Physical Volume2 Solution-20211123125008233883
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PHYSICAL CHEMISTRY
VOLUME-2
(SOLUTIONS)
INDEX
S. No. CHAPTER NAME P. NO.
1. CHEMICAL KINETICS 001 – 048
2. CHEMICAL EQUILIBRIUM 049 – 087
3. IONIC EQUILIBRIUM 088 – 123
4. ELECTROCHEMISTRY 124 – 161
CHEMIST RY
DPP
DAILY PRACTIC E PRO BLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 01
CHEMICAL KINETICS
TOPIC : AVERAGE RATE & INSTANEOUS RATE
SOLUTION
1 d[ NO 2 ] d[O 2 ]
1.
2 dt dt
d[ NO 2 ] 1
0.0036
dt 2
d[O 2 ]
= 0.0018 Msec–1
dt
d[O 2 ]
= 0.0018 × 60 Mmin–1
dt
d[O 2 ]
= 0.108 Mmin–1 Ans.
dt
1 d[ N 2O 5 ] d[O 2 ]
2. Rate = – .
2 dt dt
1 0.08mol d[O 2 ]
2 4L 0.2s dt
i.e. rate of formation of O2 = 0.05 Ans.
d[ O 2 ]
5. 2.5 105
dt
1 d[ N 2O5 ] d[ O 2 ]
2 dt dt
d[ N 2O 5 ]
= 2 × 2.5 × 10–5 5 × 10–5 M/s
dt
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1 d[ NO 2 ] d[ O 2 ]
6.
4 dt dt
d[ NO 2 ] 0.003
= 3 × 10–5
dt 100
d[ O 2 ] 1
3 105 = 7.5 × 10–6 M/s
dt 4
1 d[ N 2O5 ] 1 d[ NO 2 ]
7.
2 dt 4 dt
d[ NO 2 ] 0.004
= 4 × 10–5
dt 100
d[ N 2 O5 ] 2
4 10 5 = 2 × 10–5 M/s
dt 4
1 d[O 2 ] 1 d[O3 ]
9. Rate = . .
3 dt 2 dt
1 d[O 2 ] 1 1 7 1 1
3 . dt 2 M 96 10 g L s
O3
1 d[O 2 ] 1 1
. 96 10 7 mol L1 s 1
3 dt 2 48
d[ O3 ]
= 3 × 10–7 mol L–1 s–1 Ans.
dt
10. The correct explanation of statement (1) is law of stoichiometry
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CHEMIST RY
DPP
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TARGET : JEE(MAIN + ADVANCED)
ST
NO. 02
CHEMICAL KINETICS
TOPIC : ORDER OF REACTION
SOLUTION
PB PA
1. (A) =2
t t
1
A B
2
(B) t1/2 P0 so it is a zero order reaction
(C) It should be complex
8
(D) tcompletion = 8 6 = 40 min.
10
3. Theory based
4. A(g) B(g) + 2C(g)
Pi 20 torr
Pt=10 20–p p 2p ptotal = 20 – p + p + 2p = 40 torr
p = 10 torr
ln 2
so 10 sec is half life of A k = t = 0.07 sec–1
1/ 2
5. Pressure will be doubled only when the reaction is 100% complete.
100 % completion occurs is zero order among all above option.
6. 2A(g)
2B(g) + C(g) (zero order)
rate of disappearence of A
= rate of reaction
2
0. 1
Rate law : rreaction = Kreaction = atm/sec.
2
For zero order rate in independent of concentration of reactant and reaction take place with constant
0. 1
rate so rreaction after 10 sec. = atm/sec. = 0.05 atm/sec
2
8. 2A
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t = 10 3 – P1 3 P 2P1
1
2
t = 20 3 – P2 3 P 2P2
2
2
5 2
3+ P1 = 6.75 P1 = 3.75 = 1.5 atm
2 5
5 2
3+ P1 = 10.5 P2 = 7.5 = 3 atm
2 5
In equal interval of time equal amount react so it is zero order reaction.
1
9. [A]2 = 25 0.0002 t
d[A ] 0.0002
2[A]
dt (25 0.0002 t ) 2
d[A ] 1
[A]4 0.0002
dt 2[A ]
d[A]
= 0.0001 [A]3
dt
1
[A]0 = = 0.2 M
5
KA = 0.0001 M–1 min–1
order = 3
So answer is B
10. Rate = K[A]2
on incresing temperature K increases.
12. HCl + CaCO3 CaCl2 + H2 O + CO 2
0.1 mol 2gm
0.02 mol
Rate of reaction = K [HCl] [CaCO3]
Rate will increase on increasing concentration temperature surface area etc
13. 2NH3 N2 + 3H2
Pressure at t = 0 3 atm 0 0
Pressure at t = 10 (3–2x)atm x atm 3x atm
1 d ( NH 3 ) d( NH 3 )
rate of reaction = – = 0.1 = 0.2
2 dt dt
For zero order, CA = CA0– Kt
or (3–2x) = 3 – 0.2 × 10
or x = 1
Ptotal = 3 – 2x + x + 3x = 3 + 2x = 5 atm
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CHEMIST RY
DPP
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TARGET : JEE(MAIN + ADVANCED)
ST
NO. 03
CHEMICAL KINETICS
TOPIC : ORDER OF REACTION
SOLUTION
1. Zero order First order
C0 C0 '
C0 C0’
2 2
t1/2 = 4x t1/2 = x
t87.5 = 7x t87.5 = 3x
t 87.5 ,0 order 7x 7
st
t 87.5 ,1 order = =
3x 3
2. Rate = k[CH3NC]
ln 2
As [CH3NC] decreases, rate decreases & t1/2 =
k
1 1 1 C 2 H 6 (g ) C 2 H 4 (g ) H 2 (g )
3. k = t P x P
0 0 3 105
5
3 10 x x x
1 1 1 3 105 x 5 105
10–3 =
t 1 10 3 105
5
x 2 105
t = 0.666 × 10–2 Ans.
1 d[A ]
4. rrxn = 2 × 10–6 M/sec =
2 dt
d[ A]
= 2 × rrxn = 4 × 10–6 M/sec
dt
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5. A(g) B(g) + C(g)
d[ B] d[ A ]
rreaction
dt dt
d[ B]
K reaction [ A]
dt
R = Kreaction [A]0e–Kt
time
1 1 1
6. t1 / 2 I ·K1 t1 / 2 I
0.5 1 K1
ln 2
& t1/ 2 II K s
2
But, t1 / 2 I t1 / 2 II
1 ln 2
K K K2 = (ln2) . K1 K1 > K2 Ans.
1 2
Intial rate of Ist reaction (R01) = K1 (1M)2 = K1 M/s
Intial rate of 2nd reaction (R02) = K2 (1M) = K2 M/s
Reaction (I) is of 2nd order
It is complex
Ans. (ACD)
7. t1/2 [A0]1–n
100 [0.1]1–n ......(1)
50 [0.025]1–n ......(2)7
Dividing (1) by (2)
2 = 41–n n = 1/2
When [A0] = 1M
t1/2 [1](1 – 1/2)
and 100 [0.1]1/2
1/ 2
t1 / 2 1
t1/2 = 100 10 seconds.
100 0.1
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8. (A) r = k[A]n r1 = k[A]1n
n
r2 [A 0 ]2
r2 = k [A]2 n
r1 [A ]1
r2 [ A ]2 ln r2 ln r1
ln r n ln [A] n = ln[ A] ln [A]
1 1 2 1
n 1
1 ( t1/ 2 )1 [A 0 ]2
(B) (t1/2)1
[A 0 ]1n 1 ( t1 / 2 ) 2 [A 0 ]1
( t1 / 2 )1 [ A 0 ]2
ln ( t ) (n 1) ln [A ]
1/ 2 2 0 1
d[ A ]
(C) – k[ A ] n – d [A] = k[A]n dt
dt
d[ A] d[A ] n
– [ A ]n ln ln [A]
kdt kdt
d[A]
ln / ln [A] = n
k.dt
r
(D) r = k[A]n [ A ]n
k
r ln (r / k )
ln n ln [A] =
k ln[ A]
9. A (g) Product
1 d (n A ) dC
Rate1 = = K1 CAn = A ......(i)
V dt dt
dPA
Rate2 = = K2PAn .......(ii)
dt
PA = CA RT
dPA dC A
= RT
dt dt
For I
1 dP K1
Rate1 = Kt dt Pn
n A
(RT )
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d (P)
If n = 1 rate1 = = K1 PAn
dt
K1 = K2
d (P)
If n = 0 rate1 = = K1 (RT)
dt
K2 = K1 (RT)
K1
If n = 2 rate1 = P n
RT A
K1
K2 = K1 = K2 (RT)
RT
10.
(P) CA = C A 0 e kt
C A 0 (1 ) C A 0 e kt
(Q) CA = C A0 – kt
CA0 C A0 CA0 kt
k
or , = t straight line passing through origin.
CA0
1 1
(R) kt
CA C A0
C A0 C A
or, = C A0 kt straight line passing through origin.
CA
1
(S) t1/2 = kC Rectangular hyperbola
A0
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dB
11. = K[A]2 [B]
dt
from set 1 and set 2
[A0] >> [B0]
Order will be dependent on [B] only
hence first order reaction half life is independent of [B] x = 62.5 sec.
[If rate constant remains same]
from set 3 and set 4
[B0] >> [A0]
Order will be dependent only on [A]
hence second order reaction
half life is inversely dependent on [A0]
5 y
=
10 625
625
y= = 312.5
2
x + y = 312.5 + 62.5
375
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CHEMIST RY
DPP
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TARGET : JEE(MAIN + ADVANCED)
ST
NO. 05
CHEMICAL KINETICS
TOPIC : MIXED CONCEPT
SOLUTION
1. For zero order reaction,
[ A]0
t1/2 =
2K
With progress of reaction conc. of 'A' will decrease due to which t1/2 will also change with time.
K
2. t1/2 = C n 1 ....(i)
0
K K
t3/4 = n 1
n 1 ....(ii)
C0 C0
2
By equation (i) / eq (ii)
t3/4 = t1/2 [2n-1 + 1]
[B] mK1 1 2 1
3.
[C] nK 2 2 3 3
4. Theory based
dC K1C
5.
dt 1 K 2C
dC
At very low concentration : = K1C
dt
Order = 1
dC K1
At very high concentration : dt K
2
Order = 0
difference = 1 – 0 = 1 Ans.
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6.
0.693 1 K1 0.693
7. K1 = K2 K2 =
1
8. For nth order, n 1,
1 1
+ (n–1)t k
CnA1 CnA01
When CA = 0, t = t100%
t100% if n > 1
C1A0n
t100% =
(1 n )k
= tan–14 1 1
1
9. 2
n 1
(n 1)K rxn t
[C2F4]
[ A] [A ]n0 1
time(sec)
(n –1) Krxn = tan = 4
4
n –1 = 2, Krxn = =2
2
(A) Order of rxn = 3 n=3
3 3
(B) t1/2 = sec t1/2 for 3rd order :
2 1 2 4
3
(C) coefficent of C2F4 = 2 t1/2 = 2[A]n 1 K
0 rxn
order = 3
So reaction is complex.
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10. H2S(aq) + Cl2(aq) S(s) + 2H+(aq) + 2Cl–(aq)
d[ H 2S] 1 d[Cl ]
rrxn = = + = Krxn [H2S] [Cl2]
dt 2 dt
d[Cl ]
= 2Krxn [H2S] [Cl2]
dt
= 2 × 4 × 10–2 × 2 × 10–4 × 0.025
= 4 × 10–7
Rate of formation of Cl–1 = 4 × 10–7 M sec–1 = 4 × 10–7 × 107 = 4 M sec–1
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CHEMISTRY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 06
CHEMICAL KINETICS
TOPIC : SEQUENTIAL & PARALLEL REACTION
SOLUTION
k1[RX ] 0.1
1. k1 [RX ] 0.1 k 2 [RX ] × 100
10 k1 100 k1
= = Ans.
k1 k1 10k 2
k2
10
[ A] 2 1 20
2. = = = = 40
[B] 1 2 0. 5
ln 2
3. K300 K =
15
ln 2
K330 K =
10
K 300 KE 30
ln K a
300 K R 330 300
15 E a 1
ln
10 R 3300
2640 = 0.4 × 2 × 3300 = Ea
Ea = 2.640 Kcal/mol
5. Theory based
1
6. (A) t1/2 = for IInd order
K[A ]0
(B) Unit of A is same as K
(C) No
(D) Area under the curve = sum of fraction of molecules = 1
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7. CA + CB + CC = C A 0
dCA dCB dCC
0
dt dt dt
C A k1
CC k 2
CB k1
CA C A ( k1 k 2 )
0
11. Overall rate constant = k = k1 + k2 + k3 = 6.93 × 10–3
0.693
t1/2 = = 100 sec
6.93 103
After one t1/2 PB + PC + PD = 0.693 atm
PB k1 200 200
PB PC PD = k1 k 2 k 3 = 693 PB = 0.693 × = 0.2 Ans.
693
12. A B
t=0 x0 y0 (x0 + y0) = (x + y)
dx
t=t x y – = k xy
dt
dx
– = k x[(x0 + y0) – x]
dt
dx
– x ( x y ) x = k.dt
0 0
x dx dx
1
– ( x y ) x ( x y ) x kt
0 0 0 0
x0
1 x x 0 y0 x
– ( x y ) ln x ln kt
0 0 0 y0
x0 y0 x x0
= x y ln × y = kt
0 0 x 0
1 y x0
kt = ( x y ) ln x y Ans.
0 0 0
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 07
ST
CHEMICAL KINETICS
TOPIC : TEMPERATURE DEPENDENCE OF RATE
SOLUTION
– Ea/RT – Ea/R × ∞ 14 –1.
1. K=A×e =A×e = A = 6.0 × 10 s
2. K1 = A1e –E1 / RT and K2 = A 2 e –E2 / RT
K1 A
= 1 × e(E2 –E1 ) / RT ; A1 and A2 are not given.
K2 A2
– Ea 1 1
3. log K = × + log A at Y axies T = 0 T=∞
2.303R T
– Ea 1 Ea
at × axis log k = 0 × = – log A =T
2.303R T R ln A
K Ea (T2 − T1 ) 65 × 103 × (298 − 273)
4. log 2 = =
K1 2.303R T1T2 2.303 × 8.3 × 298 × 273
K2
calculation we find = 11
K1
5. For reaction, A
→ B.
Ea = 10 kJ/mole , ∆H = 5 kJ/mole
Rxn endothermic because ∆H (+)
∆H = Ea – Eb
5 = 10 – Eb
Eab = 10 – 5 = 5 kJ/mole. Then [B].
Ea 1
6. Now In k = In A – ×
R T
Ea −8.3 × 103
Slope = – = = 1000
R 8.3
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Ea 1
7. log k = – + constant
2.303 R T
Ea –3 103
=– × 10 × + constant
2.303 R T
Ea × 10 −3 4
thus, slope of graph will be – =–
2.303 R 0.4
⇒
4
Ea = 2.303 × 1.98 × 10 = 45600 cal
8. H2 (g) + Br2 (g) → 2HBr (g)
1/2
r = k[H2] [Br2]
Molecularity → not defined.
1 3
order = 1 + = .
2 2
9. For Rxn rate determining step is slowest step
Then in 1st Rxn
Rate = k [NO2] [O3] .....(i)
But 2nd Rxn
ka fast
O3 O2 + [O] ....(a)
kb
NO2 + O
slow
→ NO3 ....(b)
NO3 + NO2
→ N2O5 fast
....(c)
Then for Rxn (a)
ka [O2 ][O]
= = keq ....(d)
kb [O3 ]
by Rxn (b)
Rate = k [NO2] [O] ....(ii)
put value of [O] from (d) to (ii)
k eq [O3 ]
Rate = k × [NO2]
[O2 ]
k1 [NO2 ][O3 ]
Rate =
[O2 ]
10. Rate = K [X][Y2]
[X]2
Keq =
[X2 ]
K eq × [X2]
1/2
[X] =
Rate = K ×
1/2
K eq [X2] [Y2]
So the order of overall reaction is 1.5
11. H2(g) + 2ΙCl(g)
→ 2HCl(g) + Ι2(g)
Proposed mechanism
Mechanism % H2(g) + ΙCl(g)
slow
→ HCl(g) + HΙ (g)
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CHEM IST RY
MPP
MASTER PRACTICE PROB LEM S
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 01
CHEMICAL KINETICS
SOLUTIONS
d[P ] 15 5
1. = = 0.5 MS–1
dt 20 0
2. xA Y B
–1 d 1 d –d x d
[A] = y d t [B] [A] = [B]
x dt dt y dt
– d [A] x d [B] –d d x
log d t = log y d t log [A] = log d t [B] + log
dt y
x x 2
log = 0.3 y
= x:y 2:1
y
1
d 100
3. dt
[SO3] = 100 gram / min = mole / min = 1.25 mole/min.
80
–1 d –d 1 d
[SO2] = [O2] = [SO3]
2 dt dt 2 dt
–d 1.25 1.25
dt
[O2] = mole/min = × 32 gram/min = 20 gram/min
2 2
5. aA + bB Product
dx
= k[A]a [B]b
dt
(i) As on doubling concentration of A rate become four time so a = 2.
1
(ii) On four time concentration of B rate become double so b = .
2
1
So, Given equation : 2a + b Product
2
1 d[ A ] d[B ]
– =–2
2 dt dt
d[ A ] d[B ]
– =–4
dt dt
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6. 2NO (g) + 2H2 (g) N2 (g) + 2H2O (g)
1 d[NO] 1 d[H2 ] d[N2 ] 1 d[H2O]
Rate = – =– = = = K1[NO] [H2]
2 dt 2 dt dt 2 dt
d[H2O ]
(1) = 2K1[NO] [H2] = K [NO] [H2]
dt
So k = 2k1
d[NO]
(2) – = 2k1[NO][H2] = K1'[NO] [H2]
dt
k1' = 2k1
d[H2 ]
(3) – = 2k1[NO][H2] = K1" [NO] [H2]
dt
k1" = 2K1
7. Order have no relation with stoichiometric coefficient.
9. A + B product
r = K [A]1 [B]2
r1 = K [1]1 [1]2 = 1 × 10–2 (K = 1 × 10–2)
1 1 2 1
r1 = K 2 = 1 × 10–2 × = 1.25 × 10–3
2 8
10. Rate law for
Ist order IInd order IIIrd order
Rate = K[A]1 R2 = K[A]2 R3 = K[A]3
than we can say [A] = 1 r 1 = r 2 = r3 [A] < 1 then r1 > r2 > r3
y [A] > 1 then r3 > r2 > r1
11. Reaction is zero order (unit of k)
[B] = 2 × moles of A reacted
[B] = 2 × kt = 0.2 mol lit–1.
12. time Total for drop to disappears (ao – at) = kt at = 0
3.0 10 6
= t100% t100% = 6 × 10–9 sec
(0.05 10 3 ) 1 .0 10 7
13. From given graph x = Kt
i.e. it is a zero order reaction.
d [A ]
– =K
dt
14. By graph we can say log t1/2 = log a t1/2 = a .....(1)
a
t1/2 a then zero order Rxn k × t1/2 = .....(2)
2
1
then k =
2
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15. 2A + B product
d[ A ]
– = K [A]
dt
d[ A ]
– = K [a – x]
dt
Ct = C0 e–Kt
1
–K
Ct = C0 e K
Ct = C0 e–
C0
Ct =
e
16. Ct = C0 e–Kt
According to question
CA, t = CB, t
CA e –K A t = CB e –K B t
CA e–K B t CA
= (K –K )t
CB e –K A t
CB = e A B
ln 2 ln 2
5 – t
15
4 = e
ln 2 ln 2
ln4 = 5 – 15 t
ln 2 ln 2
ln(2)2 = 5 – 15 t
ln 2 ln 2
2ln2 = 5 – 15 t
1 1
2 = 5 – 15 t
2
2= ×t
15
t = 15 minute.
17.
dy 0.35
slope of graph at 20 sec = = = 7 × 10–3
dx 50
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60 CO CO C
O
18. t1/2 = 10 No. of Half life = = 6 half life Ct = n = = 64
10 ( 2) ( 2)6
19.* 2A + B C
t=0 2a a 0
t=t 2a – 2x a–x x
d[C]
= k (2 (a – x) (a – x) –1) = 2k
dt
d [c] = k dt
[C] = 2 kt
unit of k = Ms–1
[A] = 2 (a – x) and [C] = x
[B] = (a – x).
1 1
20. Ct = C0 + Kt.
1 1
= + 0.002 × t.
0.04 0.2
25 = 5 + 0.002 × t
20
t= = 10,000 sec.
2 10– 3
21. It is properties of Ist order Rxn and other all are properties of IInd order.
22.* 2A Product
1 1
= kt
[ A ]t [ A ]0
1 1
kt
[ A ] t [ A ]0
23. A + B C
t=0 a = 0.1 M b = 0.2 M 0
t = 100s a–x b–x x
From question , r = k[A][B] and hence
1 a(b x )
kt = ln
ba b(a x )
1 0.1(0.2 – x )
or 10–3 × 100 = × 2.303 × log
0.2 – 0.1 0.2 (0.1 – x )
x 0.002
[A] = 0.1 – x = 0.098 M
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24. From the unit of K, it is evident that it is a second order reaction.
1 d [NO 2 ] d [O 2 ]
– =
2 dt dt
d [NO 2 ] d [O 2 ]
– =2× = 2 × 1.5 × 10–4 = 3 × 10–4
dt dt
3 × 10–4 = K [NO2]2 = 3 × 10–3 [NO2]2 [NO2] = 0.316.
25. From figure [A]left = [B]formed = n × [A]decayed
[A0]e–t = n × A0 [1 – e–t]
n
e–t =
n1
n
[B]formed = n × A0 × 1 –
n 1
nA 0
=
n1
26. t1/2 = Ka(1 – n) , n being order k = Rate constant
log t1/2= log K + (1 – n) log a
1 – n = –1
n=2
t1/ 2 2n1 1 t3 / 4 4n1 1 42 1 15
27. = = = = =5 :1
t3 / 4 n1
4 1 t 1 / 2
n1
2 1 2
2 1 3
2n1 1
t1 / 2 =
| A |n01 K (n 1)
4 n1 1
t3 / 4 = .
| A |n01 K (n1)
28. Let r = (A)x (B)y
r 0.1 1
log 1 log log
r2 0.1 8
x= = =
a1 0.012 1
log log log
a2 0.024 2
x=3
r1 0.1
log log
r3 0.1 log(1)
y= b1
= =
0 . 035 1
log log log
b2 0.070 2
y=0
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29. Graph I – Rate independent of time, zero order Rxn.
Graph II – Half life independent of time, Ist order Rxn.
1
Graph III – between (a – x) and time, straight line, second order Rxn.
30. dt is parb parabolic graph
of y = x2
So This the graph of second order
1
y2 = x y = (x)
2
– dc 1 1
= K [C] 2 So reaction is 2 order..
dt
31. A 2 B + C
t=0 P0 0 0 P0
t=t (PO – x) 2x x P0 + 2x = 176
0 2 P0 P0 3 P0 = 270 P0 = 90
2 x = 176 – 90 = 86
x = 43
Pressure of A after 10 minute = 90 – 43 = 47
32. A (s) 2 B (g) + C (g)
1 P P0
K= ln P P P0 = 0 Pt = 150 P = 225
t t
1 225 1 225
ln 225 – 150 ln 75 = 0.05 ln 3
20 20
225 2 225
1 225 1 225
ln 75 = ln 225 P = 225 P
20 20 40 75 40
225 1
= 225 – P P40 = 200
75 75 40
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33* A(g) 2B(g) + C(g)
t=0 400 0 0
t = 20 min 400 – p 2p p
Given 400 – p + 2p + p = 1000
400 + 2p = 1000
1 400 1 ln 2
p = 300 mm ; k= ln = ln4 ; k= min–1
20 400 300 20 10
T1/2 = 10 min ; Value of K = 0.0693 min–1
400 200 100 50
10 min 10 min 10 min
After 30 min Partial Pressure of A is 50 mm, After 30 min Partial Pressure of B is 700 mm
After 30 min Partial Pressure of C is 350 mm , After 30 min total pressure become 1100 mm
34. A (g) B (g) + C(g) + D(g)
Initially Pi 0 0 0
At time t (Pi – Px) Px Px Px
total pressure at time t = (Pi + 2Px) = Pt
Pt – Pi
So Px =
2
2.303 Pi 2.303 2Pi
K= log P – P = log 3P – P .
t i x t i t
35. Initial pressure 65 105 y 185
Half life 290 x 670 820
Initial pressure of gas Initial moles of gas in above question.
