
X
1
+ P
2
X
2
) = 1000 torr
Boiling point = 100C
Q.6 Solution : Colligative property
Q.8 P =
9 . 0
30
20
6 . 0
30
10
+
= 0.2 + 0.6 = 0.8
[9]
Q.9 y
A
=
10
n
A
y
B
=
10
n
B
x
A
=
20
n 10
A

x
B
=
20
n 20
B

6 . 0
20
n 10
P
10
n
A
T
A

= 9 . 0
20
n 20
P
10
n
B
T
B

=
3
2
n 20
n 10
n
n
B
A
B
A

=
60n
A
3n
A
n
B
= 20n
B
2n
A
n
B
n
A
n
B
60n
A
+ 20n
B
= 0
n
A
(10 n
A
) 60n
A
+ 20 (10 n
A
) = 0
2
A
n
+ 10n
A
60 n
A
20n
A
+ 200
2
A
n
+ 70 n
A
200 = 0
n
A
=
2
800 4900 70 +
; n
A
=
2
5 . 75 70
=
2
5 . 5
= 2.75
n
A
= 2.75 n
B
= 7.75 P
T
=
|
.
|

\
| +
20
9 . 0 75 . 12 6 . 0 25 . 7
= 0.791
Q.10
7 . 2
2
8 . 1
1
9 . 0
3 / 2
6 . 0
3 / 1
P
1
+ = + =
P = 0.77 Ans.
Q.12 2KI +HgI
2
K
2
[(HgI
4
)]
4 ions 3 ions
Q.14 For any solution, AS
mix
= +ve and AG
mix
= ve
Q.15 (A) AT
f
= i K
f
m
i m = 0.3 [P] i m = 0.1 3 = 0.3
(B) AT
b
= 0.28 K
b
= i K
b
m
i m = 0.28 [Q] i m = 2 0.14
[R] [1 + (n1)o]m = [1 + (2)0.9]0.1
= 2.8 0.1 = 0.28
[S] i m = 1 0.28 = 0.28
(C) t = i c RT
i c = 0.19 [T ] 0.1 m HA
K
a
= 0.81
K
a
=
o
o
1
C
2
o = 0.9
i = 1 + (n 1) o
i = 1.9
[10]
(D)
f
f
f f
solvent solute
solute
o
o
K
T
18
1000
K / T
n n
n
P
P P
A
+
A
=
+
=

[P,Q,R,S,T]
When weight of solvent is 1 kg = 1000 gram
n
solute
=
f
f
K
T A
Q.16 AT
f
= K
f
m = 1.9
1000
180 500
w
B

AT
f
=
180
w 8 . 3
B
T
f
=
180
w 8 . 3
B
AT
b
= 0.6
180
w
B
2 =
180
w 2 . 1
B
T
b
= 100 +
180
w 2 . 1
B
T
b
T
f
= 105 = 100 +
180
w 2 . 1
B

180
) w 8 . 3 (
B
100 +
180
w 5
B
= 105
180
w
B
= 1 gm
w
B
= 180 gm
Q.17 Henry Law
2
N
P
=
2 2
N N
X k
;
2
O
P
=
2 2
O O
X k
2
O
X
=
bar 10 5 . 2
bar 2 . 0
4

= 0.08 10
4
= 8 10
6
;
2
N
X
=
bar 10 5
bar 8 . 0
4

= 1.6 10
5
X = m
'
A
M

2
O
m
=
'
A
O
M
X
2
=
3
6
10 18
10 8

all over
m
=
3
5
10 18
10 4 . 2

2
N
m
=
'
A
N
M
X
2
=
3
5
10 18
10 6 . 1

L
m =
3
10
3
4

AT
f
= 1.86
3
10
3
4

= 0.62 4 10
3
= 2.48 10
3
[11]
SITTING -3
Q.2 At high Pressure 2
m
V
a
can be neglected
) b V (
V
a
P
m
2
m

|
|
.
|

\
|
+
= RTT
P =
T .
) b V (
R
m

Q.3
2
3
O
O
rate
rate
=
3
2
2
3
O
O
O
O
M
M
n
n
=
3
2
2 2
3 3
O
O
O O
O O
M
M
M wt
M wt
=
3 3
2 2
O O
O O
M . M
M . M
=
48
32
48
32
2
3
O
O
rate
rate
=
3 3
2 2
Ans.
Q.4 Since for both O
2
and SO
2
(g), M T is same.
Therefore the value of
N
dN
for both gases in all range of velocities will be same.
Q.5 P
1
He 1.2
P
2
H
2
1.6
same T , n , v

P
3
O
2
4
P
4
N
2
3.2
a decreases P increases
P
1
> P
2
> P
4
> P
3
Q.7 Z =
nRT
PV

n
V
=
9
273 0821 . 0 9 . 0
= 2.24 litre/mol
Volume of 1 millimole of gas 2.24 ml Ans.
Q.8 After long time, all the I
2
will be deposited in the container (II) as solid. Hence, the pressure of the gas
is due to N
2
only let the no. of molesof gas in container (II) be x mole.
Applying n
I
T
I
= n
II
T
II
(0.1 x) T
1
= x
3
I
T
0.3 3x = x x =
4
3 . 0
mole
[12]
wt. of N
2
in the container (II) is
4
3 . 0
28 = 2.1 g
Q.9 PM = dRt
Pd =
|
.
|