Half life Initial pressure
So, it must be zero order reaction
CO P 65 65
t1/2 = = O 290 = k = = 0.112 mm of Hg/sec
2k 2k 2k 2 290
105 2 290 y 2 290
x= = 468 sec 670 = y = 150 mm of Hg
2 65 2 64
36. NH4NO2 (aq) N2 (g) + 2H2O (l)
2.303 V – VO 2.303 70 – 0
K= log V – V
V0 = 0 K= log
t t 20 70 – 40
2.303 70 2.303 7
= log K= log .
20 30 1200 3
1 0 100
37. k= ln = 0.0693 min–1
10 50 100
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38. Above question solution optically inactive if.
rt = 0
1 r r0 1 10 40 1
39. K= ln = ln = ln 2
10 60 r rt 10 60 10 15 10 60
0.0693
= = 1.15 10–3 sec–1.
60
40. t1/2 is independent of initial concentration a, for first order reaction
x Vt (= 5L at t = 20 minutes)
a Vf (= 50 L at completion)
2.303 a 2.303 50
k= log = log
t a–x 20 45
CO
41. k t = In C
t
2 N2O5 2N2O4 + O2
3
t=0 200 cm 0 0
3
t=t 20 cm 180cm3 90 cm3
t= 0 200cm3 100 cm3
3
Initial volume of N2O5 = 200 cm .
because Max. volume of O2 = 100 cm3.
200 In 10 2.303
K × 500 = In 20 k= = .
500 500
d[c ]
42. In given sequence of Rxn = k2 [B] – K3 [C]
dt
43. K = A × e– Ea/RT = A × e– Ea/R × = A = 6.0 × 1014 s–1.
44.* By using maxwell's velocity distribution curve the rise in temperature, increases the activated molecules to
form the product therefore rate of reaction increases.
45. The rate of reaction is decided by value of rate constant which depends on energy of activation not on the
value of H, definitely the comparison of rate of reactions of backward reactions can be done if H values are
also given to us.
46. K1 = A 1e – E1 / RT and K2 = A 2 e –E 2 / RT
K1 A1
K2
= A = e(E 2 – E1 ) / RT ; A1 and A2 are not given.
2
– Ea 1 1
47. log K = 2.303 R × + log A at Y axies T = 0 T=
T
– Ea 1 Ea
at × axis log k = 0 2.303 R × T = – log A R ln A = T
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K2 Ea ( T2 T1) 65 103 (298 273)
50. log K = T T =
1 2 .303R 1 2 2.303 8.3 298 273
K2
calculation we find K1 = 11
1
48. For reaction, A B.
Ea = 10 kJ/mole , H = 5 kJ/mole
Rxn endothermic because H (+)
H = Ea – Eb
5 = 10 – Eb
Eab = 10 – 5 = 5 kJ/mole. Then [B].
kt
49. k0
= (TC)t–0/10
t ln ( TC)
Taking log gives loge kt – loge k0 = loge (TC) ln kt = ln k0 + t
10 10
Comparision indicates ln (TC) = ln 3 TC = 3
50.* K = Ae Ea / RT A=K T Ea = 0
Ea 1
51. Now In k = In A – ×
R T
Ea 8.3 10 3
Slope = – = = 1000
R 8.3
Ea 1
52. log k = – 2.303 R + constant
T
Ea 10 3
=– × 10–3 × + constant
2.303 R T
E a 10 3 4
thus, slope of graph will be – =–
2.303 R 0.4
Ea = 2.303 × 1.98 × 104 = 45600 cal
53. H2 (g) + Br2 (g) 2HBr (g)
r = k[H2] [Br2]1/2
Molecularity not defined.
1 3
order = 1 + = .
2 2
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54. For Rxn rate determining step is slowest step
Then in 1st Rxn
Rate = k [NO2] [O3] .....(i)
But 2nd Rxn
ka fast
O3 O2 + [O] ....(a)
kb
slow
NO2 + O NO3 ....(b)
fast
NO3 + NO2 N2O5 ....(c)
Then for Rxn (a)
ka [O 2 ] [O]
k b = [O 3 ] = keq ....(d)
by Rxn (b)
Rate = k [NO2] [O] ....(ii)
put value of [O] from (d) to (ii)
k eq [O 3 ]
Rate = k × [NO2]
[O 2 ]
k1 [NO 2 ] [O 3 ]
Rate =
[O 2 ]
55. Rate = K [X][Y2]
[ X] 2
Keq =
[X2 ]
[X] = K eq [X2]1/2
Rate = K K eq [X2]1/2 [Y2]
So the order of overall reaction is 1.5
56. H2(g) + 2Cl(g) 2HCl(g) + 2(g)
Proposed mechanism
Mechanism
slow
H2(g) + Cl(g) HCl(g) + H (g)
K K2
58. A + A 1 A + A* A* + A
2A
Rate of decomposition
A = K1[A]2
Rate of formation A = K2[A] [A*]
At equilibrium rate of decomposition = rate of formation
K1[A]2 = K2[A][A*]
K1
[A*] = [A]
K2
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CHEMIST RY
MPP
MASTER PRACTICE PROB LEM S
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 02
CHEMICAL KINETICS
SOLUTIONS
rO2 rSO3
1.
1 2
8 1 1
rSO3 = 2 × rO2 = 2 × mol/sec. = mol/sec. = 80 = 40 gm/sec.
32 2 2
1 dNO 2 1 d[ H ] 1 dNO
6. k[ NO 2 ] [ H ][ I ¯]
2 dt 4 dt 2 dt
dNO 2
= 2 k0 X = k1 [X]
dt
d[H ]
= 4 k0 X = k2 X
dt
dNO
= 2k0 X = k3 [X]
dt
k1 k2 k3 k1
K0 = k1 = = k3
2 4 2 2
nA
7. Use PA = CART and CA =
V
d[ A]
8. Zero order reaction t1/2 a & rate of reaction is not depend on concentration of reactant]
dt
x 1 3
9. k= ; t=x. ; t3 / 4 = .a
t k 4k
10. For zero order reaction,
[ A]0
t1/2 =
2K
With progress of reaction conc. of 'A' will decrease due to which t1/2 will also change with time.
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11. 3A(g) 4B(g) + C(g)
t=0 3/5atm
3 4 1
t=0 x atm x atm x atm
5 3 3
3 4 1
x x x 1atm
4 3 3
3 2x
1
5 3
2x 2
3 5
3
x= x = 0.6 atm
5
As A(g) is disappear completely so reaction can be of zero order. If reaction zero order than
PA 0.6 atm
RODA = = 10 min = 0.06 atm min–1 = KA
t
Instant Rate of disapperance of A = KA [A]0 = 0.06 atm min–1
13. A + B C + D
t=0 1 1
‘t’ 1-x 1-x x x
rate = k[A]½ [B]½
d [ A] d 1 x dx
– = k(1–x)½ (1–x)½ – = k(1 – x) = k(1 – x)
dt dt dt
x t
dx
1 x = k dt [–ln (1–x)]0x = kt –ln(1–x) = kt
0 0
1 1
–ln(1–x) = kt t= ln
k 1 x
When [A] = 0.25
x = 0.75
1 1 103 2 103 0.693 2 103 0.693
t= ln ln 4 = = = 600 Sec.
2.3110 3 0.25 2.31 2.31 2.31
0.693 [A ]0
14. × t = 2.303 log 0.1[A ] t = 23.03 min
6.93 0
kf kf
16. = keq kb =
kb k eq
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18. The order is 1 hence for equal time intervals
time 0 t 2t 3t
conc. a 0 a 0 x a 0x 2 a 0x 3
a0 = 1
x = 0.7 a0x3 = (0.7)3 = 0.343 ]
k
20. Slope =
2.303
2 k
=
10 60 2.303
k = 7.67 × 10–3 sec–1
0.693 0.693
21. t1/2 = 200 sec.
k 3465106
After one half life moles of A remaining 0.05
and total no. of moles 0.05 + 0.15 0.2
nf 0.2
Vf = n × Vi × 2 4 litre
i 0.1
0.05
Final concentration of A = 0.0125 M Ans.
4
1 C0 0.693 1 1
22. k= . ln = . ln
t C t 1/ 2 20 0. 8
t1/2 = 62.13 min. Ans.
24. 3A (g) 2 B (g) + 2C(s)
t=0 6 atm 0
t = 20 min (6 – 3x) atm 2x atm
t= 0 4 atm
But at t = , the total pressure is 4.05 atm. The addition pressure is due to V.P. of solid, which is
(4.05 – 4) 0.05 atm
PT = PA + PB + V.P. of solid
or , 5.05 = (6 –3x) + 2x + 0.05 x = 1
t1/2 = 20 min
t75% = 40 min, t87.5% = 60 min
t93.75% = 80 min Ans
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25. A(g) + B(g) 2C(g) + D(g)
R = K [A]1/3 [B]2/3
When C A0 = 1M; CB0 = 1M
R = K[A]1
1 C A0
K = t ln C
A t
1 1
2.31 × 10–3s–1 = 600 sec ln C
A t
1
2.31 103 600 ln
C A t
1
1.386 = ln C
A t
1
4 = CA
CA t = 1/4
A(g) + B(g) 2C(g) + D(g)
At t = 0 1M 1M
At t =600 sec 1 – x 1–x 2x x
C At = 1 – x
1
=1–x
4
x = 3/4
3 11
Total concn = 2 + x = 2 + = = 2.75 mole/litre
4 4
1 110 1
26. K= ln = × 0.095 min–1
10 100 10
0.693
Time taken to double the concn = × 10 = 72.9 min]
0.095
28. From 1st and 2nd data order of reaction w.r.t. ICl is 1, from 1st and 3rd data order of reaction w.r.t. H2 is
1, so overall order of reaction is 2.
30. log(23.5) = 1.37 & log (95) = 1.97
log[( t1/ 2 )1 / (t1/ 2 ) 2 ] 1.37 1.96
n=1+ log (P2 / P1 ) 1 + log (1 / 2) = 3]
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32. rate law r = k [A]m
0.3
r1 = M/min from graph
5
0.2
r2 = M/min from graph
5
m m
r1 3 [A]1 1. 5
r2 = 2 = [A]2 = 1 m =1
0. 3 1
= k (1.5) k= min–1
5 25
1
rate = k × [A] × 2 = 0.08 Mmin–1 Ans. ]
25
33. Rate = k . [Acetone]x . [Br2]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)
y
0.025
(i) (ii), 1 =
0.050
y = 0, hence rate does not depend upon the concentration of Br2.
z z
6 0.025 1 1
(i) (iii), = ; =
12 0.050 2 2
z=1
x
3 3
(i) (iv), =
4 4
x=1
34. For second order
1
t1/2 = [A] k
0
log t1/2 = –log [A]0 + log 1/k
Hence reaction is second order.
1 1 1 4 1
k= A A = k t75%
t [A ]t [A ]0 0 0
4 1 300
3[A ]0 [A]0 = kt25% t25% =
9
= 33.33 min.
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0.01
0.02
35. 100 = K 0.02n
10 3
0.01
0.04
100 = K 0.04n
0.25 10 3
2n = 8 n = 3
ln 2 0.693
36. t1/2 = K K 0.02 0.03 = 13.86 min.
1 2
1 n
120 0.1
37. t1/2 CAO1–n =
30 0.2
n 1
1 1
or, = n–1=2 n=3
4 2
38. No backward reaction, since QP < KP . So pressure remained unchanged.
39. r = k [CH3COOCH3][H+]
r = k' [CH3COOCH3] where k' = k [H+]
2.303 V V0
Also k' = 6.93 log V V
t
2.303 50
= log
6.93 25
k' = 0.1 min–1
k' 0. 1
k= = = 1 M–1 min–1
[H ] 0. 1
40. At t
[B] final = [A] initial
so B is correct ]
41. P(g) Q(g) + R(g)
t = 0 1.5 atm
t =20 1.5 – x x x 1.5 + x = 2 atm
x = 0.5 atm
7
t =40 1.5 – x' x' x' 1.5 + x' = atm
3
7 3 5
x' =
3 2 6
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at t = 20 min
1 1.5 1 3
K= ln ln
20 1.5 x 20 2
at t= 40 min
1 1.5
K= ln
40 1.5 x '
1 1.5 1 9 1 3
K= ln ln ln ]
40 1.5 5 40 4 20 2
6
42. A(g) B(g) + C(g) + D(s)
1– nT = 1 +
1
1.75 = 0.75
1
K × t = ln 4 t =2
43. A(g) B(g) + C(g)
t=0 P 0 0
t = t P–p 2p p PT = P + 2p = P10
x
2p – x p =
2
P
Kt = ln
Pp
10 P 2P
K× = ln ln
60 P P 3p P10
P 10
2
2P
K = 2.303 × 6 log 3P P hr–1
10
P
(B) K × 10 = ln min 1
x
P
2
44. Rate of disappearance of A = KA [A]n
1
a3t =45°
Slope = KA (n–1) = 1 3 A 2B
t (min)
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1 dA
n –1 = 3 Rate of reaction = K r C nA
3 dt
dA
n=4 3K r C nA
dt
dA
3KA = 1 K A C nA
dt
1
KA =
3
1
Rate of disapperance of A = KACA4 = ( 0. 2) 4
3
1.6 10 3 16 10 4
Rate of reaction = = M min 1
9 9
45. A(g) 2B(g) + C(g) Kr = 1.386 × 10–4
At t = 0 0.1 mole volume is 1 L
After 5000 sec 0.1 – x 2x x
1 0.1
1.386 × 10–4 = ln
5000 0.1 x
0.1
0.693 = ln
0. 1 x
0.1
2=
0.1 x
0.1 = 2x
0. 1
x=
2
Now after 5000 sec , Total moles = 0.1 + 2x = 0.2 mole
Volume of reaction mixture became 2L
0. 1
0.1 x 0. 1
Concentration of A = = 2 = M = 0.025 M ]
2 2 4
46. [A] << [B]
Rate = K' [A]m K' = K[B]n
Since on keeping concentration of B same (K' same) on doubling concentration of A, t1/2 gets doubled
t1/2 a m=0
On keeping the concentration of A same, on doubling concentration of B, t1/2 remains same i.e. K'
remains same hence n = 0.]
47. for first order reaction t1/2 is independent of initial concn.
Time taken to reduce from 0.4a to 0.2a (a initial conc.) = t1/2 ]
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48. A + B C
Initial concn a (2M) b (3M)
at 't' a–x (0.5M) b–x (1.5M)
1 a (b x )
t= ln
k (b a ) b(a x )
1 2 1.5
= ln
k (3 2) 3 0.5
1
= ln 2 = 104 ln2 sec.]
k
49. r = k [A]x [B]y
0.1 = k [0.3]x [0.3]y ....(i)
0.4 = k [0.3]x [0.6]y ....(ii)
0.2 = k [0.6]x [0.3]y ....(iii)
Dividing (i) and (ii) y=2
Dividing (i) and (iii) y=1
Rate = k [A] [B]2
50. 3A(g) 4B(g) + 2C(g)
1.5 atm
t = 10 min 1.5 – 3P 4P 2P
1.5 + 3P = 3
P = 0.5
i.e. reaction has gone to completion so order should be less than 1.
51. 3A(g) 4B(g) + 2C(g)
1.5 atm
t = 10 min 1.5 – 3P 4P 2P
1.5 + 3P = 3
P = 0.5
i.e. reaction has gone to completion so order should be less than 1.
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CHEMIST RY
MPP
MASTER PRACTICE PROB LEM S
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 03
CHEMICAL KINETICS
SOLUTIONS
3. A(g) B(g) + 2C(g)
Pi 20 torr
Pt=10 20–p p 2p ptotal = 20 – p + p + 2p = 40 torr
p = 10 torr
so 10 sec is half life of A
ln 2
k= t = 0.07 sec–1
1/ 2
22. Theory based
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 04
ST
CHEMICAL KINETICS
SOLUTIONS
16. Rate = k(P)n
1 = k (0.95 P0)n
0.5 = k (0.67 P0)n
n
1 0.95P0
⇒ =
0.5 0.67P0
⇒ 2 = (1.4)n
⇒ 2' = (21/2)n ⇒ n = 2]
17. Let the rate equation be k [A]x [B]y
From Ist values,
0.045 = k[0.05]x [0.05]y …..(i)
nd
Form 2 values,
0.090 = k[0.10]x [0.05]y …..(ii)
rd
Form 3 values,
0.72 = k[0.20]x [0.10]y …..(iii)
On dividing equation (i) by (ii), we get
x
0.045 0.05
=
0.09 0.10
1 x
0.05 0.05
0.10 = 0.10
∴x= 1
Similarly on dividing Eq. (ii) by (iii) we get
x y
0.09 01 0.05
= = 0.10
072 02
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y
0.01 01 0.05
=
0.08 02 0.1
y
0.05
025 =
0.10
025 = [0.5]y⇒[0.5]2 = [0.5]y
∴y=2
Hence, the rate law for the reaction
Rate = k [A] [B]2
18. A →
K1
B →
K2
C
Rate of formation of B is
d [B]
= k1 [ A ] − K 2 [B]
dt
dB
⇒ 0 = k1[A] – k2[B] Give, 0
dt
⇒ k2[B] – k1[A]
k1
⇒ Concentration of B, [B] =
K2
[A]
19. In first order reaction, the rate expression depends on the concentration of one species only
having power equal to unity.
− d [r ]
nr→products = k [r ]
dt
On integration, in[r] = kt – In[r0]
Or In(r) = In(r0)–kt
Y = c + mx
M = slope = – k (negative)
C = intercept = In (r0)
The graph for first order reaction is
In (r)
In zero order reaction
[r] →product
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−d [r ]t
∴ = k or –d[r]t = kdt
dt
On integrating, –[r]t = kt + c
If t = 0, [r]t = [r]0
∴ –[r]t = –[r]0 –kt
Thus the graph plotted between [r]t and t gives a straight line with negative slope (–k) and
intercept equal to [r]0.
The graph for zero order reaction is
[r]
20. Only statement (4) is incorrect, Corrected statement is “Activation enthalpy to from C is 15 kg
mol–1 more than 5 kg mol–1 that is required to form D”. It can be easily explained by following
20
15
Activation
Enthalpy10
D enthalpy
(KJ mol–1)5
A+B
Reaction C
Coordinate →
Activation enthalpy (or energy) is the extra energy required by the reactant molecules that
result into effective collision between them to form the products.
21. The expression for bacterial growth is
N = N0et
N0
= e– t
N
From 0 to 1 hour N’(t) = N0et
dN
From 1 hour onwards, = −5N2
dt
On differentiating the above equation from N’ to N we get.
N t
∫
eN0
N–2 dN = −5 ∫ dt
1
[At 1 hour, N’ = eN0]
1 1
− =−
5(t 1)
N eN0
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Multiply both sides by N0, we get
N0 1 N0 1
− = 5N0 (t − 1)or, = 5N0 (t − 1) +
N e N e
N0 1
= 5N0 t − 5N0
N e
N0
N
t(h)
On comparing the above equation with equation of straight line, y = mx + c
1
We get m = 5N0, c = − 5N0
e
N0
∴ Plot of vst is shown aside.
N
22. Key Idea The Arrhenius equation for rate constants at two different temperatures is
k2 Ea T2 − T1
log = [where, T2> T1]
k1 2.30R T1T2
Where, k1 and k2 are rate constants at temperatures T1 and T2, respectively.
R = Gas constant, Ea = Activation energy
For the reaction, H2 + I2 → 2Hl
Given, k1 = 2.5 × 10–4 dm3mol–1s–1
T1 = (273 + 327)K = 600k
K2 = 1 dm3mol–1s–1 at T2 = (273 + 527)K = 800K
k2 Ea T2 − T1 1 Ea
Now, log = ⇒ log −4
=
k1 2.30R T1T2 2.5 × 10 2.303 × 8.314 × 10 −3
800 − 600
600 × 800
(10 × 103 ) Ea 200
⇒ = ×
2.5 0.019 48 × 10 4
⇒ log4 + 3log10 Ea × 0.022
2 × 10g2 + 3 3.6
⇒ Ea
= = 163.6KJmol–1
0.022 0.022
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23. In the given reaction; x A→y B
d[A ] d [B]
=
log10 log10 + 0.3010
dt dt
Value of log2 = 0.3010
Substituting 0.3010 by log2
d[A ] d [B]
log10 − = log10 + log2
dt dt
Using logarithm rules,
d[A ] d [B] 1 d [ A ] d [B]
− = 2× ⇒− = .....(i)
dt dt 2 dt dt
Using the rate equation (i) to determine the reaction involved is
2A→B
Option that fits correct in the above reaction is (3).
24. Key Idea The rate of a chemical reaction means the speed with which the reaction takes
place.
For R→P
Decrease in conc.of R ∆ [R ]
Rate of disappearance of R = = −
Time taken ∆t
Increase in conc.of P ∆ [p ]
Rate of appearance of P = = +
Time taken ∆t
Given [N2O5]nitial = 3.00 mol L–1
After 30 min, [N2O5] = 2 75 mol L–1
2N2O5(g) → 4NO2(g) + O2(g)
t=0 3.0 M
t = 30 2.75 M
1 −∆ [N2O5 ] 1 ∆ [NO2 ]
From the equation, It can be concluded that × = ×
2 ∆t 4 ∆t
−∆ [N2O5 ] −(2.75 − 3.00)molL–1 0.25 −∆ [N2O5 ] −∆ (N2O5 )
= = ⇒ and = −2
∆t 30 30 ∆t ∆t
−∆ [N2 ] 0.25
⇒ =−2 ×
∆t 30
= – 1.667 × 10–2mol L–1 min–1
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25. Let the rate expression is r ∝ [A]a [B]b
a b
r 0.1 0.25
From experiment=
I, 2 ×
r1 0.1 0.20
a b
r 0.1 0.25
⇒ 2
= ×
r1 0.1 0.20
b 0 b
5 5 5
⇒=
1 ⇒ = ⇒=
b 0
4 4 4
a b
r 0.2 0.30
From experiment=
II, 3 ⇒
r1 0.1 0.20
1.386 × 10 −2
( 2 ) × (1.5 )
a 0
⇒ =
0.693 × 10 −2
⇒ 2 = 2a × 1 ⇒ 21 = 2a = 1
⇒ So, r ∝ [A]1[B]0⇒ r ∝ [A]
Order of the reaction (n) = 1
⇒Now, let for the 1st experiment,
r1 = k ⋅ [A]
r1 6.93 × 10 −3
⇒= = 6.93 × 10 −2 s−1
[A] 0.1
0.693 0.693
⇒ t 50
= = = 10s
k 6.93 × 10 −2
26. For the reaction 2A + B → products.
Let, the rate expression is r a [A]a[B]b
a b
r 2A 2B
Expt 1 2 =
r1 A B
2.4
⇒ = 2a × 2b ⇒ 23 = 2a +b
0.3
⇒ 3 = a + b ….(i)
a b
r2 2A B
Expt 2 =
r1 A B
0.6 a
⇒ 2 × 1 ⇒ 21 = 2a⇒ a = 1 …(ii)
0.3
∴From Eq. (i), 1 + b = 3 ⇒ b = 2
⇒ Order of the reaction (n) = a + b = 1 + 2 = 3
⇒ Order of the reaction wrt. A = 1
⇒ Order of the reaction wrt. B = 1
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−Ea /RT
27. The Arrhenius equation is, k = A.e
Where, k = rate constant,
A = Arrhenius constant, Ea = activation energy, and T = temperature in K
From the equation, it is clear that k decrease exponentially with EaSo, the plot-I is correct.
In the plot-II k is plotted with temperature (in °C but not in K). So, at 0°C, k ≠ 0 and k will
increase exponentially with temperature upto 300°C, Therefore, the plot-II is also correct.
28. Let the rate law is r ∝ [A]a[B]b
∴ a and b are the order of reaction w.r.t A and B respectively
⇒ Comparing first three (I, II, III) experiments :
2.4 × 10 −2
a b
rII 0.1 0.2
= × ⇒ −3
= 1 × 2b
rI 0.1 0.1 6 × 10
⇒ 2b = 4 ⇒ b = 2
12 × 10 −2
a 2
rIII 0.2 0.1
= × ⇒ = 2a × 1
rI 0.1 0.1 6 × 10−3
⇒ 2a × 2 ⇒ a = 1
⇒ rI × k × (0.1)1(0.1)2 ⇒ 6 × 10–3 = k × 10–3
⇒ k = 6L2 mol–2 min–1
⇒ Expt. IV : rII = 6 × (X)1 ×(0.2)2
⇒ 7.2 × 10–2 = 6 × (X) × (4 × 10–2) ⇒ X = 0.3 mol L–1
⇒ Expt. V : rv = 6 × (0.3)1 ×(Y)2
⇒ 2.88 × 10–1 = 6 × 0.3 × (Y)2 ⇒ 0.4 mol L–1
29. Only statement (2) is true whereas all other statements are incorrect. A zero order reaction is
a multistep reaction because in most of the zero order reactions, free radical is the
intermediate which follow chain-initiation, chain-propagation and chain-termination like steps,
e.g., free radical substitution reaction.
(1) A second order reaction is always a single step reaction, e.g., SN2 and E2 reactions.
(3) A first order reaction may be a multi-step reaction when intermediate of the reaction, like
carbocation (l1) gets rearranged into its most stable form (l2).
Same is the case with (4).
So, options (1), (3) and (4) are not true .
30. For a reaction,
3
2A + 3B + C → 3P
2
For a reaction, aA + bB = cC
Rate of reaction,
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1d [A] 1d [B] 1 d[C]
⇒ − =
− =
a dt b dt c dt
∴ For given reaction,s
1d [A] 1d [B] 2 d[C] 1 d[P]
− =
− =
− =
2 dt 3 dt 3 dt 3 dt
d[A] 2 d[B] 4 d[C] 2 d[P]
= = =
dt 3 dt 3 dt 3 dt
31. We know that, N = N0e −kt
ln 2
K can be calculated as : K = (Here, t1/2 = half-life)
t1/2
The time required for the concentration of A to be four times that of B. Hence, A = 4B
ln2t In2t
− − ln2t ln2t
N0e 300 = 4.N0e 180 ⇒ − =ln 4 −
300 180
1 1 2 × 180 × 300
⇒ ln 2t − 2ln 2 ; t =
= = 900s
180 300 120
32. ∴ k = Ae−Ea /RT
Taking natural logarithm on both sides, the Arrhenius equation becomes.
E 1
⇒ In k = In A – a
R T
Ea 103
⇒ In k = In A – 3
×
R × 10 T
Ea 103
Slope of a graph = − =
−
R × 103 5
Ea = 2R × 103 J mol–1 ⇒ Ea = 2R kJ
33. We know that,
Rate = k (concentration)n
[n = order of reaction and k = rate constant]
Taking log both side, log (Rate) = log k + nlog [concentration]
Slope of graph is the order of reaction greater the slope, greater is the order of reaction.
∴ Concentration sequence for the order of reaction is D > B > A > C.
Hence, the correct option is (4).
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34. 2H2(g) + 2NO(g) N2(g) + 2H2O(g)
Rate law for forward reaction is given as :
Rate = kf[NO]2 [H2]
Rate of forward reaction is equal to rate of reverse reaction at equilibrium and also, at
k1
equilibrium (K) =
kb
where, K(equilibrium constant)
[N2 ][H2O]2 k f [N2 ][H2O]2
= ⇒ =
[H2 ]2 [NO]2 k b [H2 ]2 [NO]2
Rearranging :
kf[H2] [NO]2 = kb[N2] [H2O]2 / [H2]
∴ Rate of reverse reaction = kb[N2] [H2O]2 / [H2]
35. According to Arrhenius equation
Eact
k = Ae−Ea /RT ⇒ log k = log A –
2.303 RT
Eact = activation energy
1 Eact
Slope of the graph of ‘log k’ vs is −
T 2.303R
Greater the value of Eact, more will be the negative slope.
From the graph, most –ve slope = c, followed by a, d and b.
∴ Order of activation energies must be Ec > Ea > Ed > Eb
36. For catalysed reaction, let Ea be x.
Then, for uncatalysed reaction, Ea = x + 30 (given in question).
Also, rate of reaction at 700 K (without catalyst) = rate of reaction at 500 K (with catalyst).
∴ k at 700 K without catalyst = k at 500 K with catalyst.
Using relation, k = Ae−Ea /RT
Ea = Activation energy.
∴ Ae −( x +30)/700R = Ae − x/500R
x + 30 x
∴ = ⇒ 7x = 5x + 150
700 500
2x = 150 ⇒ x = 75 kJ
37. A2 + B2 2AB
Ea (forward) = 180 kJ mol–1
Ea (backward) = 200 kJ mol–1
In the presence of catalyst,
Ea (forward) = 180 – 100 = 80 kJ mol–1
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Ea (backward) = 200 – 100 = 100 kJ mol–1
∆H = Ea (forward) –Ea (backword)
= 80 –100 = –20kJ mol–1
For the value of enthalpy change of the reaction, negative sign can be neglected.
38. → H2C = HC–CH = CH2
[A]0
Kt =
n
[A]t
100
3.3 × 10–4 × t =
n
60
t = 1547.956 sec
t = 25.799 min
26 min
39. Given :
C12H22O11 + H2O 10 → C6H12O6 + C6H12O6
I order
t1/2 = hr Glucose Fructose
3
t=0 a = [A]0 – –
t = 9hr a – x = [A]t
k×t A
from I order kinetic : = log 0
2.303 At
n2× 9 1
⇒ = log
10
× 2.303 f
3
0.693 × 9 × 3 1
⇒ = log
23.03 f
1
⇒ log = 0.81246 = 81.24 × 10–2
f
⇒ x = 81
Ea
40. log K = log A –
2.303RT
Ea
|Slope| = = 10,000
2.303R
K Ea 1 1
=
log 2 −
1
K 2.303R T1 T2
T2 = 526.31 526K
Hence answer is (526)
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41. T1 = 300K, T2 = 325K, K2 = 5K,
K Ea 1 1
=
ln 2 −
K1 R T1 T2
Ea 1 1
=
or, ln 5 −
8.314 300 325
or, Ea = 0.7 × 2.303 × 8.314 × 12 × 325 = 52271 J = 52.271 kJ
Nearest integer answer will be 52 kJ
3
42. For tritium ( 1 H )
No. of neutron (n) = 2
No. of proton (p) = 1
n
= 2
p
n
is high, tritium will emit b particle.
p
43. Fraction of molecules to have enough energy to react = e–Ea/RT
Ea
So, x=
RT
80.9 × 103
= = 13.9
8.31× 700
44. K300 = 10–4 K200 = ?
Ea = 11.488 KJ/mole R = 8.314 J/mole-K
K Ea 1 1
n=
So
300
−
K 200 R 200 300
K 11.488 × 1000 × 100
n 300 =
K 200 8.314 × 200 × 300
= 2.303
= n10
K 300
so = 10
K 200
1
K200 = 10−4
× K 300 =
10
= 10 × 10–5 sec–1
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45. Given t2 = 54 min T1/2 = 18 min
A B
t = 0 'x' M t = 0 'x' M
⇒ To calculate : [At] = 16 × [Bt] ...(1) time = ?
A0
⇒ For I order kinetic : [A t ] =
(2)n
n → no of Half lives
⇒ Now from the relation (1)
[At] = 16 × [Bt]
x x
⇒ = × 16 ⇒ (2)n2 (2)nt × (2)4
(2)nt (2)n2
t t
⇒ n2 = n1 + 4 ⇒ = +4
(t1/2 )2 (t1/2 )1
1 1 4 × 18 × 54
⇒ t − = 4⇒ t = ⇒ t = 108min
18 54 36
46. For 1st order reaction,
2.303 [A ] 2.303 100
= = = 1.999 × 10 sec ≈ 2 × 10 sec
–3 –1 –3 –1
K .log 0 .log
t [A t ] 570 sec 32
47. Reaction : 2A + B2 → 2AB
As the reaction is elementary, the rate of reaction is is
r = K. [A]2 [B2]
on reducing the volume by a factor of 3, the concentrations of A and B2 will become 3 times
and hence, the rate becomes 32 × 3 = 27 times of initial rate.
48. r = k[NO]m [Cl2]n
= k(0.1)m (0.1)n ...(1)
= k(0.1)m (0.2)n ...(2)
m
= k(0.2) (0.2) ...(3)
n=1
m=2
m+n=3
1 100
t 99.9% K ln 0.1 ln1000 3ln10 3 × 2.3
49. = = × t 50% = ×1 = = 10
t 50% 1 ln2 ln2 0.69
ln 2
K
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN)
ST NO.01
CHEMICAL EQUILIBRIUM
SOLUTIONS
5. H2 + Ι2 2HI
0.4 0.4 2.4
2.4 × 2.4
K= = 36 (Since volume term is cancelled)
0.4 × 0.4
7. Mol. mass of HI = 1 + 127 = 128
64 g HI = 64 / 128 = 0.5 mole
0.5
[HI] = M = 0.25 M
2
9. Kp = Kc (RT)∆n
2Kc = Kc (RT)∆n
2 = (RT)1
2
T= = 24.36 K
0.0821
12. N2 + 3H2 2NH3
1 3 0
0.5 1.5 1
1.5
PH2 = P = P/2
3
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN)
S NO.02
CHEMICAL EQUILIBRIUM
SOLUTIONS
4. KC = (mole/litre)∆n
where ∆n = no of moles on product side – no. of moles on reactant side
Hence ∆n = – 2
so moles on reactant side > moles on product side
so on increasing pressure reaction will get shifted in forward direction.
5. A B+C
1 0 0
1–α α α = (1 + α)
α2
Kp1 = . p1
1 − α2
D 2E
1 0
1– α 2α = (1 + α)
4α 2
K p2 = . p2
1 − α2
K p1 p1
=
K p2 4p2
p1 Kp1
so =4. = 4 × 9 = 36 : 1
p2 Kp2
8. H2(g) + Br2(g) 2HBr(g)
Intial pressures 0 0 10.0 bar
At equilibrium p/2 p/2 (10.0-p)
p2HBr
Kp =
pH2 × pBr2
(10 − p)2
=
(p / 2)(p / 2)
Taking square root of both sides
10 − p
4 × 102 =
p/2
10
200 p = 10 - p ; p= bar
201
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1 10
=
p p=
/2 =
bar =
2.5 × 10-2bar ; P p=
/2 2.5 × 10–2 bar ; .
2 201
H2 Br2
PHBr = 10 − p ≈ 10 bar
9. (i) Molar concentrations:
mol 1
[PCI5] = = = 0.5 mol L–1
L 2
2
[PCI3] = = 1.0 mol L–1
2
2
[CI2] = = 1.0 mol L–1
2
(ii) Mole fractions :
Total moles at equilibrium = 1 + 2 + 2 = 5
nPCI5 1
∴ XPCI5 = = = 0.2
ntotal 5
nPCI3 2
XPCI3 = = = 0.4
ntotal 5
nCI2 2
XCI2 = = = 0.4
ntotal 5
(iii) Equilibrium constants :
[PCI3 ][CI2 ] 1× 1
Kc = = = 2 (mol L–1)–1 = 2 L mol–1
[PCI5 ] 0.5
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN)
S NO.03
CHEMICAL EQUILIBRIUM
SOLUTIONS
1. in one litre 16.6 × 2 = 33.2 mg of solid can be dissolved
so in 2 litre amount dissolved = 66.4 mg
so undissolved solid = (100– 66.4) mg
= 33.6 mg
3. Equilibrium will shift in the forward direction by increasing the concentration of reactant.
5. CaCO3(s) CaO(s) + CO2(g)
K p = PCO2
∆H r0
log Kp = log A –
2.303 RT
∆H r0 l
log PCO2 = log A – ......... (i)
2.303 R T
Graph (1) represents (i) and its slope will be used to determine the heat of the reaction.
7. If 1 mole neon gas is removed pressure will decrease and piston will come down as V.P.
remains unchanged therefore some water vapour will be condensed and amount of water will
increase.
8. Let reaction be
N2 + 3H2 2NH3
3
[NH3 ] (2)2 2 8
Kc = = = =
[N2 ] [H2 ]3
1 3 3 27
2 (3)
Now after distrubing equilibrium
then N2 concentration will be > 0.5 M and there will be some time taken for attainment of
equilibrium hence graphs (2) and (3) can be discarded from calculations it can be proved that
the amount by which N2 should reaction should be less than 0.2 Hence the result.
9. CH3Cl (aq) + OH¯ CH3OH (aq) + Cl¯ (aq)
t = 0 0.05 0.1 0 0
teq. →0 0.1 – 0.05 = 0.05 0.05 0.05
As equilibrium constant is very large so reaction will be almost 100% complete.
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10. (1) As reaction is endothermic therefore it will go in the forward direction hence moles of CaO
will increase.
(2) With the increase or decrease of volume particle pressure of the gases will remain same.
(3) Due to the addition of inert gas at constant pressure reaction will proceed in the direct in
which more number of gaseous moles are formed.
11. AB A+ + B¯ K1
y y–x
AB + B¯ AB2– K2
y–x x
x
⇒ K1 = (y – x)y K2 =
y−x
k1 y
⇒ = (y – x)2
k2 x
12. N2O4 2NO2
t=0 a 0
t a(1 – α) 2aα
46
vapour density = = 30.67
1+ α
so 1 + α = 1.5 = 0.5 = 50 %
1.5 × 1.5 × 0.082 × 300
Total pressure = = 6.75 atm
8.2
4α 2
so Kp = P = 9 atm
1 − α2
138
and for density of mixture = gm/L = 16.83 gm/L
8.2
13. On adding Cl– ion the equilibrium will shift in the backward direction so. [COCl4]2– will increase
on dilution the volume will increase. Now as
n[CO(H2O)6 ]2+ .nCl
4
− 1
KC = 2−
.
nCOCl4 V4
so. Q will get decreased and equilibrium will shift in the forward direction. Though the amount
of [CO(H2O)]2+ will get increased but its concentration can not get doubled as volume has
increased.
As reaction is exothermic in nature so increasing temp will shift equilibrium is backward
direction.
14. (1) KP = KC (RT)∆n
KP KP
= (RT)∆n as ∆n < 0 ⇒ <1 ⇒ KP < KC
KC KC
(2) ∆n > 0
(3) gaseous products is more than gaseous reactants,
(4) As the reaction is not containing any gaseous component therefore KP is not defined for
this.
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN)
S NO.04
CHEMICAL EQUILIBRIUM
SOLUTIONS
1. N2 + 3H2 2NH3 + Heat for the Haber’s process
(g) (g) (g)
Hence as per Le-Chatelier principle use high P & low T to maximize yield.
2. kp = 16
∴ pc2 = 16 or pc = 4 atm
∴ 4 × 20.5 = nc × 0.082 × 1000 ∴ nc = 1.0
eq (Total moles)
It means one mole of c (out of 2 added) will react with 0.5 mol of B to produce 0.5 mole of A.
10. A2 + B2 2AB ; K = 49
1 1 0
1–x 1–x 2x
2x
=7
1− x
⇒ 2x = 7 – 7x
⇒ 9x = 7
7
⇒ x=
9
2/9 1
∴ XB2 = =
2 9
11. If the value of KC is very large the reaciton is almost complete.
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CHEM IST RY
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TARGET : JEE(ADVANCED)
ST
NO . 05
CHEMICAL EQUILIBRIUM
SOLUTION
Q.2 Q equilibrium is " dynamic" in nature
ammonia obtained will have tritium & hence will be radioactive .
1
Q.3 10 2 = KC [0.08 × 500]–2
9
1
10 2 = KC × (40)–2
9
1 KC 16
KC =
9 100 40 40 9
Q.4 N2O4 (g) 2NO2 (g)
at P1 (t=Eq) 1–0.4 2(0.4)
= 0.6 = 0.8
at P2 (t=Eq) 1–0.5 2(0.5)
= 0.5 =1
Q temperature is same , KP is same
2 2
0. 8 1
P1 P2
1.4 1 . 5 P1 1.4 0.6 7
= 0.5
0.6
P1 P2 P2 (0.8) 2 1.5 0.5 = 4
1.4 1.5
Q.5 N2O3 NO + NO2
1 –
Dd 38 23.75
Q= = 0.6
d (n 1) 23.75(2 1)
wt. of N 2O 3
Mass % of N2O3 in the equilibrium mixture = 100
Total wt.
0.4 76
= 100 = 40 %
0.6 30 0.6 46 0.4 76
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2
6
2
Q.6 QC = 3 1.125
2 4
2 2
Q QC > KC so reaction will proceed in backward direction.
N2(g) + 3H2 (g) 2NH3 ;
at equilibrium : 2 + x 4 + 3x 6 – 2x
Q At equilibrium [H2(g) ] = [NH3(g)]
4 3x 6 2 x
= x = 0.4
2 2
2 x
[N2(g) ] at equilibrium = 1.2 M ]
2
Q.7 Let initial mole of SO2Cl2 (g) is one
SO2Cl2 (g) SO2(g) + Cl2(g)
Initial mole 1 0 0
At eq m 1–
Total no. of moles at equilibrium = 1 +
Now,
1
PSO P ; PSO PCl P
2 Cl 2 1 2 2 1
2
P
PSO .PCl 1
2 2 2
Kp = P 1 P
SO 2Cl 2 P 1 2
1
2
1.125 = 2 ; 2 = 0.36 ; = 0.6
1 2
1
Mole fraction of SO2Cl2 0.25 ; Mole fraction of Cl2 = SO2 =
1 1
0.6
0.375
1.6
Average molar mass of mixture = (64 + 71) × 0.25 + 64 × 0.375 + 71 × 0.375
33.75 + 24 + 26.625
84.375 g/mole Ans.
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**
SO2Cl2 (g) SO2(g) + Cl2(g)
At eqm 2–x x x
x2
1.125 = x2 – 2.25 – 1.125x = 0
(2 x )
1.125 1.265 4 2.25
x= 1.04
2
PSO 0.96 ; PSO 1.04 ; PCl 1.04
2Cl 2 2 2
Ptotal = 2 + x 3.04
0.96
M.f.of SO2Cl2 = 0.315 ; M.f. of SO2 0.342
3.04
M.f. of Cl2
Average Molar mass (64+71) × 0.316 + 0.342 × 64 + 0.342 × 71
42.66 + 21.888 + 24.282 88.83 Ans.
(1.5 / 5) 2
Q.8 QC = 0.5625 ; Q > KC
(2 / 5) 2
reaction will proceed in backward direction
N2 (g) + O2(g) 2NO(g)
Initial moles 2 2 1.5
moles at eq m 2+x 2+x 1.5 – 2x
2 x 2 x 1.5 2x
conn at eqm
5 5 5
2
1. 5 2 x
2
[ NO(g)] 5
2
KC = [ N 2 (g)][O 2 (g )] 2x
5
1. 5 2 x
0.04 0.2
2x
1.5 – 2x = 0.4 + 0.2 x
x = 0.5
1.5 2x
Equilibrium concentration of NO = 0.1 M Ans.
5
Q.9 Ptotal = PHNO 3 + PNO 2 + PH 2O + PO 2
Q PNO 4 P & PH O = 2 P
2 O 2 2O 2
Ptotal = PHNO 7 PO 30 – 2 = PO × 7
3 2 2
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28
PO 4
2 7
4
PNO . PH
2O
PO (4 4) 4 (2 4) 2 4
KP 2
4
2
4 = 220
2
PHNO
3
n g
KP = KC ( RT ) KC (0.08 × 400)3
2 20 220
KC = 32 Ans.
(32)3 215
Q.10 KP = p CO 2 = 8.21 atm
8.21 × 10 = n CO 2 × 0.0821 × 1000
n CO 2 = 1
n CO 2 = nCaO = 1
weigth of CaO in gm = 1 × 56 = 56 gm Ans.
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CHEM IST RY
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ST
NO . 06
CHEMICAL EQUILIBRIUM
SOLUTION
Q.1 CO(g) + H2O(g) CO2(g) + H2(g) , Keq = 10 ....(i)
CH4(g) + H2O(g) CO(g) + 3H2(g) , Keq = 40 ....(ii)
On adding e.q. (i) & e.q. (ii)
Keq = K1 × K2 = 400
Q.2 S8(s) 8S(g)
0.01 0
0.01 (1–x) 0.01x × 8
960
0.01 x × 8 = = 0.043 x = 0.54
22400
Fraction of undissociated
S8 = 1 × 0.54 = 0.46 approx Ans (D)
Q.3 NH2COONH4(s) N2(g) + H2(g) + CO(g) + O2(g)
at equilibrium P 3P P P/2
PTotal = PN 2 PH 2 PCO PO2
11P
22 atm = P = 4atm
2
KP = PN 2 ( PH 2 ) 3 PCO ( PO 2 )1 / 2 = 4533 2
Q.4 A .3H2O(s) A. H2O (s) + 2H2O(g) KP = 9 atm2
x mole KP = PH2 2O
PV = nRT
3 at × 24.63lt = n H 2O × 0.0821 × 300
n H2O = 3 mole
5 mole of H2O (g) should be added.
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Q.5 PCl5(g) PCl3 (g) + Cl2(g)
Initially 10 0 0
At equilibrium : 10 (1–) 10 10
2
KP = PT
(1 2 )
Q = 50%
(0.5) 2 20
KP = 2
20 =
(1 0.5 ) 3
2 20
Q.6 Q KP = PT =
1 2 3
2 20
2
35 =
1 3
2 20 4 4
= = =
1 2 3 35 3 7 21
212 = 4 – 42
4
2 =
25
2
=
5
10 mole
Q PCl5 PCl5 + Cl2
10(1 – ) 10 10
Total mole at equilibrium = 10(1 + )
Partial pressure of PCl5 = X PCl5 PT
2
101
10(1 ) 5 35 = 15 atm
= 35 =
10(1 ) 2
101
5
Q.7 As Kp & P are same , also remain same
V2 30(1 )
V1 = 10(1 ) = 3.0 ]
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1
Q.8 SO3 (g) SO2 (g) + O
2 2
Dd
=
d (n 1)
2 40 d
=
3 3
d 1
2
d = 30
Q.9 2AB(s) A2(g) + B2(g)
0.5 + x x
Kp = PA 2 .PB2 0.06 = (0.5 + x) x
x2 + 0.5 x – 0.06
0.5 (0.5) 2 4(0.06) 0.5 0.7
x= 0.1
2 2
Ptotal = PA 2 PB2 0.6 + 0.1 0.70 atm
(1.5 / 5) 2
Q.10 QC = 0.5625 ; Q > KC
(2 / 5) 2
reaction will proceed in backward direction
N2 (g) + O2(g) 2NO(g)
Initial moles 2 2 1.5
moles at eq m 2+x 2+x 1.5 – 2x
2 x 2 x 1.5 2x
conn at eqm
5 5 5
2
1. 5 2 x
2
[ NO(g)] 5
2
KC = [ N 2 (g)][O 2 (g )] 2x
5
1. 5 2 x
0.04 0.2
2x
1.5 – 2x = 0.4 + 0.2 x
x = 0.5
1.5 2x
Equilibrium concentration of NO = 0.1 M Ans.
5
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CHEM IST RY
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ST
NO . 05
CHEMICAL EQUILIBRIUM
SOLUTION
Q.1 A(s) 2B(g) + C(g)
20 mm 10 mm
KP = (20)2 × 10 = 4000 mm3 of Hg
2 H 1 1
ln K R T T
1 1 2
2 60 103 1 1
ln
4000 2 300 400
2 60 103 100
ln 25
4000 300 400 2
K2 = 4000 e25
A(s) 2B(g) + C(g)
2x x
4x3 = 4000 e25 x3 = 1000 e25 x = 10 e25/3
Pressure = 3x = 3 × 10 e25/3 = 30 e25/3
Q.2 (A) On adding more water into the solution, solubility in terms of moles dissolved per litre will be same.
(B) As pressure of the gas increases solubility will increases.