\
|
RT
M
P
2
;
dP
) Pd ( d
=
RT
PM 2
10 ;
T 0821 . 0
2 21 . 8 2

= 10
T = 40 K
Q.11 At constant pressure & temperature
V o n
2
1
V
V
=
2
1
n
n

3
1
w
w
2
1
=
Ans
Q.12
dt
dn

=
4
1
c
V
n
AA
ln
t
0
n
n
= (
4
1
c
V
A
)t
t
1/2
=

) V / A ( c ) 4 / 1 (
693 . 0

=
6 2
3
10 10
1 10 4 693 . 0



= 0.693 4 10
5
= 277200 sec
Q.13
2 2 / 1
1 2 / 1
) t (
) t (
=
1
2
c
c

=
2
1
M
M
=
4
= 2
(t
1/2
)
2
=
2
1
(t
1/2
)
1
= (277200)/2 = 138600 sec
Q.14 Given : That at speed around 270330 m/s the number of molecules is substantially greater as compared
to extremes (in the comprehension part )
option (A) {Rest options to be discussed in class (if required)}
Q.15
2 2
SO O
M
2
1
M =
if
2 2
SO O
T
2
1
T =
then
2
2
O
O
T
M
=
2
2
SO
SO
T
M
All other parameters are same the curves will be same
option (B) {Rest options to be discussed in class (if required)}
[13]
Q.16
Volume = V Volume = V
Flask-A Flask-B
Mass = m gm Mass = m gm
400 K 800 K
H gas
2
He gas
o = (Given) o
He H
2
(A) (U
rms
)
A
= (U
rms
)
B
as
B
B
A
A
m
T
m
T
=
(B)
2
H
.) E . K (
=
2
3
R (n. T) =
|
.
|

\
|
400
2
m
R
2
3
He
.) E . K ( =
2
3
R (n. T) =
|
.
|

\
|
800
4
m
R
2
3

2
H
.) E . K (
=
He
.) E . K (
(C)
) He ( Z
) H ( Z
1
2 1
=
( )
* 2
N 400 2 o t
,
He H
N N
2
>

He 1 H 1
) Z ( ) Z (
2
> as V is same
Q.17
O H
2
P
remains constant P
remaining
= 1.025 .025 = 1 atm
If volume of container is reduced half then pressure become double= 2 atm
Total pressure = 2 + .025 = 2.025 atm
If volume of container is doubled
the P = 0.5
Total = 0.5 + .025 = .525 atm.
Q.18 (A) V
C
= 3 b
= 3 4 [Volume occupied by 1 mole gaseous molecules]
= 12 [Volume occupied by 1 mole gaseous molecules]
(B) T
B
=
Rb
a
T
C
=
Rb 27
a 8
T
C
=
B
T .
27
8
T
B

C
T .
8
27
= 3.375 T
C
(D) At Boyles temperature, as PV is constant

dP
) PV ( d
= 0
[14]
Q.19 (A)
R
b 8
b 27
a
Rb 27
a 8
P
T
2
C
C
= =
(B) T
b
=
Rb
a
, T
C
=
Rb 27
a 8
T
C
=
27
8
T
b
T
C
< T
b
Q.21 At high pressure : Z = 1 +
RT
Pb
so,
10
1
RT
b
dP
dZ
= =
b =
10
300 8 . 0
10
RT
=
= 2.4 t/mole
b = 4 volume of 1 mole gaseous molecules (V)
V =
4
4 . 2
4
b
=
= 0.6 t.
0.6 10
3
= 600 Ans.
Q.22 At low pressure conditions b is neglected
RT V
V
a
P
m
2
m
=
|
|
.
|

\
|
+
PV
m
= RT
m
V
a
Intercept = RT = 32.84
T = 400 K
At high pressure conditions
Z = 1 +
RT
Pb
RT
b
= 0.02
b = 0.02 0.0821 400
b = 0.6568
[15]
Q.23 As P 0, real gas behaves like ideal gas

4
RT
M
P
d
= =
M = 4 0.08 300 = 96
Q.24 Let initial mixture contains n
1
& n
2
moles of NH
3
& N
2
H
4
respectively
Total moles of gases originally present = n
1
+ n
2
Total moles of gases aftre decomposition of gases = 2n
1
+ 3n
2
Now, using ideal gas law PV = nRT
0.5 V = (n
1
+ n
2
) R 300
4.5 V = (2n
1
+ 3n
2
) R 1200
2 1
2 1
n n
n 3 n 2
+
+
=
4
9
;
2
1
n
n
=
1
3
2 1
1
n n
n
+
100 = 75 % Ans.