(C) As temperature of the gas increases solubility also decrease
Q.3 2A(g) + 3B(g) 4C(g) + 5D(g)
4 mole 6 mole 0 0
0 0 8 mole 10 mole
2x 3x 8 mole 10 mole
Total mole at eq. 18
mole fraction
2x 3x 8 10
18 18 18 18
partial pressure
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2x 10 3x 10 8 10 10 10
18 18 18 18
5 4
10 10 8 10
39
10 18 18
KP = 2 3
6 2x 10 3x 10
18 18
1039 109 84 1030 212
6 2x 2 3x 3 184 3 2 2 2 33 x 5 38 2 4
1030 27
10 5
3 3 x
27 / 5
x= 10 6
9
PA = 2x
10 10
PD = 5.55
18
20 –1
Q.4 PCl3(g) + Cl2(g) PCl5(g) ; KC = M
3
t = teq x 0.1+x 0.1–x
20 (0.1 x )
3 (0.1 x )x
On solving x = 0.05
2
PNO 2
Q.5 N2O4 2NO2 K= =1
PN 2O4
At 60 atm PN2O4 = 40 atm
PNO2 = 20 atm
and reaction will backward so PN2O4 will be more than 40.
Q.6 C2H2(g) + O2(g) CO2(g) + H2O(g) H = –ve
To increase [CO2] , reaction should go in forward direction
On increases temperature, reaction goes in backward direction
On increasing pressure, reaction goes in direction of decreasing gaseous moles i.e. in forward direction.
On increasing volume, reaction goes in backward direction
On adding inert gas at constant pressure and temperature, reaction goes in direction of increasing gaseous
moles i.e. in backward direction.]
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Q.7 No effect of adding C (graphite)
KP = KC as ng = 0
A(l) A(g)
On increasing pressure, Boiling point increases
So normal boiling point (boiling point at 1 atm) > Standard boiling point (Boiling point at 1 bar)
Q.8 For water
A B
l
VP O g
S
C
TC
T
O is triple point and B is critical point.
(A) At absolute zero vapour pressure of solid will be zero.
(B,C) Beyond triple point it will get convert into other phases and liquid phase has minimum pressure
at this point.
(D) Beyond critical point phase of liquid will get changed.
Q.9 4HNO3(g) 4NO2(g) + 2H2O(g) + O2(g) ; KP = 1.28 × 10–20 bar3 at 300 K.
initial 2 0 0 0
finally 2–4x 4x 2x x
[ NO 2 ]4 [H 2 O]2 [O 2 ]
KP =
[HNO3 ]4
(4x )4 .(0.05) 2 .x
1.28 × 10–20 = [Neglect 4x in compare to 2]
( 2) 4
16 × 1.28 × 10–20 = (256 x4). (25 ×10–4). x
8 10 22
x5 = ;
25 105
x5 = 0.32 ×10–17 = 32 ×10–20
x = 2 × 10–4 × 1 × 105
x = 20
Partial pressure of NO2 = 4x = 80 Pa
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CHEMI STRY
MPP
M ASTER PRACTICE PR OBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 01
CHEMICAL EQUILIBRIUM
SOLUTIONS
no. of moles of O 2 96 1
3. Molar conc. = = × = 1.5 M
volume (in litre) 32 2
4. At equilibrium rates of backward and forward reactions become equal.
6. From given reactions. (nh xbZ vfHkfØ;kvksa ls)
1 1
(i) = – (iii) ;
(i) = – (iv) ; (iii) = – (ii)
2 2
7*. For endothermic reaction, Hº is positive so, if T2 > T1 then K2 > K1.
For exothermic reaction, Hº is negative so, if T2 > T1 then K2 < K1.
K1 b x
8. A B Kc = =
K2 ax
K1a K 2b
a-x b+x x = K K Therefore, (A) option is correct.
1 2
9. A+B C+D
3n n 0 0 t=0
(3n–x) (n–x) x x t = teq.
(n–x) = x
n
n = 2x x= 2
2 2
C 2
V V
10. KC = 3 9= 3 V=6L
B A 2 2
VV VV
14. A + B C + D
Initial 1 1 0 0
At equili. (1 – x) (1 – x) x x
[C] [D]
Kc = [ A ] [B] = 9
x .x
=9
(1 x )2
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or x2 = 9 + 9x2 – 18 x
or 8x2 – 18x + 9 = 0
3 3
x= or
2 4
Hence, among the given options, the option (3) i.e., 0.75 is correct.
16. N2(g) + 3H2(g) 2NH3(g)
P P
At equilibrium P , + P + PNH3 = 2P
3 3
2P 2P
2P 3 3 1 4 4
PNH3 = Kp = P 3 =
. Kp =
3 P P2 3 3 P2
3
17. 2SO2 (g) + O2 2SO3(g)
Kp = 4.0 atm–2
SO3 3
Kp = SO 2
2 O2
Given that at equilibrium the amount of SO2 and SO3 is the same so
SO3 2 1
SO2 2 O2 = 4 = 4 = 0.25 atm.
16 18
18*. (A) [ CH4] = = 0.1 M (B) [H2O] = = 0.1 M
16 10 18 10
35.5 44
(C) [Cl2] = = 0.05 M (D) [CO2] = = 0.1 M
71 10 44 10
19. A2(g) + 2B2(g) 2C2(g)
PA = 0.80 atm., PB = 0.4 atm.
2 2
Total pressure of the system = 2.8 atm.
PC = 2.8 – 0.8 – 0.4 = 1.6
2
PC2 (1.6)2
2
Kp = = = 20
PA 2 PB3 0 . 8 ( 0 . 4 )2
2
21. 2H2O (g) + 2Cl2 (g) 2HCl (g) + O2 (g)
Kp = 0.03 T = 427oC = 700 K
Kp = KC(RT)1
KP 0.03
KC = = 0.082 700
RT
–4
KC = 5.23 × 10
kc 1
22.* log k = log
p (RT )
kp = kc (RT) n = 1
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23. Using KP = KC (RT)ng
KP
so log K = ng log RT
C
so ng = –1.
25. C2H5OH (l) + CH3COOH (l) CH3COOC2H5 (l) + H2O (l).
a a 0 0
a 0.33a a – 0.33a 0.33a 0.33a
(0.33a) (0.33a)
KC = = KC = 1/4.
(0.67a) (0.67a)
28. 2SO3(g) 2SO2 (g) + O2(g)
t=0 a 0 0
t=teq. a(1–) a a 2
Total mole at eq. = a 1 2
1– 2(1 – )
PSO3 = P = × P0 ;
1 ( / 2) 0 2
2
PSO2 = P = ×P
1 ( / 2 ) 0 2 0
/2
PO2 = 1 ( / 2) P0
4 2 (P º )2
Pº
( 2 ) 2 2 3Pº
KP = = 2
2
4(1 – ) 2 ( 2 )(1 – )
(P0 )
[2 ]2
(1 ) 92 2 46
29. N2O4 2NO2 Mmix =
1
92
1– 2 Mmix =
1
D 46
= = (1 + ). Therefore, (A) option is correct.
d 46 /(1 )
D – d D D
30. = ; = – 1 . ; = + 1.
d d d
D–d D–d D
= ; = ; = – 1.
(n – 1)d d d
The point at which = 0.
D D
d – 1 = 0 ; So, = 1.
d
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CHEMI STRY
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M ASTER PRACTICE PR OBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 02
CHEMICAL EQUILIBRIUM
SOLUTIONS
Mmix M
1. (VD)mix = =
2 2 (1 )
so, as increases (VD)mix decreases.
PV 10 2 2.5
2.* 10–10 atm = PH52O PH2O = 10–2 atm. n= = 1 = 10–3
RT 300
12
3. KC = [CO2] = 0.05 mole/litre
so moles of CO2 = 6.50 × 0.05 moles = 0.3250 moles
CaCO3 CaO + CO2
1 mole of CO2 = 1 mole of CaCO3
0.3250 moles of CO2 = 0.3250 moles of CaCO3 = 0.3250 × 100 gm of CaCO3 = 32.5 gm of CaCO3
4. C(s) + CO2(g) 2CO(g)
3P
P–P/2 P= = 12
2
P2
so KP = = 2P = 2 × 8 = 16 atm.
(P / 2)
5. Gas product concentration increases while that of solid reactant is constant.
2
2 x
6. SO3(g) + CO(g) SO2 (g) + CO2 (g) 9=
2x
2 2 2 2
2+x 2+x 2-x 2-x x=1
n(SO 2 ) 1
neq = 3 + 3 + 1 + 1 = 8 n(SO3) + n(CO2) = 4 = <1
n(CO) 2
Therefore, (D) option is correct.
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7. (I) N2O4 2NO2 , Kc = 4
at point — A
Product
Q = Re ac tan t = 0
So, Q have minimum value at point A.
(II) at point [N2O4] = [NO2] = 0.1 M
NO2 2 0.1 0.1
Q= = = 0.1
N2O4 0.1
Q < Kc
So, reaction proceeds left to right
(III) Kc = Q at point [D & F].
11. H2(g) + I2(g) 2HI(g)
K2 H 1 1 50 H 1 1
log K = – ; log = –
1 2 .303R T1 T2 66 .9 2 .303R 623 721
After calculation negative value of H is obtained.
12. From thermodynamics.
H 1 1
13. log K2 / logK1 =
2.303 T2 T1
H = Positive
14. CuSO4 . 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g) KP = 2.25 × 10-4
KP = p 2 H2O = 2.25 × 10-4 p H O = 1.5 × 10-2
2
22.8 PH2O
Vapour Pr = = 3 × 10-2 R.H. = × 100 = 50%
760 V.P.
Therefore, (B) option is correct.
PPCl3 ( g) PCl2 (g) (nPCl3 ( g) )eq. (nCl2 (g) )eq.
15.* According to KP = PPCl5 (g) = V (nPCl5 ( g) )eq.
and on adding inert gas at constant pressure effect on equilibrium will be similar to as if volume of container
has been increased.
16. (A) As reaction is endothermic therefore it will go in the forward direction hence moles of CaO will increase.
(B) With the increase or decrease of volume partial pressure of the gases will remain same.
(C) Due to the addition of inert gas at constant pressure reaction will proceed in the direction in which more
number of gaseous moles are formed.
17. Na2HPO4 .12H2O(s) Na2HPO4.7H2O (s) + 5H2O (g) KP = 31.25×10–13
KP = (PH2O )5
(PH2O )5 = 31.25×10–13
(PH2O ) = (3125)1/5 × (10–15)1/5
(PH2O ) = 5×10–3
18. On adding any reactant equilibrium shifts in forward direction, so amount of product increases.
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19. On adding inert gas at constant pressure effect on equilibrium will be similar to as if volume of container has
been increased.
20. Addition of inert gas at constant volume has no effect on equilibrium concentrations.
21. High temperature will favour backward reaction as reaction is exothermic. While on increasing pressure
reaction will shift in direction higher density.
22. For constant volume, reaction quotient (Q) will remain constant.
For constant pressure, reaction quotient (Q) will remain constant when ng = 0.
23.* H2(g) + 2(g) 2HI (g)
(A) For changing pressure volume has to be changed, though number of moles of HI(g) do not get changed
but its concentration will get changed.
(B) Temperature change will change KP and hence concentration.
(C) Volume change will change concentration, not the number of moles.
(D) Same equilibrium will be attained from either direction.
(E) Catalyst does not change equilibrium concentrations.
24. N2 (g) + O2 (g) 2NO (g)
1mole 2mole 3mole
( 3) 2 9
KC = = 2.
1 2
Let a mole of O2 is added, Then,
N2 (g) + O2 (g) 2NO (g)
1mole 2mole 3mole
t=0 1 (2 + a) 3
(1–x) (2 + a)–x (3 + 2x)
[NO] = 3 2 x = 0.04 ; (3 + 2x) = 4.
100
2x = 1, x = 0.5.
(3 2 x )2 9
KC = = .
(1 – x )(2 a – x ) 2
( 4 )2 9
KC = = .
0.5[(1.5 ) – a] 2
16 9
= = .
0.5(1.5 a) 2
35
= = [1.5 + a]
4.5
7.11 = 1.5 + a .
101
a= = 5.61
18
25. AB A+ + B– AB + B– AB2–
[ A ][B ] [ AB 2 ]
K1 = K2 =
[ AB ] [ AB][B ]
[ A ][B ] [ AB ][B ] [A ] [A ] K1 1
K1/K2 = . = . [B–]2 = . 2
[ AB ]
[ AB 2 ]
[ AB 2 ]
[ AB 2 ] K2
B
Therefore, (D) option is correct.
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26. AB A+ + B– AB + B– AB2–
a–x–y y (y–x) (a–x–y) y–x x
y( y – x ) x
K1 = (a – x – y) K2 = (a – x – y)( y – x )
y( y – x )
(a – x – y )
K1 K1 y
= x 2
K2 (a – x – y )( y – x )
K 2 = x (y–x)
27. Cl2 (g) will get consumed and PCl5 will furnish Cl2 in the first reaction.
22 1
29. Moles of CO2 = =
44 2
3
Moles of H2 =
2
7 1
Moles of N2 = =
28 4
Ratio of active masses = 1/2 : 3/2 : 1/4 or 1 : 3 : 0.5.
30.* (A) Backward shifting will take place. (B) Forward shifting will take place.
(C) Backward shifting will take place. (D) Forward shifting will take place.
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CHEMI STRY
MPP
M ASTER PRACTICE PR OBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 03
CHEMICAL EQUILIBRIUM
SOLUTIONS
1. N2 + O2 2NO
Initial 2 moles 4moles
1 1 1
At Eq. 2– 4– 2× = 1 mol
2 2 2
1
Molar concentration of NO at equilibrium = = 0.4
2.5
2. A2(g) + B2(g) 2AB(g)
Moles at eqm 2–x 4–x 2x
4x2
KC =
( 2 – x)( 4 – x )
32
x= = 1.33 mole
24
2 1.33
[AB(g)] = = 0.66 M
4
3. X2 + Y2 2XY
1 2
x x 2x 2x = 0.6 x = 0.3
3 3
1 2
[x2] = - 0.3 [y2] = - 0.3
3 3
Therefore, (A) option is correct.
b c
P' PCl3 P' Cl2 .P P
(a b c ) (a b c )
4. Kp = =
P' PCl5 a
P
(a b c )
bc.P
Kp = a (a b c )
5.* Addition of solids have no effect on equilibrium and temperature favours endothermic direction while increasing
pressure will shift equilibrium in backward direction as ng is +ve.
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6. 2NO2 2NO(g) + O2(g)
(pNO )2 (pO 2 )
Kp = (pNO 2 )2
given
PO = 0.25 ; PNO = 0.5
2
(0.5)2 (0.25)
100 = (pNO 2 )2
(0.5 )2 (0.25 )
(PNO )2 =
2 100
PNO = 0.025
2
7. N2O4 2NO2(g)
n = 2 – 1 = 1, KP = KC (given)
We know, KP = KC (RT)n
1
1 = RT, T= = 12.19 K
.0821
8. Use Kp = Kc (RT)ng
9. 2O3(g) 3O2(g) Kp = 4 × 1014 pO >> pO
2 3
3
p o2
Kp = p 2 pO + PO = 8 PO ~ 8 atm.
o3 2 3 2
83
4 × 1014 = p2O = 11.3 × 10-7 Therefore, (B) option is correct.
p 2O3 3
10. Ni+2 + 6NH3 [Ni (NH3)]+6 Kf = 6 × 108
t =0 0.01 mole 0.1 mole 0
At equilibrium x (0.1 – 0.06) 0.1
Ni(NH ) (0.1)
6
3 6
Kc = = 6 × 108 . [Ni+2] = 4 × 10–8.
Ni NH = Ni 0.4
2
3
6 2 6
3
11. 2AB4(g) A2(g) + 4B2(g) n =1+ ~ 1
2
1- 2x 1- ~
1
2
4
2
P P
2 1
KP = 2
= 8P35
P
2
12. KP = P 2P.
1 2
KP
so , .
P
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3
Po 3 Po
2(1 ) 2(1 )
13. 2NH3(g) N2(g) + 3H2(g) Kp =
1 2
Po
1
3
1-
2 2
1- ~
1 and 1+ ~
1
27
27 × 10-8 P2o = P 2 × 4
16 o
= 2 × 10-2
1 0.9 0.082 1000
14. SO3(g) SO2(g) + O (g) Mmix = = 60
2 2 1.23
.MSO 2 .MO (1 )MSO 3
2 2
1- Mmix =
2 1
2
80 20
1+ = =
2 60 2 60
2
=
3
15. 2A2B(g) 2A2(g) + B2(g) KP = P
4(1 – ) 4 2 n = 4 + 2
2
4 2
p p
4 2 4 2
KP = 2 =P 23 = (1 – )2 (4 + 2)
4(1 – )
P
4 2
23 = (1 + 2 – 2) (4 + 2)
23 = 4 + 2 + 42 + 23 – 8 – 42
2
=
3
16. Let reactions is started with a mole of AB2 and b mole of B2C
AB2 (g) + B2C(g) AB3(g) + BC(g)
a b 0 0
a–x b–x–y x x–y
BC(g) + B2C(g) B3C2 (g)
x–y b–x–y y As y>x
Clearly [AB3]eq > [B3C2]eq
and [AB3]eq > [BC]eq
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17. P1 = 15 atm ; T1 = 300 K.
Equilibrium temperature is 300ºC that is 573 K.
So first of all we have to calculate pressure of NH3 at 573 K.
P1 P2 15 P2
T1
= T2
= =
300 573
P2 = 28.65 atm at 300ºC.
1 3
NH3 (g) N2(g) + H2(g).
2 2
t=0 28.65 atm 0 0
x 3
t = teq. [28.65–x] atm x
2 2
But according to question.
x 3
Ptotal = 28.65 – x ++ x
2 2
or 28.65 + x = 40.11.
x = 11.46.
11.46
Degree of dissociation of NH3 = = 0.4.
28.65
19. Kp = 0.800 atm = PCO2 = maximum pressure of CO2 in the container to calculate maximum volume of
container the PCO2 = 0.8 atm and none of CO2 should get converted into CaCO3(s).
so V(0.800 atm) = (10 L) (0.2 atm)
so v = 2.5 L
20. N2 + 3H2 2NH3, KP = 4.28 × 10–5 atm–2
2
PNH3 32 9
Reaction Quotient, QP = 3 = 3 =
PN2 (PH2 ) 1 ( 2) 8
QP > KP, Reaction will go Backward.
conc. of isobu tan e
21. From given information, Q = tan 75º = > Kc = 3
conc. of n bu tan e
so backward reaction
23. T Kc Endothermic
24. K = A e–H/RT
H
log K = log A – .
2.303RT
H 1
log K = log A – 2.303 R × .
T
H 1
log K = – 2.303 R × + log A.
T
–H
2.303 R = 1. H = – 2.303 R = – 4.606 cal.
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K2 Ho 1 1
25. log =
K1 2.303R T1 T2
K2 597 .4 10 3 1 1
log =
0.0118 2.303 8.314 1300 1200
log K2 = – 2 + log (0.0118) = – 3.928 K2 = 1.18 × 10-4 Therefore, (A) option is correct.
26. LaCl3(s) + H2O(g) + heat LaClO(s) + 2HCl(g)
2
pHCl p2
Kp = HCl pHCl 2 PHCl.
pH2O 2pH2O
27. Br2(l) + Cl2(g) 2Br Cl(g)
t=0 1 0
(1 – x) 2x
(PBrCl )2
kp = P = 1 so, PCl2 = (PBrCl )2 = 0.01 atm
Cl2
nBrCl 0.1 2x
then at equilibrium, n Cl2 = 0.01 = 10 = 1 x
10 5
So, 10 – 10x = 2x or x= = moles
12 6
Moles of Br2(l) required for maintaining vapour pressure of 0.1 atm
5 10
=2× moles = moles = moles of BrCl(g).
6 6
5
Moles required for taking part in reaction = moles of Cl2 used up = moles.
6
5 10 15
Hence total moles required = = moles.
6 6 6
28. H2O(l) H2O(g)
KP = (PH2O )
When neon is added at constant pressure, we have to increase volume of the container. So more water will
evaporate to mantain equilibrium.
29. Solubility of gas is directly proportional to the pressure of gas above liquid.
30. For any physical equilibrium on increasing pressure equilibrium shifts in the direction of higher density.
31. On increasing temperature though reaction equilibrium shifts in the backward direction but for rate of reaction
to be higher, higher temperature is required and particle 500ºC is found to be optimum temperautre.
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32. Let x is partial pressure of A and y is partial pressure of C when both equilibrium simultaneously established
in a vessel
X(s) A(g) + 2B(g)
x (2x + 2y) ;
Y(s) C(g) + 2B(g)
y (2y + 2x) ;
K P1 x
K P2 = y x = 2y
K P1 = x(2x + 2y)2
x = 0.1 atm;
y = 0.05 atm
Total pressure of gases = PA + PB + PC
= 3(x + y)
= 0.45 atm.
34. (1) A(s) D(g) + C(g) Kp = (20)2
20 atm 20 atm
(2) B(s) E(g) + F(g) Kp = (30)2
30 atm 30 atm
(3) container Kp is same so on doubling the volume partial pressure does not change but moles of C, D, E,
F will change to maintain their partial pressure. So total pressure = 40 + 60 = 100 atm.
35. A(s) X + Y
+
B(s) Y + Z
+
K P1 = ( + )
K P2 = ( + )
Ptotal = ( + ) + + = 2 ( + )
2 ( + ) = 50 + = 25
250 25 = 10 , = 15
K P2 = ( + ) = 15 × 25 = 375
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CHEMI STRY
MPP
M ASTER PRACTICE PR OBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 04
CHEMICAL EQUILIBRIUM
SOLUTIONS
Q.1 In presence of catalyst, no effect on equilibrium constant.
Q.2 H2O(g) + CO(g) H2(g) + CO2(g)... (i) K1= 2
FeO(s) + CO(g) Fe(s) + CO2(g) ...(ii) K2= 4
Required reaction : Fe(s) + H2O (g) FeO (s) + H2 (g) .... (iii)
Equation (iii) = Equation (i) – Equation (ii)
K1 2 1
K3 = K 4 2
2
Q.3 A2(g) + B2(g) 2AB(g)
2 2
initial
5 5
2 2
equilibrium x x 2x
5 5
2x = 0.7
x = 0.35 M
[A2] = [B2] = 0.4 – x = 0.05 M
Q.6 A(l) A(g)
revaporation = constant
re
r
rcondensation = increases till equilibrium rc
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Q.8 NH4HS(g) NH3(g) + H2S(g)
Ist eqb x 4 6 KC = 12
46
12
x
x = 2 moles
NH4HS(g) NH3(g) + H2S(g)
2 4 6
Let x moles of H2S be added
NH4HS(g) NH3(g) + H2S(g)
new eq b 2+y 4–y 6 +x –y
at new equilibrium moles of NH3 = 2
So, 4 – y = 2
y=2
( 2)(4 x )
= 12
4
4 + x = 24
x = 20 moles
Q.17 N2O4 (g) 2NO2 (g)
1 2 4 2
P P KP = P
1 1 1 2
1 1
1 = at P1 and 2 = at P2
3 2
1 2 1 2
4 4
3 2
P
2 1
P
2 2
1 1 1 1
3 2
8
P1 9 1 8
P2 4 3 3
9 4
Q.18 2NOBr(g) 2NO(g) + Br2(g)
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1 /2
P P P
1 2 1 2 1 2
P 2
PBr2 P
9 1
2
1 1
=
2 9 4
1 34 2
so p NOBr P P P
1 98 3
2
P 1 4 2
pNO = = 9 8 P 9 P
1
2
P
p Br2
9
2
2 P
P
9 9 P
KP = 2 2 81
P
3
1
KP / P
81
Q.23 Only decreasing temperature, Keq increasing so reaction is exothermic in forward direction.
Q.25 Fe3+(aq) + SCN–(aq) Fe(SCN)2+(aq)
(A) For given system Q V on addition of water Q > K reaction move backward
(B) Fe+3 + 3OH¯ Fe(OH)3 (s) reaction moves backward
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Q.27 Theory based
Q.31 PM = dRT
0 . 9 ( 0 . 08 ) (1000 )
Mmixture = = 60
1 .2
1
SO3(g) SO2(g) + O (g)
2 2
1–
2
M SO3
Mmixture = 60
1
2
80
60
1
2
4
1
2 3
2
=
3
Q.38 N2O4 (g) 2NO2(g)
42
t = told eqm at V = V0 2 atm 4 atm KP = = 8 atm
2
1 22
t = tdistrub at V= 2V0 1 atm 2 atm QP =
1
QP < KP so reaction moves for ward.
t = new eqm 1–x 2 + 2x
(2 2x ) 2
KP = = 8 (1 +x)2 = 2(1 – x)
1 x
1 + x2 + 2x = 2 – 2x
x2 + 4x –1 = 0
4 16 4 4 16 4
x= = = 0.24
2 2
PN2O4 at new eqm = 1 – x = 1 – 0.24 = 0.76 atm Ans.
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Q.39 Theory based
Q.41 Triple point is (200 K, 5 × 10–3 atm)
(200 K, 5 × 10–3 × 760 mm of Hg)
(200 K, 3.8 mm of Hg)
Boiling point slightly less than 400 K
Above 500 K, gas-liquid transition can not occur without change in temperature as 500 K is critical
point.
2
PNO
Q.42 N2O4 (g) 2NO2(g) KP = 2
PN 2O4
a0–a 0 2a0
4 2
KP = .P 4 2 .Pt
2 t if << 1
1
(A) KP = 4 × (0.3)2 × 100 = 36 atm
KP = 4 22 P2
4 × (0.3)2 × 100 = 4(0.4)2 P2
900
(B) P2 = = 56.25 atm
16
(C) QP = 42.Pt so if Pt increases then decreases to reset QP = KP.
(D) As reaction is endothermic in forward direction so on increasing temperature, it favour
endothermic step i.e. increases.
Q.46 N2O4 2NO2
a 0 M.Wt.N 2O4
a0 – a0 2a0 Mavg = a 0 (1 )
PM = dRT
1 × Mavg = 2.5 × 0.08 × 400
92 1
Mavg = = 80 p N 2O 4 Pt
1 1
92 0.85
1+= p N 2O 4 1 = 0.74 atm
80 1.15
= 0.15 p NO2 1 p N2O4
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Q.47 N2O4(g) 2NO2 (g)
at eqm. 0.74 atm 0.26 atm
Q.48 CS2(g) C(s) + S2(g) K=0
11 atm
x atm 11-x atm
PS2 11 x
K = 10 = P
CS2 x
10 x = 11 – x
11x = 11
x=1
CS2(g) = 1 atm
S2(g) = 10 atm ]
Q.50 CS2(g) C(s) + S2(g)
n S2 / V
K= n = 10
CS2 / V
n S2 n CS2 = 22
11 n CS2 = 22
n CS2 = 2
n S2 = 20
PV = nRT
22 0.08 1000
V= = 160 L ]
11
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 05
CHEMICAL EQUILBRIUM
SOLUTION
OFFLINE JEE-MAIN
1. In this reaction the ratio of number of moles of reactants to products in same i.e., 2 : 2, hence
change in volume will not alter the number of moles .
2. If in the reaction the ratio of number of moles of reactants to products in same i.e., 1 : 1, then
change in volume will not alter the number of moles .
1 3 1 Kc
3. Kp = Kc (RT)∆n ; ∆n = 1 – 1 + = 1 – = − . ∴ = (RT)1/2 .
2 2 2 Kp
4. The conversion of SO2 to SO3 is an exothermic reaction, hence there is no need to increase
the temperature. There is also a decrease in volume or moles in product side. Thus the
reaction is favoured by low temperature and high pressure. (Le-Chatelier’s principle).
5. C[N2O4 ] = 4.8 × 10–2 mol L–1, C[NO2 ] = 1.2 × 10–2 mol L–1
[NO2 ]2 1.2 × 10 −2 × 1.2 × 10 −3
=Kc = = 0.3 × 10–2 = 3 × 10–3 mol L–1
[N2 O4 ] 4.8 × 10 −2
[P4 O10 (s)]
6. P4(g) + 5O2 (g) P4O10(g) Kc =
[P4 (s)][O2 (g)]5
7. CO(g) + CI2(g) COCI2(g)
Kp 1
∆n = 1 – 2 = – 1; Kp = Kc(RT)∆n ∴ = (RT)
= −1
Kc RT
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[NO]2
8. N2(g) + O2(g) 2NO(g); Kc = = 4 × 10 −4
[N2 ][O2 ]
1 1 [N2 ]1/ 2 [O2 ]1/ 2 1 1 1 100
NO(g) N2(g) + O2(g) ; =
Kc = = = = −2
= 50
2 2 [NO] Kc 4 × 10 −4 2 × 10 2
9. Kp = Kc (RT)n ∆n = 3 – 2 = 1.
Kp = Kc (0.0821 × 457)1 . Kp > Kc.
10. CI2(g) + 3F2(g) 2CIF3(g) ; ∆H = – 329 kJ. Favourable conditions:
(i) Decrease in temperature, (ii) Addition of reactants, (iii) Increase in pressure i.e., decrease
in volume.
11. NH4HS(s) NH3(g) + H2S(g)
Initial presens 0 0.5 0
At equi. 0 0.5+x x
Total pressure = 0.5 + 2x = 0.84 ∴ x = 0.17 atm
Kp = PNH × PH S = 0.11 atm2.
3 2
12. Given : PCI5(g) PCI3(g) + CI2(g)
t=0 1 0 0
teq 1–x x x
Total number of moles = 1 – x + x + x = 1 + x
x
Thus partial pressure of PCI3 = P.
1+ x
1
13. SO3(g) SO2(g) + O2(g)
2
[SO2 ][O2 ]1/ 2
= KC = 4.9 × 10–2 ...........(i)
[SO3 ]
SO3(g) + 1/25 O2(g) SO3(g) ...........(ii)
[SO3 ] 1
= K'C = For 2SO2(g) + O2(g) 2SO3(g)
[SO2 ][O2 ]1/ 2 4.9 × 10 –2
[SO3 ]2 1 10000
= KC2 = −4
= = 416.49
2
[SO2 ] [O2 ] 4.9 × 4.9 × 10 24.01
14. c=a+b
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15. X 2Y Z P + Q
1–α 2α 1–α α α
2
2α α α
1 + α PT1 1 + α PT2 1 + α PT2
K p1 = Kp2 =
1− α 1− α
1 + α PT1 1 + α PT2
2
2α 1− α
1 + α PT1 1 + α PT2
K P1
= ×
K P2 1− α α α
1 + α PT2 1 + α PT2 1 + α PT2
1 4PT1 PT1 1
= ; =
9 PT2 PT2 36
16. CO2(g) + C(s) 2CO (g)
0.5 atm
0.5–p 2p
Total pressure = 0.5 – P + 2P = 0.8
P = 0.3
2
PCO (2P)2 (0.6)2
Kp = = =
PCO2 (0.5 − P) (0.5 − 0.3)
Kp = 1.8
17. N2 + O2 → 2NO K = 4 × 10–4
1 1 1 1
NO → N2 + O2 K’ = = = 50
2 2 K 4 × 10 −4
1
Kp = Kc (RT )
∆ng
18. ∆ng = –
2
19. ∆G = ∆G° + RT ln Q
= 2494.2 + 8.314 × 300 ln 4
= positive
Q
∆G = RTλn
K
Since, ∆G is positive so, Q > K, so reaction shifts in reverse direction.
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20. A + B C + D
t=0 1 1 1 1
teq 1–x 1–x 1+x 1+x
(1 + x)2 1+ x
⇒ = 100 ⇒ = 10
(1– x)2 1– x
⇒ 1 + x = 10 – 10x ⇒ 11x = 9
9 9
⇒ x= ⇒ [D] = 1 + ⇒ [D] = 1.818
11 11
ONLINE JEE-MAIN
MTh
5. = 1 + (2 – 1) α = 1.2.
MOb
92 PM 1× 92
⇒ MOb = and d= = = 3.116 g/L
1.2 RT 1.2 × 0.082 × 300
6. On increasing pressure, reaction shifts in the direction of increasing density. Water has higher
density than ice. So reaction shifts in forward direction.
7. XY(s) X(g) + Y(g)
At eq. P P
Total pressure = 2P = 10 bar
⇒P=5
Now, KP = (PX)(PY) = P2 = 25
8. Addition/ removal of a solid component from an equilibrium system causer no shift in
equilibrium (Both Q & K remain unaffected)
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C HE M IS T RY
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DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 01
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
n × 0.4 0.5
11. = ⇒n=3
96 40
weigth of A = 96 – 3 = 93
Ka
12. For weak acid α at infinite dilution a → 1
C0
Ka 1
% dissociation = 100 α = 100 × α
C0 C0
100α 100α
Conc. Dilution
On increasing dilution ⇒ C0 decreasing
= 100 × α increasing
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 02
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
7. Initially pH = 7
finally [NaOH] = 10–3 so pOH = 3
pH = 11
so ∆(pH) = 4
1
10. pH = {pKa – log C}
2
1 1
so, ∆(pH) = [log Ci – log Cf] = {–1 + 2} = 0.5 [pH will increase].
2 2
14. pH + pOH = 14
pOH = 14 –10.48 = 3.52
[OH–] = 3 ×10–4 mol/litre
3 × 10 −4
NO. of OH– moles in 250 ml = = 7.5 ×10–5
4
1
No. of moles of Ca(OH)2 dissolved = × 7.5 ×10–5 = 3.75 ×10–5
2
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 03
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
4. At 65ºC
Kw = 16 × 10–14 = [H+] [OH–].
[H+] = 4 × 10–7.
pH = 7 – log4 = 6.4.
6. NH3 + NH3 NH4+ + NH2–.
in self ionisation of NH3.
[NH4+] = [NH2–].
K(Amm) = [NH4+] [NH2–] = 1 × 10–30.
8. Strongest acid HF; weakest acid HS— and weakest acid (HS—) has the stongest conjugate
base.
9. Strongest base NH3 ; weakest base C5H5N and NH3 has the weakest conjugate acid.
10. For H2O Kw ∝ T.
∴ [H+] ∝ T.
∴ pH ∝ .
16. pKa (H3O+) = –1.74 = pKb of OH–
pKa + pKb = 14 only for conjugate acid base pair.
α = 1.8 × 10–9 or 1.8 × 10–7 % for H2O.
23. SA – HNO3, H2SO4 ; SB – H–, O2–
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24. Reaction proceed to words the side favoring formation of weak acid and weak base.
25. (a) Acid strength H2SO4 > H2CO3.
Basic strength HCO3– > HSO4–.
(b) Acid strength HCl > HF.
Basic strength F– > Cl–.
(c) Acid strength HF > NH4+
Basic strength NH3 > F–.
(d) Acid strength HSO4– > HCN.
Basic strength CN– > SO42–.
c and d will move to the right
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 04
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
7
1. HClO4 with highest oxidation number and its conjugate base is resonance stabilised, hence it
is most acidic.
3. Anionic hydrolysis give basic solution.
Kw 10 −14 10 −9
5. Kh = = −5
= = 5.65 × 10–10.
Ka 1.77 × 10 1.77
6. Ka.Kh = Kw ⇒ Ka ↑ ⇒ Kh ↓ .
7. (NH4)2SO4 → 2NH4+ + SO42–
1 1
pH = [pKw – pKb – log10C] = [14 – 4.7 + 1.7] = 5.5.
2 2
8. Cationic hydrolysis result in acidic solution. So,
Fe3+ + 3H2O → Fe(OH)3 + 3H+
acidic solution
9. pKb > pKa
i.e. Ka > Kb
i.e. acidic.
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 05
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
K w.K a
3. [H+] = is valid for salt of weak acid and strong base.
C
4. pOH = 7 – 0.5 pKa + 0.5 pKb
or
pH = 7 + 0.5 pKa – 0.5 pKb is valid for salt of wA and wB.
10. K = [HCOOH2+] [HCOO–] = 10–6.
[HCOO–] = 10–3 mol/L.
1 liter solution of HCOOH has = 1150 g mass.
1150
moles of (HCOOH) in 1 litre solution = = 25 mol.
46
out of 25 mol HCOOH 10–3 mol are ionised into HCOO– ions.
10 –3
∴ % dissociation = × 100 = 0.004%
25
11.* Degree of dissocation of WA & WB will increase.
[H+] in WA and [OH–] in WB will decrease so pH of WA and pOH of WB will increase.
13. (a) Acid strength H2SO4 > H2CO3.
Basic strength HCO3– > HSO4–.
(b) Acid strength HCl > HF.
Basic strength F– > Cl–.
(c) Acid strength HF > NH4+
Basic strength NH3 > F–.
(d) Acid strength HSO4– > HCN.
Basic strength CN– > SO42–.
c and d will move to the right.
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 06
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
1. For the buffer solution of CH3COOH & CH3COO–
[CH3 COOH] m.moles of CH3 COO −
pH = pKa + log ⇒ 4.04 = 4.74 + log
[CH3 COO – ] (100 × 0.1)
⇒ m. moles of CH3COO– = 50
∴ moles of (CH3COO)2Ba required = 0.025.
[salt] [salt]
2. From the information, =2 ; so, pH = pKa + log = 5.05.
[acid] [acid]
3. H2PO4– HPO42– + H+.
HPO2– HPO2– 2
8 × 10–8 = 4
–
× 4 × 10–8. ⇒
4
–
= .
2 4
H PO 2 4
H PO 1
In–
5. pH = pKIn + log10
HIn
1
pH = [6 – log10 5] + log10 = 4
20
In–
pH = pKIn + log10
HIn
40
= pKIn + log10
1
= 6 – log10 5 + log10 40
= 6 – 0.7 + 1.6 = 6.9
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[Salt]
6. pOH = pKb + log
[Base]
[Salt]
7. (1) is incorrect because pH = pKa + log for acidic buffer.
[Acid]
If [Salt] increases, pH of acidic buffer will increase.
[Salt]
(2) is correct because pOH = pKb + log for basic buffer.
[Base]
If [Base] increases, pOH will decrease, pH will increase as pH = 14 – pOH.
8. For basic buffer
salt
pOH = pKb + log
base
salt
pH = 14 – pOH = 14 – pKb – log
base
9. HC2H3O2 + NaOH → C2H3O2Na + H2O
1 0.5 0 0
0.5 0 0.5 0.5
This solution contains weak acid + its salt with strong base and thus acts as buffer.
11. Ka = 1 × 10–5 pKa = 5
Ionised
pH = pK HIn + log
un Ionised
The dissociation equilibrium for acid Indicator
HIn H+ + In–
Colour A Colour B
[H+ ] [In− ]
KIn =
[HIn]
the middle point of the colour range of an indicator HIn is the point at which [HIn] = [In]
pH = pK HIn = 5
Thus colour change in Indicator will be noticed at pH = 5
[Ionised] 80
(ii) pH = pK a + log = 5 + log = 5.6
[unIonised] 20
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 07
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
1. Weak acid and its conjugate base form a buffer.
2. CH3COOH (weak acid) and CH3COONa (conjugated salt) form acidic buffer and for acidic
buffer,
[salt]
pH = pKa + log and [H+] = –antilog pH
[acid]
[salt]
pH = – log Ka + log [pKa = – log Ka]
[acid]
(0.20)
= – log (1.8 × 10–5 ) + log = 4.74 + log 2 = 4.74 + 0.3010 = 5.041
(0.10)
Now, [H+] = antilog (– 5.045) = 9.0 × 10–6 mol/L
3. pOH = pKb = 10
pH = 14 – pOH = 14 – 10 = 4.
NH4 Cl
4. pOH = pKb + log
NH4 OH
0.1
14 – 9.25 = pKb + log ⇒ pKb = 4.75.
0.1
2
5. pH = 4.7 + log
1
pH = 5
∴ pOH = 9.
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6. pH = pKa = 4.75
[salt]
7. pOH = pKb + log
[base]
As [salt] = [base]
pOH = pKb
11. Ag2SO4 2Ag+ + SO4–2
2s' (s' + 10–2) ≈ 10–2
Ksp = (2s')2 (10–2) = (2 × 2 × 10–8)2 (10–2) = 16 × 10–18 .
13. [H+] = 10–10 M from Hendersen equation.
10.8 × 10 −9
17. 10.8 × 10–9 = (0.5S × 2)2 (0.5S) ⇒ S3 =
0.25 × 0.5
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 08
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
NH4 Cl
1. pOH = pKb + log
NH4 OH
0.1
14 – 9.25 = pKb + log ⇒ pKb= 4.75.
0.1
Kw 10 −14
3. Kh = = −12 = 10–2
K a3 10
Ch 2
Kh =
(1 − h )
Kh 10 −2
as 1 – h = 1, h = = = 0.316
C 0.1
as h > 0.1 ⇒ 1 – h ≠ 1
10 −1 × h 2
∴ 10–2 = or 0.1 (1 – h) = h2
(1 − h )
or, 0.1 – 0.1 h = h2
or, h + 0.1 h – 0.1 = 0
−0.1 + (0.1)2 + 4 × 0.1
or, h = = 0.27
2
as, PO43– + H2O HPO42– + OH–
c(1 – h) ch ch
–
[OH ] = ch
= 0.1 × 0.27
= 27 × 10–3
pOH = 3 – log 27 = 3 log33 = 3 – 3 log 3
= 3 – 3 × 0.48 = 1.56
pH = 14 – 1.56 = 12.44
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[Salt]
5. (A) is incorrect because pH = pKa + log for acidic buffer.
[Acid]
If [Salt] increases, pH of acidic buffer will increase.
[Salt]
(B) is correct because pOH = pKb + log for basic buffer.
[Base]
If [Base] increases, pOH will decrease, pH will increase as pH = 14 – pOH.
6. For the buffer solution of CH3COOH & CH3COO–
[CH3COOH]
pH = pKa + log
[CH3COO – ]
(100 × 0.1)
⇒ 4.04 = 4.74 + log
m.moles of CH3COO –
⇒ m. moles of CH3COO– = 50
∴ moles of (CH3COO)2Ba required = 0.025.
[salt]
7. pOH = pKb + log =5
[base]
3 [salt] [salt]
pOH = pKb + log = pKb + log [base] + log3 = 5 + log3 = 5 + 0.48 = 5.48.
[base]
[salt]
10. pOH = pKb + log
[base]
As [salt] = [base]
pOH = pKb
1
12. (A) pH = (pKw + pKa – pKb)
2
pK a1 + pK a2
(B) pH =
2
1
(C) pH = (pKw + pKa2 + log10C)
2
(D) pH = 7
13. FeCl3, CuSO4, CO2, NH4Cl ; C6H5NH3+Cl– ; BCl3.
1 1
14. pH = (pKw + pKa – pKb) = [14 + 3.4814 – 4.7447] = 6.368.
2 2
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 09
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
1. pH = pKa = 4.75
5. Ag2SO4 2Ag+ + SO4–2
2s' (s' + 10–2) ≈ 10–2
Ksp = (2s')2 (10–2) = (2 × 2 × 10–8)2 (10–2) = 16 × 10–18
7. (A) As reaction is endothermic therefore it will go in the forward direction hence moles of PbO
will increase.
(B) With the increase or decrease of volume partial pressure of the gases will remain same.
(C) Due to the addition of inert gas at constant pressure reaction will proceed in the direction
in which more number of gaseous moles are formed.
8. [H+] = = 8 × 10–3 M
[H+ ][HCOO − ]
for HCOOH, Ka = 2.4 × 10–4 =
[HCOOH]
∴ [HCOO¯] = 3 × 10–3 M
[H+ ][OCN− ]
for HOCN, Ka = 4 × 10–4 =
[HOCN]
∴ [OCN¯] = 5 × 10–3 M
9.* pKa (H3O+) = –1.74 = pKb of OH–
pKa + pKb = 14 only for conjugate acid base pair.
α = 1.8 × 10–9 or 1.8 × 10–7 % for H2O.
10.* (A) Correct statement
(B) Due to common ion effect on H2O H+ + OH–
(D) relative strength of strong acids can not be determined in water due to levelling effect.
11.* (a) pH = 11.08 (b) pH = 13 (c) Kb = 1.44 × 10−5 (d) will suppress it.
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0.5 0.1
12.* Total [H+] = K a1C1 + K a2C2 = 3.6 × 10 −4 × × 100 + 8 × 10 −4 × × 400
500 500
∴ [H+] = 10–2 M.
K a [HN3 ] 3.6 × 10 −4 × 0.5
For HN3, [N3–] = = × 100 = 3.6 × 10–3 M.
[H+ ] 0.01 × 500
K a [HOCN] 8 × 10 −4 × 0.1 × 400
For HOCN, [OCN–] = = = 6.4 × 10–3 M.
[H+ ] 0.01 × 500
13. H2S H+ + HS– .....(i)
0.1 – x 0.25 x
– +
HS H + S– .....(ii)
x–y 0.25 y
HCl → H+ + Cl– .....(iii)
0.25
0.25 × [HS – ]
(i) 10–7 = [HS–] = 4 × 10–8.
0.1– x
0.25 × [S2 − ]
(ii) 1.3 × 10–13 = [S2–] = 2.08 × 10–20.
4 × 10 –8 – y
14. Calculation of [H+] and [HSac] at start
4 × 10 −4 × 1000
[HSac] = = 0.002 M
200
The dissociation of HSac is as below
HSac H+ + Sac–
At start 0.002 0.001 0
At equi. 0.002-x 0.001 + x x
[H+ ][Sac − ] (0.01 + x)x
∴ Ka = = = 2 ×10–12
[HSac] 0.002 − x
x = 4 ×10–12 M
[Sac–]equi. = 4 ×10–12 M.
−7 −7
15. [H+] = K1C1 + K 2C2 = 10 × 0.1 + 4 × 10 × 0.2 = 3 × 10–4 M
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 10
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
3. H2PO4– HPO42– + H. +
HPO2– HPO2– 2
8 × 10–8 = 4
–
× 4 × 10–8 ⇒ 4
–
=
H2PO4 H2PO4 1
[H3 AsO4 ] [H+ ] 10 −8 1
4.* (A) = = −4
= ∴ [H3AsO4] << [H3AsO4–].
[H2 AsO4 − ] K1 2.5 × 10 25000
[H2 AsO4 − ] [H+ ] 10 −8 1
(B) = = =
[HAsO42 − ] K2 5 × 10 −8 5
[AsO43 − ] K3 2 × 10 −13 1
(C) = = = ∴ [AsO43–] << [HAsO42–].
[HAsO42 − ] [H+ ] 10 −8
50000
5.* [OH–] = C1K b1
[N2H5+] = C1K b1 .
[N2H6+] = K b2 .
8. NaOH + H2SO4 → NaHSO4 + H2O
initial m mole 10 5 0
reaction 5 0 5
NaOH + NaHSO4 → Na2SO4 + H2O
5 5 0
0 0 5
5
2 + log 200 = 7 + 2 [ 2 + log5 − log200] = 7 + 2 [2 + 0.7 – 0.3 – 2] = 7.2
1 1 1
pH = 7 +
2
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 11
ST
IONIC EQUILIBRIUM
TOPIC : DEVELOPMENT OF PERIODIC TABLE & MODERN PERIODIC TABLE
SOLUTIONS
2. m.moles of Ag+ in 100 ml of saturated solution of AgCl = K sp × 100 = 1.4 × 10–3
Now Ag+ + SCN– → AgSCN (s)
m.moles of SCN– = m.moles of Ag+
1 × 10–5 × V = 1.4 × 10–3 ⇒ volume = 140 mL.
3. S2– + Zn2+ → ZnS (s)
m.moles 0.4 0.2
0.2 –
so in solution,
0.2
[S2–] = = 0.01 M
20
K 4 × 10 −24
∴ [Zn2+] = 2sp− = = 4 × 10–22 M
[S ] 0.01
∴ mass of Zn2+ remain unprecipitated in 20 ml of solution
4 × 10 −24
= × 20 × 65 = 5.2 × 10–22 gm.
1000
1 1
6. Initial pH = (pKa – log C) = (5 – log 2 – log 0.01) = 3.35
2 2
After adding HCl, pH of solution = 2
Change in pH = 1.35
7. 29Cu → 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Nodes 0 1 1 2 2 2 3 (but incompletely filled)
Orbitals 1 3 5
So 9.
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13. FeSO4 + Na2S → FeS + Na2SO4
a a
a a
KSP = = 6.25 × 10–18
2 2
a2 = 4 × 6.25 × 10–18 = 4 × 625 × 10–20
a = 2 × 25 × 10–10 = 5 × 10–9 M
14. (A) For AgBr, Ksp = [Ag+] [Br–]
so on increase in [Br–], solubility of AgBr decreases.
(B) For AgCN, Ksp = [Ag+] [CN–]
CN– undergoes hydrolysis so solubility in water is more than expectation.
In acidic solution, CN– gets protonated so solubility of AgCN increases.
AgCN forms complex Ag(CN)2– with excess of CN–.
(C) For Fe(OH)3, Ksp = [Fe3+] [OH–]3.
In acidic solution OH– decreases so solubility increases.
Solubility decreases in presence of OH–.
(D) For Zn(OH)2, Ksp = [Zn2+] [OH–]2
Zn(OH)2 is amphoteric in nature so its solubility increases in both acidic as will as
strongly basic solution.
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CHEMI STRY
MPP
M ASTER PRACTICE PR OBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 01
IONIC EQUILIBRIUM
SOLUTIONS
1. HCl (aq) + CH3COOH (aq) Cl– (aq) + CH3 COOH2+(aq).
Acid-1 base-2 base-1 acid-2
2. HC2O4– (aq) + PO43–(aq) HPO42–(aq) + C2O42–(aq)
Acid-1 base-2 base-1 acid-2
3. Conjugate acid base pair are differ by an proton (H+).
– H
HF + HF
(acid) (base)
4. H3BO3 =
So it will behave as Lewis acid.
5. Amphoteric means species which can accept as well as loose H+.
6.* Let BA be this salt BA B+ + A–
A does not undergo hydrolysis because HA is strong acid. B+ undergoes hydroysis
–
Kh Kw
h= h = degree of hydrolysis where Kh = Hydrolysis constant = K b .
c
h Kh greater the hydrolysis constant greater the h(degree of hydrolysis).
1
h Kb greater the Kb lesser the h.
Hydrolysis is endothermic, Kh increases with temperature and h also increase with temperature.
Kw
h V V = volume of salt solution hence h increases with dilution. Kh = K
b
Both Kw and Kb change with temperature, hence Kh changes with temperature.
Hence, statement(B) is correct. h increases if Kb decreases, statement(C) correct.
It is found that as temperature increase, Kw and Kb increase but increase in Kw is greater than increase in Kb.
Hence, h increases with increase in temperature. or h decrease in temperature., hence statement.
(D) is correct.
(D) is not correct from explanation of (B).
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7. Fact based
8. Fact based
9. [OH–] = K w in pure water..
So as temperature increases Kw decreases [OH–] decreases.
10*. H2SO4 is a strong acid and it completely dissociated in H2O. Hence its K a1 and K a2 are determined in
CH3COOH.
Also H2SO4 is neutral while HSO4– because the – ve charge has more affinity towards H+ ion. Hence choices
(A) and (B) are correct while (C) is incorrect.
11. pKw = – logKw = – log 1 × 10–12 = 12.
Kw = [H+][OH–] = 10–12 .
[H+] = [OH–]
[H+]2 = 10–12 ; [H+] = 10–6 ; pH = – log[H+] = – log 10–6 = 6.
H2O is neutral because [H+] = [OH–] at 373 K even when pH = 6.
(D) is not correct at 373 K. Water cannot become acidic.
13. T pH
14*. (A) In 0.6 m M HCOOH solution
[H ]2 [H ]2
Ka = 8 × 10–4 =
C [H ] 6 10 4 [H ]
[H+] = 4 × 10–4 M.
So solution in (A), (C) & (D) are SOHYDRIC.
15. K = [HCOOH2+] [HCOO–] = 10-3 × 10-3 = 10-6
1
16. Ka = 10–6 for HA + H2O H3O+ + A– Thus K for reverse reaction is = 106
10 6
17. pKa + pKb = 14.
1 Ka
19. (A) Kb = Kw (B*) Ka . Kb = Kw (C) K b (D) Kw
Kw Ka
20. (A) At 25ºC, [H+] in a solution of 10–8 M HCl > 10–7 M.
(B) [H+] = 10–8 M.
(C) [OH–] = 4 × 10–6 M
[H+] = 2.5 × 10–9 M.
(D) [H+] = 10–9 M.
21. [H+] = 0.016 M
100 1016
[H+] [OH–] = 10–14 [OH–] = = 6.25 × 10–13 M
16 10 3
22. Inital Final
pH = 12 pH = 11
[H+] = 10–12 M [H+] = 10–11 M
– –2
[OH ] = 10 M [OH–] = 10–3 M
– –2
Inital No. of mole of OH = 10 Final No. of mole of OH– = 10–3
–
So no. of mole of OH removed = [.01 – 0.001] = 0.009
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23. (a) HCI NaOH
1 1
No. of mili e = × 100 = 10 × 100 = 10
10 10
So solution is Neutral
1 1
(b) × 55 = 5.5 × 45 = 4.5
10 10
1
[H+] = = 10–2 M, pH = 2
100
1 1
(c) × 10 = 1 × 90 = 9 Basic
10 10
1 1
(d) × 75 = 15 × 25 = 5
5 5
[H+] = 0.1 M, pH = 1
24. As V , effect of water dominates so pH become 7.
25. HCI NaOH
N = 0.4 N = 0.2
V = 50 ml V = 50 ml
No. of milieq = 0.4 × 50= 20 0.2 × 50 = 10
[H+] = 0.1 M, pH = 1
26. As concentration of solution decreases, degree of dissociation of weak electrolyte increases.
27*. (A) [H+] = 10–2 and [OH–] = 10–2
H+ + OH– H2O
This leads complete neutralisation
2 12
so pH = 7 =
2
(D) [H+] = 10–5 and [OH–] = 10–5
[H+] + [OH–] H2O
This leads complete neutralisation
59
so, pH = 7 =
2
28. As Ka of acid increases, Kb of its conjugate base decreases.
29. At infinite weak electrolytes are 100% dissociated.
30. AB3 A3+ + 3B–
Initial mole 1 0 0
Mole at. E 1– 3
1 3
If volume is v, Therefore, 3c.
v v v
31. Ostwald's dilution law is valid for weak electrolysis.
32. Concentration of Solutions are same therefore [H+] depends only on Dissociation constant.
33. Factual.
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34. On the basis of ostwald dilution law, number of H+ ions will increase but increase in volume will be more.
Therefore, [H+] decreases, pH increases.
35. In this solution, source of OH– is water
C = [OH–]
109
= = 1.8 × 10–111 M
1000 / 18
% ionisation = 1.8 × 10–9 M
36. For each weak polyprotic acid Ka > Ka > Ka ................
1 2 3
37. pH of 0.1 M H2S solution can be derived by :
H2S H+ + HS– ; K1 = 1 ×10–7
K1
[H+] = C = C = K1 C = 1 10 – 7 0.1 =
–4
10 8 = 10 pH = 4
C
38. H3PO4 H2PO4– + H+
0.1 – x x x
x2
Ka1 = = 10–3
0.1 x
x = 0.01 = [H+] = [H2PO 4–]
and [HPO 42–] = 10–7 M
3
[H ] [PO 4 ] (0.01) [PO 4 3 ]
Ka3 = 10–12 =
[HPO 4 2 ] 10 7
[PO 43–] = 10–17 M
[OH–] = 10–12 M
[H ] [OCN ]
39. For HOCN– , Ka = ; Here [H+] = total H+ concentration of solution.
[HOCN]
40. CH3COOH (aq) H+ (aq) + CH3COO– (aq)
t=0 0.01
t = eq 0.01 – x x x
[H+] = x + 0.01 0.01 M
[H ] [CH3COO ] 0.01 [CH3COO ]
Ka = 1.69 × 10–5 =
[CH3COOH] 0.01
[CH3COO–] = 1.69 × 10–5 M
1.69 105
So, degree of dissociation of CH3COOH = = 1.69 × 10–3
0.01
41. Factual
42. Factual
43. h = .03 C = 0.1 M
Kh = Ch2 = 9 × 10–5
Kw 10 14
Kh = = 9 × 10–5 Ka = = 1.11 × 10–10 1 × 10–10
Ka 9 10 – 5
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44. CH3COOH + OH– CH3COO– + H2O
t=0 20 20
t = eq – – 20
20
So, [CH3COO–] = = 0.1 M
200
1 1 1
pH = 7 + pKa + log C = 7 + 2.37 + log 10–1 = 7 + 2.37 – 0.5 = 8.87
2 2 2
46. Solution of HCl & NH4Cl will be acidic, solution of NaCl neutral whereas solution of NaCN will be basic.
47. HCl H+ + Cl–
(x + x) (x)
H2O H + OH–
+
(x + x) (x)
Ionic product = Kw = (2x) (x) = 10–14
2x2 = 10–14 x= 50 × 10–8
1 1
49. Initial pH = (pKb – log C) = (5 – log 2 – log 0.1) = 2.85
2 2
After adding NaOH, pOH of solution = 1
Change in pOH = 1.85
50. m. moles of HCl = 0.1 × 20 = 2
m. moles of CH3COOH = 0.1 × 20 = 2
After titration of HCl by NaOH
2 1
[CH3COOH] = = M
40 20
1 1 1
pH = (pKa – log C) = [5 – log 2 – log ( )] = 3.
2 2 20
52. pH of amphioprotic salts and weak acid-weak base salt is independent of its concentration.
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 04
ST
IONIC EQUILIBRIUM
SOLUTION
1. Given : [K sp ]PbI2= 8 × 10 −9
To calculate : solubility of PbI2 in 0.1 M sol of Pb(NO3)2
+2 −
(I) Pb(NO3)2 → Pb(aq) + 2NO3 (aq)
0.1 M – –
– 0.1 M 0.2 M
(II) PbI2(s) Pb+2(aq) + 2I–(aq)
s 2s
= s + 0.1
= 0.1
Now : Ksp = 8 × 10–9 = [Pb+2] [I–]2
⇒ 8 × 10–9 = 0.1 × (2s)2
−4
⇒ 8 × 10–8 = 4s2 ⇒ s = 2 × 10
⇒ S 141× 10 −6 M
=
⇒ x = 141
K sp s2 K sp +
2. = +
; s= (H )
Ka (H ) Ka
2.2 × 10 −16
=s −10
× 10−3
6.2 × 10
s = 1.9 × 10–5
Hence answer is (2)
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3. Ca(OH)2 Ca2+(aq) + 2OH–(aq)
s 2s
ksp = s(2s)2 ⇒ 5.5 × 10–6 = 4S3
1
5.5 3
=
⇒ s × 10−2 = 1.11 × 10–2
4
4. Since (NH4)3PO4 is salt of weak acid (H3PO4) & weak base (NH4OH).
1
pH = 7 + (pKa – pKb)
2
1
= 7 + (5.23 – 4.75)
2
= 7.24 ≈ 7
5. (For A2X)
A2X → 2A+ + X2–
2S1 S1
Ksp = 4S13 = 4 × 10–12
S1 = 10–4
For MX
MX → M+ + X–
S2 S2
Ksp = S22 = 4 × 10–12
S2 = 2 × 10–6
S 2X 10−4
so=
A
=−6
50
SMX 2 × 10
6. H2SO3 [Dibasic acid]
C = 0.588 M
⇒ pH of solution ⇒ due to First dissociation only since Ka, >> Ka2
⇒ First dissociation of H2SO3
H2SO3(aq) H⊕(aq) + HSO3–(aq) : ka1 = 1.7 × 10–2
t=0 C
t C–x x x
⊕ −
1.7 [H ][HSO ]
⇒ Ka1 = = 3
100 [H2SO3 ]
⇒ 1.7 × 0.588 – 1.7x = 100 x2
⇒ 100x2 + 1.7x – = 0
−1.7 (1.7)2 + 4 × 100 × 1
⇒ [H⊕] = x = = 0.09186
2 × 100
Therefore pH of sol. Is : pH = log [H⊕]
⇒ pH = –log (0.09186) = 1.036 �1
7. HA H+ + A–
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Initial conc. 0.01M 0.1.M 0
Equ. conc. (0.01 – x) (0.1 + x) xM
Q 0.01m ≈ 0.1 M
+
[x ][A ] 2 × 10
– –7
Now, Ka = = = 2 × 10−5
[HA] 0.01
[CB]
8. pH = pKa + log
[WA]
[CB]
5.74 = 4.74 + log
1
⇒ [CB] = 10 M
9. In pure water,
Ksp = S2 = (8 × 10–4)2
= 64 × 10–8
In 0.01 M H2SO4
H2SO4(aq) → 2H+ (aq) + SO42–(aq).
0.02 0.01
BaSO4(s) Ba2+(aq.) + SO42–(aq)
X x (x + 0.01)
–8
Ksp = x (x + 0.01) = 634 × 10
x + 0.01 ≅ 0.01 M
So, x (0.01) = 64 × 10–8
x = 64 × 10–6 M
10. An acidic buffer is a mixture of weak and its salt with strong base. Now, let us study the
composition of each mixture obtained by mixing of two solutions.
+
(A) CH3COOH + NaOH → CH3COONa + H2O
t =0 100 × 0.1 100 × 0.1 0 0
milimol
t=a 0 0 10 10
So, it is not a buffer.
NaCl, a salt of strong acid (HCl) and strong base (NaOH) is not hydrolysable by HCl also. So,
it is not a buffer.
+
CH3COOH + NaOH → CH3COONa + H2O
t=0 100 × 0.1 200 × 0.1 0 0
(Limiting)
milimol
= t a 0= 20 − 10 10 10 10
After mixing, the solution contains equimolar amounts by NaOH(a strong base) and
+
CH3COONa (salt). So, it is also not a buffer.
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+
CH3COONa + HCl → + CH3COOH + NaO
t =0 200 × 0.1 100 × 0.1 0 0
(Limiting)
milimol
= t a 20 − 10
= 10 0 10 10
Now, the resultant solution contains equimolar amount of CH3COOH (an week acid) and
CH3COONa (a salt of CH3COOH with strong base, NaOH).
So, it is an acid buffer.
3 1
11. 3g CH3COOH (M = 60) = = mol
60 20
250
250 mL of 0.1 M HCl = M × V = × 0.1
1000
= 25 × 10–3 mol
After mixing these two, solution is diluted to 500 mL.
Then from that solution, 20 mL is taken.
20 1
Number of moles of both CH3COOH and HCl will be now only = of original solution.
500 25
1 1 1
nCH3COOH = × = = 2 × 10–3 mol
20 25 500
1
nHCl = 25 × 10–3 × = 10–3 mol
25
1
nNaOH added = M × V = × 5 × 10–3 = 2.5 × 10–3
2
After mixing, all HCl and NaOH will be neutralized. Remaining number of moles.
nNaCl = 10–3
= 1.5 × 10−3
nCH3COONa
nCH3COOH (unreacted) = 0.5 × 10–3
∴ Now the solution is a buffer solution.
[salt]
pH = pKa = log
[acid]
(nCH3COONa )
= pKa + log
(nCH3COOH )
= 4.75 + log 3 = 4.75 + 0.4771 = 52271 = 5.23
12. Both (A) and (R) are correct, but (R) is not the correct explanation of (A).
[A] Cu2 (aq) and S2–(aq) ions undergo ionic reaction whose are of reaction is very fast.
Cu2+(aq) + S2–(aq) → CuS(s) ↓
[R] For the reaction :
Cu2+(aq) + S2–(aq) CuS(s)
The expression of equilibrium constant is,
[CuS]
K eq =
[Cu2+ ][S2− ]
But, the expression of solubility product (Ksp) of CuS(s) will be
CuS(s) Cu2+(aq) + S2–(aq)
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Ksp = [Cu2+] [S2–]
[CuS] 1
So, =K eq is,K eq ∝
K sp K sp
Because of high stability CuS, the value of Keq is high, i.e. the value of Ksp of CuS will be low.
13. (A) 4 g NaOH in 100 L
4 / 40
⇒ =M = 10 −3 mol L–1.
100
(B) 9.8 g H2SO4 in 100 L
9.8 / 98
⇒=M = 10 −3 mol L–1
100
40 L of solution A contains
= 40 × 10–3 mol NaOH (Q n = M × V)
= 40 × 10–3 mol OH–
10 L of solution B contains
= 10 × 10–3 mol H2SO4
= 20 × 10–3 mol H+
When they are mixed, total volume = 50 L and all H+ is neutralized by OH–.
Number of moles (nOH− ) of excess OH–.
= (40 – 20) × 10–3 = 20 × 10–3
nOH−
[OH− ] = (in liter)
Vsolution
−
nOH−
or [OH ] =
Total volume
20 × 10 −3
= = 4 × 10 −4 M
50
As we know,
pOH = log[OH–]
∴ pOH = –log 4 × 10–4 = 4 – log 4
or pH = 14 – pOH
= 14 – (4 – log 4) = 10 + log 4 = 10.602
14. Units given for all option is M3, or (mol L–1)3, which implies that, the equilibrium has three ions.
Therefore,
XY2 X2+ (aq) + 2Y–(aq), Ksp = [X2+] [Y–]2
or X2Y 2X+(aq) + Y2–(aq), Ksp = [X+]2 [Y2–]
(i) Ksp in case of XY2,
Ksp = (1 × 10–3) (2 × 10–3)2 = 4 × 10–9 M3
(ii) Ksp in case of X2Y,
Ksp = (1 × 10–3)2 (2 × 10–3) = 2 × 10–9M
The only matching value of Ksp from options that satisfies the concentration values from graph
is [X2+] = 1 mM = 1 × 10+ M and [Y–] = 2 × 10–3 M
thus, salt is XY2 and Ksp = (10–3) (2 × 10–3)2 = 4 × 10–9 M3
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15. The strength of aqueous NaOH solution is most accurately determined by titrating aqueous
NaOH in burette and aqueous oxalic acid in conical flask with phenolphthalein as an indicator.
(For weak acid-strong base titration, methyl orange cannot be used).
Thus, solution turns colourless to pink at the end point. (Phenolphthalein has pink colour when
pH > 10 and it is colourless when pH < 8 (approximately) which is easily to perceive.
If NaOH is taken in conical flask and oxalic acid is added from burette, the end point will be
the decolourisation of pink colour which is more difficult to perceive by human eye quickly.
16. The dissociation of water into H+ and OH– is an endothermic reaction.
∴ As temperature increase, its equilibrium constant also increases :
∴ [H+] and [OH–] in water at equilibrium increases with increases in temperature.
∴ pH = – log[H+] decreases, as temperature increases.
So, both Assertion and Reason are false.
17. PbCl2(s) Pb2+(aq) + 2Cl–(aq); Ksp = 1.6 × 10–5
For mixture, 300 mL 0.134 M Pb(NO3)2 and 100 mL 0.4 M NaCl
After mixing, total volume = 400 m
[Pb2+] after mixing (before any precipitate forms)
300 × 0.134 3 × 0.134 1
= = =
400 4 10
[Cl–] after mixing (before any precipitate forms)
100 × 0.4
= = 0.1
400
As we know,
3 × 0.134
Q = [Pb2+] [Cl–]2 = × 10–2 = 10–3
4
18. Ksp of Cr(OH)3 at 298 K is 6.0 × 10–31.
[OH–] in saturated solution of Cr(OH)3 = ?
Cr(OH)3 �Cr3+ + 3OH–
S S
In a saturated solution, Ksp = [Cr3+] [OH–]3
= S(3S)3 = 27S4 = 6.0 × 10–31
1
6.0 × 10 −31 6.0 × 10 −31 4
∴ =S4 = ⇒S
27 27
1 1
6.0 × 10 −31 4 6.0 × 3 4 −31
4
−31 4
1
[OH–] = 3S = 3 = 3
× 10 (18 × 10 )
27 3
19. Given 100 mL of 0.1 M HCl is taken in beaker and to it 100 mL of 0.1 M NaOH is added. This
is acid (HCl) and base (NaOH) titration. Here, phenolphthalein act as an indicator and colour
change is pink. The correct graph that depicts the change in pH is as follows. At first HCl
(acid) is take in beaker and base (NaOH) is taken in burette.
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When base is added drop wise then acid-base reaction is occurs and following changes are
observed.
pH → 0 to 7 is acidic. pH → 7 is neutral
pH → 7 to 14 is basic.
Initially, the graph increases steeply but when concerntration of acid becomes equal to base
then no change is seen in graph.
This point is called neutral point or equivalence point. Equivalence point, where pH = 7.
After the equivalence point (pH = 7, base (NaOH) is continuously mixed drop by drop then pH
increases by 7 and graph also increases slowly. At the point B solution become basic, again
base (NaOH) is mixed drop by drop and the solution becomes basic at point B. Following
inference can be seen in the graphs.
(A) According to this graph, pH = 7 is equivalence point and use of naOh (base) drop by drop
leads to basic solution as a result, value of pH increases slowly. This is correct option.
(B) According to graph, it shows straight line that mean graph increases instantly but this
titration show pH increases slowly because base (NaOH) is mix drop by drop.
(C) After equivalence point (pH = 7) graph is constant. It is wrong because graph increases
and the solution becomes pure basic then graph show constant value.
(D) According to graph, equivalence point (pH = 7) graph should increases but it decreases.
20. The concentration of a substance in a saturated solution is defined as its solubility(S).
For AxBy xAy+ + yBx– ; Ksp = [Ay+]x[Bx–]y
For, Zr3(PO4)4,
Zr3(PO4)4(s) 3Zr 4 + (aq) + 4PO34− (aq)
3SM 4 SM
[PO34− ]4
4+ 3
Ksp = [Zr ]
1
K sp 7
Ksp = (3S)3 (4S)4 = 6912 S7 or S =
6912
1
K sp 7
Thus, the relation between molar solubility(S) and solubility product (Ksp) will be S =
6912
21. The explanation of given statements are as follows:
In statement (I), millimoles of H+ = 400 × 0.1 × 2 = 80
Millimoles of OH– = 400 × 0.1 = 40 (Limiting reagent)
∴ Millimoles of H+ left = 80 – 40 = 40
40 40 1
[H+] = = = M M
400 + 400 800 20
1
⇒ pH = –log[H+] = –log
20
= –log1 + log2 + log10
= –0 + 0.301 + 1 ⇒ 1.30
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Hence, the option (A) is correct.
In statement (II), ionic product of H2O is temperature dependent.
Kw = [H+] [OH–] ≈ 10–14(mol/L)2 at 25°C
With increases in temperature, dissociation of H2O units into H+ and OH– ions will also
increase. As a result, the value of ionic product, [H+] × [OH–] will be increased. e.g.
Temperature Kw (mol/L2)
5°C 0.186 × 10–14
25°C 1.008 × 10–14
45°C 4.074 × 10–14
Hence, the option (B) is correct.
In statement (III), for a weak monobasic acid HA
HA H⊕ + AΘ
(1 – α) αCM αCM
⇒ pH of the solution is 5, i.e.
[H+] = 10–5 M = αC
αC × αC 10 −5 × α
⇒ Ka = =
(1 − α )C 1− α
10−5 × α
⇒ –5
10 = ⇒ α = 0.5 ⇒ a% = 50
1− α
Hence, the option (C) is correct.
In statement (IV), Le-Chatelier's principle is applicable to common ion effect. Because, in
presence of common ion (given) by strong electrolyte (say, Na+ + A ), the product of the
concentration terms in RHS increases. For the weaker electrolyte, HA H⊕ + AΘ.
As a result dissociation of HA gets suppressed.
Hence, the option (D) is incorrect.
22. NH4Cl is a salt of weak base (NH4OH) and strong acid (HCl). On hydrolysis, NH4Cl will
produce an acidic solution (pH > 7) and the expression of pH of the solution is
1
pH = 7 – (pKb + logC)
2
Given, kb(NH4OH) = 10–5
∴ pKb = –logKb = – log(10–5) = 5
C = concentration of salt solution = 0.05 M = 2 × 10–2 M
1
Now, pH = 7 – (pKb + logC)
2
On substituting the given values in above equation, we get
1
= 7 – [5 + log(2 × 10–2)]
2
1
= 7 – [5 + log2 – 2]
2
1
= 7 – [5 + 0.301 – 2]
2
= 7 – 1.65 = 5.35
23. Concentration of substance in a saturated solution is defined as its solubility (S). Its value
depends upon the nature of solvent and temperature. For reaction,
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AB A+ + B–
Ksp = [A+] [B–]
Al(OH)3 Al3+ + 3OH–
Initially 1 0 0
At equilibrium 1 – S S 3S + 0.2
NaOH → Na + OH + –
0.2 0.2
Ksp of Al(OH)3 = 2.4 × 10–24 (Given)
Ksp = [Al]3+ [OH–]3
2.4 × 10–24 = [S] [3S + 0.2]3 [Q 0.2 >> S]
2.4 × 10–24 = [S] [0.008]
[S] = 3 × 10–22
24. Depression in freezing point (∆Tƒ) is given by ∆Tƒ = iKƒm
i = vant Hoff factor
Kƒ = molal depression constant, m = molality
Kƒ = 4.0 K kg mol–1 (Given)
m = 0.03 mol kg–1 (Given)
∆Tƒ = ?
For K2SO4, i = 3
It can be verified by the following equation :
K2SO4 2K+ + SO24−
Using formula
∆Tƒ = iKƒ × m
∆Tƒ = 3 × 4 × 0.03 = 0.36 K
25. Let solubility of Ag2CO3 is S. Now,
0.1 M of AgNO3 is added to this solution after which let the solution of Ag2CO3 becomes S'
∴ [Ag+] = S + 0.1 and CO32− = S'
Ksp = (S + 0.1)2 (S') ...(i)
Given, Ksp = 8 × 10–12
Q Ksp is very small, we neglect S' against S in Eq.(i)
∴ Ksp = (0.1)2S'
or 8 × 10–12 = 0.01 S'
or S' = 8 × 10–12 × 102 = 8 × 10–10 M
Thus, molar solubility of Ag2CO3 in 0.1 M AgNO3 is 8 × 10–10 M.
26. Its given that the final volume is 500 mL and this final volume was arrived when 50 mL of 1 M
Na2SO4 was added to unknown Ba2+ solution. So, we can interpret the volume of unknown
Ba2+ solution as 450 mL i.e.
450mL + 50mL → 500mL
Ba2 + Na2SO4 BaSO4
solution solution solution
From this we can calculate the concentration of SO−42 ion in the solution via
M1V1 = M2V2
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1 × 50 = M2 × 500
(as 1 M Na2SO4 is taken into consideration)
1
M2 = = 0.1 M
10
Now for just precipitation,
lonic product = Solubility product (Ksp)
i.e. [Ba2+] [ SO24− ] = Ksp of BaSO4
Given Ksp of BaSO4 = 1 × 10–10
So, [Ba2+] [0.1] = 1 × 10–10
or [Ba2+] = 1 × 10–9 M
Remember This is the concentration of Ba2+ ions in final solution.
Hence, for calculating the [Ba2+] in original solution we have to use
M1V1 = M2V2
as M1 × 450 = 10–9 × 500
so, M1 = 1.1 × 10–9 M
27. Among the given salts
FeCl3 is acidic in nature i.e., have acidic solution as it is the salt of weak base and strong acid.
Al(CN)3 and Pb(CH3COO)2 are the salts of weak acid and weak base.
CH3COOK is the salt of strong base and weak acid.
Hence, the solution of CH3COOK will be most basic because of the following reaction.
CH3COOK + H2O CH3 COOH+ KOH
(Weak acid) (Strongbase)
28. Methyl orange show pinkish colour towards more acidic medium and yellow orange colour
towards basic of less acidic media. Its working pH range is
←
Pinkish
3.9 − 4.5
Yellow
→
Re d Orange
Weak base have the pH range greater than 7, When methyl orange is added to this weak
base solution it show yellow orange colour.
Now when this solution is titrated against strong acid the pH move towards more acidic range
and reaches to end point near 3.9 where yellow orange colour of methyl orange changes to
pinkish red resulting to similar change in colour of solution as well.
29. For a salt of weak acid and weak base,
1 1
pH = 7 + pKa – pKb
2 2
Given, pKa(HA) = 3.2, pKa(BOH) = 3.4
1 1
∴ pH = 7 + (3.2) – (3.4)
2 2
= 7 + 1.6 – 1.7 = 6.9
30. pH = 1
∴ [H+] = 10–1 = 0.1 M
pH = 2
∴ [H+] = 10–2 = 0.01 M
For dilution of HCl,
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M1V1 = M2V2
0.1 × 1 = 0.01 × V2
V2 = 10 L
Volume of water to be added = 10 – 1 = 9 L
31. HQ = H+ + Q–
[H+] = K aC by Ostwald's dilution law
[H ] = 10–pH = 10–3 M
+
C = 0.1 M
Thus, 10–3 = K a × 0.1
–6
10 = Ka × 0.1
∴ Ka = 10–5
Alternate method
HQ H+ + Q–
Initial concentration 0.1 M 0 0
+ –3
Given, pH = 3, this suggest [H ] = 10 M at equilibrium
Thus, [Q–] at equilibrium = 10–3 M
Hence, [HQ] = 0.1 M – 10–3 M
≈ 0.1 M [Q 10–3 M <<< 0.1 M]
Ka for the above reaction is given by
[H+ ][Q− ] [10 −3 ][10 −3 ]
Ka = =
[HQ] [0.1]
Ka = 1 × 10–5
32. Let molar solubility of Cr(OH)3 = s mol L–1
Cr(OH)3(s) Cr 3+ (aq) + 3OH– (aq)
s 3s
Ksp = 106 × 10–30
= [Cr3+] [OH–]3 = (s) (3s)3 = 27s4
1.6 × 10 −30
∴ s4 =
27
1.6 × 10 −30
∴ s= 4
27
33. [AgBr] = [Ag+] = 0.05 M
Ksp [AgBr] = [Ag+] [Br–]
K sp ( AgBr )
⇒ [Br–] =
Ag+
5.0 × 10−13
= = 10–11 M [mol L–1]
0.05
Moles of KBr needed to precipitate AgBr
= [Br–] × V = 10–11 mol L–1 × 1L = 10–11 mol
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Therefore, amount of KBr needed to precipitate AgBr
= 10–11 mol × 120g mol–1 = 1.2 × 10–9 g
34. Mg(OH)2 Mg2+ + 2OH–
Ksp = [Mg2+] [OH–]2
K sp 1× 10−11
[OH–] = =
[Mg2+ ] 0.001
pOH = –log [OH–1] = –log [10–4]
pOH = 4 and pH = 10
∴ pH = 14 – pOH = 14 – 4 = 10
35. Na2CO3 2Na+ + CO32−
[Na2CO3] = [ CO32− ] = 1 × 10–4 M
BaCO3 Ba2+ + CO32−
K sp(BaCO3 ) = [Ba2+] [ CO32− ]
K sp (BaCO3 )
[Ba2+] =
[CO32− ]
5.1× 10 −9
[Ba2+] =
1× 10−4
[Ba2+] = 5.1 × 10–5 M
Hence, at 5.1 × 10–5 M concentration of Ba2+, a precipitate will begin to form.
36. Conjugate bases of the given species are
species Conjugate base
HCO3− CO32−
H3O+ H2O
−
HSO 4 SO24−
HSO3F HSO3−
Since, strong acid has a weak conjugate base.
Thus, the basic strength of the conjugate bases of the given acid is opposite to their acidic
strength. The basic strength of the conjugate bases of the given acids follows the order
HSO3− < H2O < SO24− < CO32− .
Hence, the acidic strength follows the order
HSO3F > H3O+ > HSO4− > HCO3−
37. For salt of weak acid and weak base
1
pH = [log Ka + log Kw – log Kb]
2
1 1 1 1 1
= pKa + pKw – pKb = × 4.80 + 7 – × 4.78 = 7.01
2 2 2 2 2
38. AgIO3(s) Ag+(aq) + IO3− (aq)
Let the solubility of AgIO3 be S
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Ksp = [Ag+] IO3−
1.0 × 10–8 = S2 or S = 1 × 10–4 mol/L
In 1000 mL moles of AgIO3 dissolved
= 1 × 10–4 moles
In 100 mL moles of AgIO3 dissolved
= 1 × 10–5 moles
Mass of AgIO3 in 100 mL
= 1 × 10–5 mol × 283 g mol–1 = 2.83 × 10–3 g
39. When HA is 50% ionised. [HA] = [A–]
Buffer solution of weak acid HA → acidic buffer
[A − ]
pH = pKa + log
[HA]
or pH = pKa = 4.5
pOH = pKw – pH
pOH = 14 – 4.5 = 9.5
40. The overall dissociation constant of the acid is
K = K1 × K2
= 1.0 × 10–5 × 5.0 × 10–10 = 5 × 10–15
41. H3PO4 is a tribasic acid, thus ionisec in three steps.
−
I. H3PO4 H+ + H2PO4
− 2−
II. H2PO4 H+ + HPO4
2− 3−
III. HPO4 H+ + PO4
2−
conjugate base is formed when an acid loses its proton. Thus, HPO4 is the conjugate base
−
of H2PO4 (Which is an acid in step II, but is the conjugate base of H3PO4 in step I).
42. MX4 M4+ + 4X–
Ksp = [M4+] [4X–]4
Ksp = (S) (4S)4
⇒ Ksp = 256 S5
1/5
K sp K sp
S = 5
⇒ S=
256 256
43. AB2 A2+ + 2B–
S 2S
Ksp = [A ] [B ] = (S) (2S)2 = 4S3
2+ – 2
=4(1 × 10–5)3 = 4 × 10–15
44. In 1 × 10–8 M HCl solution, H2O is also present which also undergoes self ionisation.
H2O H+ + OH–
10–7 M at 25°C
[Concentration of water (H2O)]
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If it is taken simply even without common ion effect, higher concentration must be considered
which is 10–7 M but H+ from HCl decreases self ionisation of water and hence [H+] from H2O.
Hence, net concentration must be smaller than 10–7M.
45. According to Bronsted Lowry concept of acids and bases, an acid is a proton donor whereas a
base is a proton acceptor.
2−
Thus, according to this concept, HPO4 can easily donate a proton and also accepts a proton
on reaction with water.
HPO24− + H2O PO34− + H3O+
HPO24− + H2O H2PO24− + OH–
46. Ca(OH)2 Ca2+ + 2OH–
Ksp = [Ca2+] [OH–]2
= (S) (2S)2 = 4S3
47. NaCl is salt of strong acid and strong base. Its not the case of buffer.
NaCl + H2O NaOH + HCl
Aqueous NaCl, itself exact neutral solution.
HCl + H2O H3O+ + Cl–
makes solution acidic.
48. Calcium acetate is a salt of weak acid and weak base.
0.005 M calcium acetate, (CH3COO)2Ca
(CH3COO)2Ca → Ca2+ + 2CH3COO–
0.005 M (2 × 0.005 = 0.01)
∴ [CH3COO ] = 0.01M
–
CH3COO– + H2O CH3COOH + OH−
Alkaline
pK a logC
pH = 7 + +
2 2
log0.01
= 7 + 2.37 +
2
= 7 + 2.37 – 2.30 = 7.06
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 01
S
ELECTROCHEMISTRY
TOPIC : ELECTRODE POTENTIAL
SOLUTIONS
1. In galvanic cell/electro chemical cell electrical energy is produced due to some chemical
reaction.
2. Salt bridge complete the electrical circuit and minimises the liquid-liquid junction potential.
3. Agar-Agar is a gelatin, it used in salt bridge along with KCl electrolyte.
4. Ecell = E°Ni / Ni2+ + E° Ag+ / Ag = 0.25 + 0.80 = 1.05 Volt.
5. E0 is intensive property and it does not depend on mass of F2 taking part.
6. Lowest S.R.P., highest reducing power.
7. E0Cu2 + / Cu = 0.34 0
EFe 2+
/ Fe
= –0.44 volt
So Cu can't displace Fe2+ .
8. Cu can't displace Al3+ ion from aluminium nitrate.
9. Lower S.R.P. containing ion can displace higher S.R.P. containing ion.
10. KCl can make precipitate with AgNO3, Pb(NO3)2 so can't be used along these electrolyte.
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 02
S
ELECTROCHEMISTRY
TOPIC : ELECTRODE POTENTIAL
6. Lowest S.R.P., highest reducing power.
8. Fe3+ + 3e– → Fe , – 0.036 volt
Fe → Fe2+ + 2e– 0.44 volt
Fe3+ + e– → Fe2+
+ 3 × 0.036f –2 × 0.44 × f = – 1 × E° × f
E° = 0.772 Volt
9. Cu+ + e– → Cu, E° = x1 Volt
Cu2+ + 2e– → Cu, x2 Volt
Cu → Cu+ + e– – x1Volt
Cu2+ + e– → Cu+
– 2 × x2 × f + 1 × x1 × f = –1 × Eº × f
Eº = 2x2–x1
10. For spontaneous reaction in every condition
Ecell > 0, ∆G < 0 and Q (reaction quotient) < K (equilibrium constant).
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 04
S
ELECTROCHEMISTRY
TOPIC : ELECTROLYSIS
SOLUTIONS
4. At anode Ag → Ag+ + e–
At cathode Ag+ + e– → Ag
So conc. of Ag+ will remain same .
5. equivalence of H2 = equivalence of O2
0.224 volume of O2
×2= ×4
22.4 22.4
0.112 litre = volume of O2.
8. In presence of inert electrode, the cell reaction is -
Anode : H2O → 4H+ + 4e– + O2
Cathode : {Cu++(aq) + 2e– → Cu(s)} × 2
Net cell reaction 2Cu++ aq. + 2H2O → 4H+ + 2Cu(s) + O2 ↑
Due to increases in [H+], pH decreases.
∴ (B) is answer
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 05
S
ELECTROCHEMISTRY
TOPIC : FARADAY LAW'S
SOLUTIONS
1. +
8H + 5e + –
MnO4– →
Mn +2
+ 4H2O
(1 mole)
5 mole e– = 5 Faraday.
1
2. Mole of Fe deposited = × 3 = 1.5 mole
2
WFe = 1.5 × 56 = 84 g.
63.5
3. W= × 2 × 60 × 60 = 2.37 g
2 × 96500
3
% of efficiency = ×100.
2.37
4. 2H2O + 2e– → H2 + 2OH–
9.65 × 1000
No. of Faraday passed = = 0.1 F
96500
nOH– formed = 0.1 mol
nNaOH = 0.1 mol ≡ 4 g.
5. According to Faraday’s second law
mass of A mass of B mass of C
= =
equivalent mass of A equivalent mass of B equivalent mass of C
4.5 2.7 9.6
= =
15 / n1 27 / n2 48 / n3
0.3n1 = 0.1n2 = 0.2n3 = k
10
n1 = k
3
n2 = 10k
n3 = 5k
10 1 1
n1 : n2 : n3 = : 10 : 5 = : 1 : =2:6:3
3 3 2
0.3 : 0.1 : 0.2
3:1:2
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 06
S
ELECTROCHEMISTRY
TOPIC : ELECTROLYTIC CONDUCTANCE
SOLUTIONS
1. For strong electrolyte
Λ MC = Λ M∞ – b C
2. Molar conductivity α no. of ions per mole of electrolyte.
5. Ka = 25×10–6 ∧eq = 19.6 Scm2 eq–1 , C = 0.01
⇒ 25 × 10 –6
Ka = 0.01 × α2 α= –2
= 5 × 10–2
10
19.6 ⇒ 19.6
α = 5 × 10–2 = ∧°eq = = 392 Scm2 eq-1.
∧°eq 5 × 10 –2
1000 × 3.06 × 10 –6
6. 1.53 =
Normality
Normality = 2 × 10–3 M
2 × 10 –3
Molarity = = 10–3 M
2
Ksp = 10–6 M
2
7
7. Ka = Cα2 = 0.1× = 3.38 × 10–5
380.8
8. K = 1.382 × 10–6 s cm–1
1000 × 1.382 × 10 –6
ΛAgCl = 61.9 + 76.3 = 138.2 = S
⇒ S = 10–5 M.
∧ eq.,BaSO4
9. ∧m,BaSO4 = (x1 + x2 x – 2x3) ⇒ ∧ eq.,BaSO4 =
n − factor
(x + x – 2x3 )
∧ eq.,BaSO4 = 1 2
2
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 07
S
ELECTROCHEMISTRY
TOPIC : FUEL CELL & CONDUCTANCE
SOLUTIONS
1. Discharging reaction
Pb(s) + PbO2(s) + 2H2SO4 → 2PbSO4 + 2H2O.
2. H2–O2 fuel cell
At anode : 2OH– + H2 → 2H2O + 2e–
At cathode : 2 H2O + O2 + 4e– → 4OH–
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C HE M IS T RY
DPP
DAILY PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
NO. 08
S
ELECTROCHEMISTRY
TOPIC : MIXED PROBLEM
SOLUTIONS
1. H3 O + has highest Λ∞m among cations. A doubly charged cation has higher Λ∞m than unipositive
cation.
3.907
2. α= = 0.1
390.7
HA + aq H+ + A–
Cα Cα
Cα – Cα
[H+| = Cα = 0.01 × 0.01 = 10–4
pH = –log [H+] = 4
3. Ksol = KBa2+ + K Ag+ + KNO3–
λBa
o
2+
×[Ba2 + ]
λ oAg+ × [Ag+ ] λNO
o
–
× [NO– ]
3 3
5.3 = + +
10 –3 10 –3 10 –3
13 × 10 –3 × 0.1 6 × 10 –3 × 0.2 λ(NO
o
– × 0.4
)
∴ 5.3 = + + 3
10 –3 10 –3 10 –3
∴ λ(NO3– ) = 7 × 10–3 × 1000 Sm2mol–1 = 7 Sm2 mol–1
o
4. (A) H4XeO6 has more SRP, so better oxidizing agent then F2
(B) O3 has more SRP, so will oxidize Cl2
o
(C) EClO
4 / ClO3 is more in acidic medium than in basic medium
– –
o
(D) E[Fe(CN) 3– 4–
= 0.36 V
6 ] |[Fe(CN)6 ]
Hence [Fe(CN)6]4– can be easily oxidized by ClO¯, Ce4+ Br2O– but not by Li+
o o o
EClO EClO
(E) / Cl– (OH– ) is more than EBrO– / Br – and 4 / ClO3 (OH ) so true.
– – – –
(F) Ce4+ can’t oxidize Cl2 in acidic medium.
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1000 × ( κsol − κH2O )
5. λ0 =
S
1000 × (3.4 − 2.02) × 10 −6
138 =
S
S = 1 × 10–5
6. Cu2+ + 4NH3 → [Cu(NH3)4]2+
1 a 0
0 2 1
[Cu(NH3 )4 ]2+
Kf =
[Cu2+ ] [NH3 ]4
1
or 1 × 1012 = 2+ 4
or [Cu2+] = 6.25 × 10–14.
[Cu ] (2)
0.059 [Zn2+ ] 0.059 1
Now, ECell = E0Cell – log = 1.1 – log = 0.71 V.
2 2
[Cu ]+ 2 6.25 × 10 −14
K × 1000
7. λm =
M
K × 1000
200 =
0.04
200 × 0.04
K= = 8 x 10–3 S cm–1.
1000
l1
K = 9 x
R
8 1
8 x 10–3 = 4 x
R
2 1
R= = x 103 Ω .
8 × 10 −3 4
Again ⇒ V = IR
10
V
So, I= = 1 × 103 = 4 x 10–2A.
R 4
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λºm (Ba(OH) ) + 2 λºm (HCl) − λºm (BaCl2 )
8. λºm (H2O) = 2
2
= 5.5 × 10–2 S m2 mol–1.
Now, in SI units,
−3 K × 10 −3
λºm = K × 10 ∴ λºm (H2O) =
M [H2O] diss
5.5 × 10 −6 × 10 −3
5.5 × 10—2 =
[H2O] diss
[H2O] diss = [H+] = [OH–] = 10—7 M
For equilibrium: H2O H+ + OH–
10 −7 × 10 −7
Dissociation constant K =
[H ][OH ]
+ –
1000
=
[H2O] 18
= 1.8 × 10—16
Reported answer = 18
9. H2 → 2H+ + 2e–
1 atm 10–10
( )
2
10−10
EH / H+= 0 −
0.059
log ⇒ EH / H+
= +0.59 V
2
2 2 1
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 01
ELECTROCHEMISTRY
SOLUTIONS
1. Lower S.R.P. containing ion can displace higher S.R.P. containing ion.
2. ∆G0 = – nFE0cell
If E0cell = +ve then ∆G° = –ve and reaction is spontaneous.
3. (A) Anode : 2H2O → O2 + 4H+ + 4e–
(B) Anode : 2H2O → O2 + 4H+ + 4e–
(C) Anode : Cu →Cu2+ + 2e–
(D) Anode : 2H2O → O2 + 4H+ + 4e–
4. At Cathode : Cu2+ + 2e– → Cu(s)
At Anode : Cu (s) → Cu2+ + 2e–
2.68 × 3600 63.5
Increase in mass of cathode = decrease in mass of Anode = × = 3.174 g.
96500 2
5. Ag Cu Au
equivalent 1 : 1 : 1
ratio
1 1 1
Mole ratio : :
1 2 3
6 : 3 : 2
6. Resistance of cell is not due to vibrations of ion but actually it is due to collisons of ions.
7. Fe2+ + 2e– → Fe [in FeSO4] ; Fe3+ + 3e– → Fe [in Fe2 (SO4)3]
Fe3+ + 3e– → Fe [in Fe (NO3)3]
Q 56
Amount of Fe deposited in FeSO4 = ×
96500 2
Q 56
Amount of Fe deposited in Fe2(SO4)3 = ×
96500 3
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8. Anode : Pb(s)
Cathode : PbO2(s)
H2SO4(conc.) about 38% solution of H2SO4 is taken.
Anode : Pb(s) → Pb2+ (aq) + 2e–
Pb2+(aq) + SO24− (aq) → PbSO4(s)
Pb(s) + SO24− (aq) → PbSO4 + 2e–
most of the PbSO4(s) ppt sticks to the lead rod.
Cathode : 2e– + 4H+ + PbO2(s) → Pb2+(aq) + 2H2O(l)
Pb2+(aq) + SO24− (aq) +4H+ + 2e– → PbSO4(s) + 2H2O(l)
PbSO4(s) sticks to cathode rod.
Over all reaction : Pb(s) + PbO2 (s) + 2H2SO4 (aq) → 2PbSO4(s) + 2H2O(l), Ecell = 2.05 V
11. καc
Hence κ1 = a x 0.1
κ 2 = a x 0.01
κ3 = a x 0.005
κ 4 = a x 0.0025
κ
G=
cell constant
a × 0 .1 a × 0.01
So, G1 = ; G2 =
1 10
= 0.1 a = 0.001 a
a × 0.005 a × 0.0025
G3 = G4 =
.5 ; 25
= 0.001a = 0.0001 a
Hence G1 > G2 = G2 > G4
λºm
λºeq
13. = Vf
Vf for cation/anion – charge; Vf for salt = total cationic/anionic charge
Also, λºm (Al (SO ) ) = 2 λºm (Al3+) + 3 λºm SO 24–
2 4 3
( )
&
λºeq
(Al2(SO4)3) =
λºeq
(Al3+) + (
λºeq SO 24– )
14. Li+ Na+ K+ Rb+ Cs+
degree of Hydration decreases
Size of ions decreases
ionic mobility increases
H(+aq) has smallest size therefore show maximum mobility.
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29. At cathode :
1
Hg2Cl2(s) + e → Hg (l) + Cl¯ (aq)
2
At anode : Ag(s) + I¯ (aq) → AgI (s) + e
1
Hg2Cl2(s) + Ag(s) + I¯ (aq) Hg (l) + Cl¯ (aq) + AgI (s)
2
0.06
30. o
=
EI¯/ Agl/ Ag EoAg+ / Ag + log10 −16
1
= 0.8 – 16 × 0.06
= 0.8 – 0.96 = – 0.16
Eocell = 0.26 – (–0.16) = 0.42 volt
32. From given latimer diagrams.Cl2 – Cl– is independent of H+ cocentration.
0.42 + 1.36
33. ∆G0 = ∆G10 + ∆G20 , using this E0 = V = 0.89 V
2
34.
∆Gº
35. As is low, stability is higher.
F
∆Gº
36. As is low, stability is higher so, + 2 and 0 state is more stable than +1.
F
37. λm
C
= λm∞ – b C
when C1 = 4 x 10–4 λm
C
= 107
and when, C2 = 9 x 10–4 Λm = 97
so, 107 = λm∞ – b x 2 x 10–2 ... (1)
97 = λm∞ – b x 3 x 10–2 ... (2)
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b = 1000
Λm = λm∞ – b C
∞
λm = Λm + b C
= 107 + 103 x 2 x 10–2
∞ –1
λm = 127 ohm cm2 mole–1
38. For 25 x 10–4 (M) NaCl solution
Λm = λm∞ – b C
Λm = 127 – 103 (25 x 10–4)1/2
Λm = 127 – 103 x 5 x 10–2
Λm = 77
K x 1000 1
But Λm = K = x
M a R
1 1000
Λm = x x
a R M
1000
Λm = [Cell constant] x
R x M
1000
⇒ 77 = [Cell constant] x
1000 x 25 x 10 −4
Cell constant = 77 x 25 x 10–4 = 0.1925 cm–1
39. For Na2SO4 solution
1 0.1925
K = x = = 4.81 x 10–4 ohm–1 cm–1
a R 400
K x 1000 4.81 x 10 −4 x1000
Λm = =
M 5
x 10 −3
2
Λm (Na2SO4) = 192.4 ohm–1 cm2 mole–1
40. At the equivalence point the concentrations will be [Br–] = 100 mol/m3, [Na+] = 100 mol/m3
Therefore κtotal = κ Br − + κ Na+ = 1.2 Sm–1 = 12 × 10–1 Sm–1.
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 02
ELECTROCHEMISTRY
SOLUTIONS
PART-1
– 2+
1. MnO4 ion can oxidise both Fe to Fe as well as Cl– to Cl2. So Fe(NO3)2 cannot be estimated
3+
quantitatively with MnO4– ion in HCl.
EºCell for the cell Pt, Cl2(g) (1 atm) | Cl– (aq) | | MnO4– (aq) | Mn2+ (aq). is euqal to (1.51 – 1.4)
= 0.11 V.
0.06 [Zn2+ ]
2. E + 0.03 = Eº – log .
2 0.5
0.06 [Zn2+ ]
E = Eº – log . C = 0.05 M.
2 C
3. Zn | Zn2+ (0.01 M) | | Fe2+ (0.001 M) | Fe, E = 0.2905.
2+ 2+
cell reaction, Zn + Fe Zn + Fe.
0.0591 0.01
0.2905 = Eº – log .
2 0.001
Eº = 0.32 Volt.
At equilibrium, Ecell = 0.
0.0591
0 = 0.32 – log Keq
2
Keq = 100.32/0.0295.
4. In+ → In3+ + 2e–, 0.42 volt.
In + e → In ,
2+ +
– 0.4 volt.
______________________________
In2+ → In3+ + e–
______________________________
Eº = 0.44 volt.
Eºcell = 0.15 + 0.44 = 0.59 volt.
0.059
0 = 0.59 – log K.
1
K = 1010.
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5. Fe → Fe2+ + 2e–, 0.44 V.
1
2H+ + O2 + 2e– → H2O, 1.23 V.
2
______________________________________
1
Fe + 2H+ + O2 → Fe2+ + H2O, Eº = 0.44 + 1.23 = 1.67 volt.
2
∆Gº = – 2 × 1.67 × 96500 = – 322.3 kJ.
6. 2Ag+ + C6H12O6 + H2 →2Ag(s) + C6H12O7 + 2H+, Eº = 0.8 – 0.05 = 0.75 volt.
0.0592
0 = 0.75 – log K.
2
ln K = 2.303 × log K = 2.303 × 25.34 = 58.38.
7. [H+] = 10–11 M.
0.0591
Eoxide = – 0.05 – log(10–11)2 = – 0.05 + 0.65
2
or, ∆H = 0.65 volt.
8. Standards electrode potential does not depend upon on concentration.
9. AgBr (s) Ag+ + Br–
(S + 10–7) × S = KSP = 12 × 10–14 .
S = 3 × 10-7 M.
[Ag+] = 4 × 10–7 M ; [Br–] = 3 × 10–7 M ; [NO3–] = 10–7 M.
Ktotal = Λº(Ag+) Λº(Ag+) + ΛºBr– ΛºBr– + Λº(NO3–) Λº(NO3–)
ΛºKCl = ΛºK+ + ΛºCl– .
KKCl = 4 × 10–4 × 6 × 10–3 + 3 × 10–4 × 8 × 10–3 + 1 × 10–4 × 7 × 10–3.
KKCl = 24 + 24 + 7.
KKCl = 55 Scm–1.
10. Mol of NaCl = 4 × 0.5 = 2 mol.
1 1
No. of mole of Cl2 evolved = × mol of NaCl = × 2 = 1 mol.
2 2
11. Taking the 1 : 1 molar combination of Na–Hg amalgam.
weight = 2 × 23 + 2 × 200 = 446 g.
12. 2Na+ + 2e– → 2Na.
No. of Faraday required = 2.
∴ total charge = 2 × 96500 = 193000 coulomb.
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13. Cl2 + 2I– → I2 + 2Cl–.
Eº = 1.36 + (– 0.54) = 0.82 V (+ ve). Spontaneous.
14. Mn3+ + e– → Mn2+, 1.50 volt.
2H2O → O2 + 4H+ + 4e–, 1.23 volt.
______________________________
4Mn3+ + 2H2O → 4Mn2+ + O2 + 4H+, Ecell = 1.5 – 1.23 = 0.27 volt. (+ ve).
Mn3+ will oxidise H2O.
Ι × t (sec)
15. Faraday law equivalents of H2 produced =
96500
10 × 10−3 × t
0.01 x 2 = = 96500 x 2 = t
96500
19.3 x 104 sec = t
16. The species having less reduction potential with respect to NO3– (Eº = 0.96 V) will be oxidised
by NO3–.
These species are V, Fe, Hg.
17. M (s) | M+ (aq, 0.05 M) || M+ (aq, 1 M) | M(s)
Anode : M (s) → M+ (aq) + e–
Cathode : M+ (aq) + e– → M (s)
_____________________________________
M+ (aq) |c M+ (aq) |a
0.0591 M+ (aq) |a
Ecell = E°cell – log +
1 M (aq) |c
0.0591 0.05
=0– log
1 1
= + ve = 70 mV and hence ∆G = – nFEcell = – ve.
−0.0591 0.0025 0.0591 0.05
18. Ecell = log = − log
1 1 1 20
0.0591
= 70 mV + log 20 = 140 mV.
1
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19.
0.059 [Fe2+ ]2
20. E = Eº – log + 4
4 [H ] PO2
0.06 (10 −3 )2 0.03
= 1.67 – log −3 4
= 1.67 – log107
4 (10 ) × 0.1 2
0.03
= 1.67 – × 7 = 1.67 – 0.105 = 1.565 = 1.57 V.
2
21. M|M2+ (aq) || M2+ (aq) | M
0.001 M
Anode : M → M2+ (aq) + 2e–
Cathode : M2+ (aq) + 2e– → M
______________________
M2+ (aq)c M2+ (aq)a
0.059 M2+ (aq)a
Ecell = 0 – log −3
2 10
0.059 M2+ (aq)a
0.059 = − log −3
2 10
M2+ (aq)a
– 2 = log −3
10
10–2 × 10–3 = M2+ (aq)a = solubility = s
Ksp = 4s3 = 4 × (10–5)3 = 4 × 10–15
22. ∆G = – nFEcell = – 2 × 96500 × 0.059 × 10–3 kJ/mole
= – 11.4 kJ/mole.
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X Y
23. (P) (C2H5 )3 N + CH3 COOH → CH3COO– (aq) + (C2H5)3NH+ (aq)
As CH3COOH is a weak acid, its conductivity is already less. On addition of weak base, acid-
base reaction takes place and new ions are created. So conductivity increases.
(Q) KI (0.1 M) + AgNO3 (0.01 M) → AgI ↓ (ppt) + KNO3 (aq).
As the only reaction taking place is precipitation of AgI and in place of Ag+, K+ is coming in
the solution, conductivity remain nearly constant and then increases.
(R) CH3COOH + KOH → CH3COOK (aq) + H2O
OH– (aq) is getting replaced by CH3COO–, which has poorer conductivity. So conductivity
dereases and then after the end point, due to common ion effect, no further creation of ions
take place. So, conductivity remain nearly same.
(S) NaOH + HI → NaI (aq) + H2O
As H+ is getting replaced by Na+ conductivity dereases and after end point, due to OH–, it
increases.
So answer of 39 is : (P) – (3) ; (Q) – (4) ; (R) – (2); (S) – (1). Answer is (D).
24. (P) EºFe3+, Fe
⇒ 1 × 0.77 + 2 × (– 0.44) = 3 × x
0.11
⇒ x=– V ~ – 0.04 V.
3
(Q) 4H2O 4H+ + 4OH–
2H2O → O2 + 4H+ + 4e– – 1.23 V
+ O2 + 2H2O + 4e → 4OH
– –
+ 0.4 V
_____________________________________
4H2O 4H+ + 4OH– – 0.83 V
(R) Eº(Cu2+ + Cu → 2Cu+)
x × 1 + 0.52 × 1 = 0.34 × 2
x = 0.16 V.
⇒ Cu2+ + e– → Cu+ 0.16 V
+ Cu → Cu+ + e– – 0.52 V
______________________________________________________________
Cu2+ + Cu → 2Cu+ – 0.36 V
However, in the given option, – 0.18 V is printed.
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(S) Eº(Cr3+, Cr2+)
x × 1 + 2 × (– 0.91) = 3 × (– 0.74)
x – 1.82 = – 2.22
⇒ x = – 0.4 V
Hence, most appropriate is (D).
(P) – (3) ; (Q) – (4) ; (R) – (1) ; (S) – 2.
25. Salt bridge is introduced to keep the solutions of two electrodes separate, such that the ions in
electrode do not mix freely with each other. But it cannot stop the process of diffusion.
It does not participate in the chemical reaction. However, it is not necessary for occurence of
cell reaction, as we know that designs like lead accumulator, there was no salt bridge, but still
reactions takes place.
26. m+ → m3+ + 2e–
∆G0 = –nFE0 For 1 mole of m+
∆G0 = –2 × 96500 × (–0.25) J
= + 48250 J/mole = 48.25 KJ/mole
Energy released by conversion of 1 mole of
x → y ∆G = –193 KJ
Hence mole of m+ convert
193
=4
48.25
27. λ° − ≈ λ° −
X Y
⇒ λ° + + λ° − ≈ λ° + + λ° −
H X H Y
° °
⇒ λHX ≈ λHY (1)
λm ° °
Also = α, So λm (HX) = λm α1 and λm (HY) = λm α2
λm °
(Where α1 and α2 are degrees of dissociation of HX and HY respectively.)
Now, Given that
λm (HY) = 10 λm (HX).
° °
⇒ λm α2 = 10 × λm α1
α2 = 10 α1 (2)
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Cα 2
Ka = , but α << 1, therefore Ka = Cα2 .
1– α
2
K a (HX) 0.01α12 0.01 1 1
⇒ = = × = .
K a (HY) 0.1α 2
2 0.1 10 1000
⇒ log (Ka (HX)) – log (Ka (HY)) = –3. ⇒ pKa (HX) – pKa (HY) = 3.
[M2+ ][H+ ]2
28. Ecell = E°cell – 0.059 log10 4 +
2 [M ] pH2
0.092 = 0.151 = 0.059 log10 10x
2
∴x=2
29. C = 0.0015M l = 120 cm
G = 5 × 10–7s a = 1 cm2
a
G=κ×
1
5 × 10–7 = κ ×
120
κ = 6 × 10–5 s cm–1
κ × 1000 6 × 10 –5 × 1000
Λm
c
= =
M 0.0015
pH = 4
[H+] = 10–4 = c α = 0.0015 α
10 –4
α=
0.0015
6 × 10 –5 × 1000
Λm
c
10 –4
0.0015
α= ⇒ =
Λm
o 0.0015 Λmo
Λm
o
= 6 × 102 s cm2 mole–1
[ Zn2+ ]
30. ∆G = ∆G° + 2.303 RT log10Q ; Q =
[Cu2+ ]
= –2F(1.1) + 2.303 RT log1010
= 2.303 RT –2.2 F
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31. Mg → Mg2+ + 2e–
Cu2+ + 2e– → Cu
________________________
Mg + Cu2+ Mg → Mg2+ + Cu
RT x
E = 2.67 = 2.7 –
n
nF 1
300
0.03 = lnx
2 × 11500
2.3 = lnx
X = 10
32. A(s)|An+ (aq, 2M) || B2n+ (aq, 1M) | B(s)
Reactions
Anode (A → An+ + ne) × 2
Cathode B2n+ + 2ne → B
______________________________
Overall reaction :
2A(s) + B2n+ → 2An+ + B.
RT
E = Eº –
nQ
2nF
RT [A n+ ]2
O = Eº –
n
2nF [B2n+ ]
RT
Eº =
n4
2nF
−2nFRT
Now ∆Gº = –2nFEº = n4 = –RTln4.
2nF
∆Gº = ∆Hº –T∆Sº = 2∆Gº = –T∆Sº
T∆Sº = ∆Gº
∆Gº –RTn4
∆Sº = = = –Rln4
T T
= –8.3 × 2 × 0.7 = –11.62 JK–1mol–1
PART-1
OFFLINE (JEE-MAIN)
o
33. The E of cell will be zero.
34. Here Cr3+ is oxidised to C2O72 −
35. At LHS (oxidation) 2 × (Ag → Ag+ + e– ) Eºox = –x
At RHS (reduction) Cu2+ + 2e– → Cu Eºred = + y
2Ag + Cu2+ → Cu + 2Ag+, Eºred = (y – x)
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1 1
36. K= =
ρ RA
0.059
37. 0 = 0.295 – logK ; log K = 10 ; K = 1010.
2
38. A B C
Eored +0.5 V –3.0 V –1.2 V
The reducing power follows the following order : B > C > A.
39. Eºcell = 0.77 + 0.14 = 0.91 volt.
0
40. ∧ = 126 + 152 – 150 = 128 S cm2 mol–1.
NaBr
41. Zn + 2H+(aq) → Zn2+ (aq) + H2 (g)
0.0591 [Zn2+ ] pH2
E = Eº – log
2 [H+ ]2
Adding H2SO4 means increasing H+ and therefore Ecell will increase and reaction will shift to
forward direction.
42. Cr 2+ | Cr 3 + = +0.41V Mn2+ | Mn3 + = −1.57V
Fe2+ | Fe3 + = −0.77V Co2+ | Co3 + = −1.97V
As Cr will have maximum oxidation potential value, therefore its oxidation will be easiest.
43. Difluoroacetic acid will be strongest acid due to electron withdrawing effect of two fluoring
atoms so as it will show maximum electrical conductivity.
44. Al3+ + 3e– → Al.
5.12 × 103
=189.62 mol.
27
Charge = 189.62 × 3 × 96500 = 5.489 × 107 coulomb.
45. CH3COONa + HCI → CH3COOH + NaCI From the reaction,
Λ 0CH3COONa + Λ = Λ 0CH3COOH + ΛoNaCI or Λ 0CH3COOH = Λ 0CH3COONa + Λ – ΛoNaCI
o o
HCI HCI
Thus to calculate the value of one should know the value of ΛoNaCI along with and ΛoHCI.
0.059
46. 0.152 = – 0.8 – log KSP ; log KSP = – 16.11.
1
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47. C = 0.1 M, R = 100 Ω
1
K = 1.29 Sm-1 = × .
100 A
C = 0.02 M, R = 520 Ω.
1
K= × 129
520
1
× 129
ÅM = 520 = 124 × 10–4 Sm2mol-1.
1000 × 0.02
48. According to Kohlrausch's law the molar conductivity at infinite diluation (Λo) for weak
electrolyte CH3COOH is
ΛoCH3COOH = ΛoCH3COONa + ΛoHCI – Λo NaCI
So for calculating the value of ΛoCH3COOH , value of ΛoNaCI should also be known.
0.0591 [Zn2+ ] [Zn2+ ] [Zn2+ ]
49. 0 = + 1.1 – log ; log = 37.3.; = 1037.3 Ans.
2 [Cu2+ ] [Cu2+ ] 2+
[Cu ]
0.059 [Cr +3 ]2
50. Ecell = E0cell – log
6 [Fe+2 ]3
0.056 (0.1)2
= 0.3 – log = 0.3 – 0.04 = 0.26 V
6 (0.01)3
51. Fe3+ + 3e– → Fe ∆G1 = –3 × F × EFe
0
3+
/ Fe
Fe2+ → Fe ∆G2 = –2 × F × EFe
0
2+
/ Fe
Fe3+ + e– → Fe2+ ∆G = ∆G1 – ∆G2
∆G = 3 × 0.036F – 2 × 0.439 × F = – 1 × E0 (Fe3+/Fe+2) × F
E0 (Fe3+/Fe+2) = 2 × 0.439 – 3 × 0.036
= 0.878 – 0.108 = 0.770 V
2 4
52. Al2 O3 → Al + O2
3 3
∆rG = +966 kJ mol–1 = 966 × 103 J mol–1
∆G = – nFEcell
966 × 103 = – 4 × 96500 × Ecell
Ecell = 2.5 V
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53. 2H+ (aq) + 2e– → H2 (g)
0.0591 PH 0.0591 2 0.0591
Ered = Eºred – log + 2 2 ; Ered = 0 – log 2 ; Ered = – log2
n (H ) 2 (1) 2
∴ Ered is forund to be negative for (3) option.
54. X + Y2+ → X2+ + Y
For reaction to be spontaneous Eº must be positive.
EºZn / Zn+2 + EºNi2+ / Ni = 0.76 + (– 0.23) = + 0.53 (positive)
55. Higher the SRP, better is oxidising agent
Hence MnO4- is strongest oxidising agent
56. x = 1.4 S/m.
R = 50 Ω
M = 0.2
1
K= ×
R A
⇒ = 1.4 × 50 m–1.
A
Now, new soltuion has M = 0.5, R = 280 Ω
1 1 1
⇒K= × = × 1.4 × 50 =
R A 280 4
1
K 1
⇒ ΛM = = 4 = = 5 × 10 −4
1000 × M 1000× 0.5 2000
57. λc = λ∞ − B C (Debye Huckel onsagn equation)
58. Reason : Higher the position of element in the electrochemical series, more difficult is the
reduction of its cations.
If Ca2+ (aq) is electrolysed, water is reduced in preference to it. Hence it cannot be reduced
electrolytically from an aqueous solutions.
E0 =1.51V E0 = −1.18V
59. Mn2+
1
→ Mn2+
2
→ Mn
∴ for Mn2+ disproportionation, E0 = – 1.51 V –1.18 V
= – 2.69 V < 0
Reaction is non-spontaneous.
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60. Cu2+ + 2e– → Cu
2F 1 mole
= 63.5 g.
61. Galvanization is applying a coating of Zn.
62. For strongest reducing agent E°OP should be maximum.
E°OP Cr / Cr +3 = 0.74 V
Whereas
E°OP Mn2+ / MnO − = –1.51 V
4
E°OP Cr 3 + / Cr O−2 = –1.33 V
2 7
E°OP Cl– / Cl2
= –1.36 V
63. B2H6 + 3O2 → B2O3 + 3H2O
1 mol 3 mol
3 mol O2 is required for Burning 1 mol B2H6
H2O 1 (V.F. of O2 = 4)
→ H2 + O2
Electrolysis
2
Equivalent of O2
= mol of O2 = 3
V.F.of O2
(100A) × t sec. 1 = 3
× 4
96500
∴ t = 3 × 96500 × 4 hr. = 3.22hrs.
100 × 3600
ONLINE (JEE-MAIN)
68. Electrons flow from anode to cathode always.1
69. MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
0.059 [Mn2+ ]
E = 1.51– log
5 [MnO4– ][H+ ]8
Taking Mn2+ and MnO4– in standard state i.e. 1 M,
0.059 1 0.059
E = 1.51 – × 8 log + = 1.51 – × 8 × 3 = 1.2268 V
5 [H ] 5
Hence at this pH, MnO4– will oxidise only Br– and I– as SRP of Cl2/Cl– is 1.36 V which is greater
than that for MnO4– /Mn2+.
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70. If a block of copper metal is dropped into a beaker containing solution of 1 M ZnSO4, no
reaction will occur because EoZn2+ / Zn = –0.76 V
EoCu2+ / Cu = +0.34 V
Hence Cu can’t displace Zn from ZnSO4 solution.
71. Fact
72. Fe2+ + 2e– → Fe + E1o = –0.47 V
Fe3+ + e– → Fe2+ + Eo2 = +0.77 V
Fe3+ + 3e– → Fe + Eo3
n1E1o + n2Eo2 2 × ( −0.47 ) + 1× ( 0.77 )
Eo3 = = = – 0.057V
n1 + n2 2 +1
73. EoT/ T+ = + 0.34V
= EoA/ A+ = + 0.55V
Therefore Tl+ more stable
74. o
EMn2+
/ Mn3 +
= 1.57V ; EHo + / H = OV
2
2+ +
Mn cannot reduce H to H2
75. Cell reaction :
M(s) + 3Ag+ (aq) → M3+ (aq) + 3Ag(s)
Applying Nernst equation :
0.059
Ecell = Eocell − log10 Q
n
0.059 0.001
∴ o
0.421 = (0.8 × EM 3+ )– log10
( 0.01)3
/M
3
∴ o
EM 3+
/M
= 0.32V
76. Cathode
2e– + 2H2O → H2 + 2OH– (v.f.)H2 = 2
i× t
mole =
v.f. × 96500
112 i × 965
=
22400 2 × 96500
1 i
=
2 2
i = 1 amp
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OH
77. C6H5NO2 →
NH2
4e– + 4H+ + C6H5NO2 → C6H4 (OH)(NH2 ) + H2O
M.W. = 109 g
E M
(v.f.) = 4 W = ZIt = ×I×t E = 4
F
109 × 9.65 × 60 × 60
W=
4 × 96500
W = 9.81 g
78. PbSO 4 (s) + 2e – → Pb(s) + SO 24 –
For 2F current passed, PbSO4 electrolyzed = 303g/mol
0.05 × 303
For 0.05F; PbSO4 electrolyzed = = 7.6g
2
79. ∆Gº = –RTlnK
–2 × 96000 × 2 = –8 × 300 × lnK
or, lnK = 160
or, K = e160
80. Higher the SOP, higher will be reducing power.
1
81. A: H2 (g) → H+ (aq.) + e– E° = 0.0 V
2
C : AgCl (s) + e– → Ag (s) + Cl– E° = x V
0.0591
Ecell = E°cell – log {[H+] [Cl–]}
1
0.06
0.92 = x – log (10–12)
1
0.92 = x + 0.72
x = 0.92 – 0.72 = 0.2 Volts
82. Fact
83. E ocell = E oZn( s)|Zn+ 2 + E oAu3 + / Au
= SOPanode + SRPcathode
= 0.76 V + 1.40 V = 2.16V
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0.0591 0.0591
84. E°cell = log Kc = log(1× 1016 ) = 0.4728 V
n 2
dE
85. ∆H = – nFEcell + nFT
dT
= –2 × 96000 × 2 + 2 × 96000 × 300 × (–5 × 10–4)
= – 384000 – 28,800 = – 412.8 kJ/mol
86. Λºm(HA) = Λ°m(HCl) + Λ°m(NaA) – λ°(NaCl)
= 425.9 + 100.5 – 126.4 = 400
° K × 1000 5 × 10 –5 × 103
=
Λm ⇒ = 50
M 10 –3
50
=
α = 0.125
400
87. 2Cu+(aq) Cu(s) + Cu2+(aq)
For the cell reaction,
=º
ECell º
ECu +
/Cu
− ECu
º
2+
/Cu
= (0.52 – 0.16) V = 0.36 V
⇒ ∆Gº = – nF ECell
º
⇒ –RTlnK = – nF ECell
º
E 1
⇒ lnK = n × × ECell
º
= 1× × 0.36 =14.4 = 144 × 10
–1
RT 0.025
88. NaCl is a strong electrolyte, whereas BaSO4 is a sparingly soluble (weaker) electrolyte. So,
even in saturated solution, NaCl will almost remain in dissociated form to give free Na+ and
Cl–. But availability of Ba2+ and SO24− in water will be very poor. But degree of dissociation of
BaSO4 will increase with a temperature to give more ions.
BaSO4(s) Ba2+(aq) + SO24+ (aq)
Again, with increase in temperature ionic mobility alos increases. So options(a), (b) and (d)
are true but (c) is false.
Solubility of NaCl in water remains almost constant with increase in temperature. So, option ©
is false.
Solubility
NaCl
Temperature (ºC)
(Solubility curve)
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89. Given Cr2O72− + 14H+ + 6e– → 2Cr3+ + 7H2O
8 × 60 × 2
Number of moles = [Q F = 96000 C]
96000
Using stoichiometry,
neused nCr 3 + Pr oduced
=
6 2
2 8 × 60 × 2 1
⇒ nCr 3+ produced = × =
6 96000 30
Theoritically produced
1
Weight=
Cr 3 + 30 × 52 g [Q Mass of Cr = 52]
Weight actual = 0.104 g
Weight(actual)
Efficiency = × 100
Weight(theoritical)
0.104g
Efficiency of the process = × 100 =
60%
1
30 × 52
90. ∴ ∆Gº = –nF Ecell
º
Here ∆Gº = 14.37 kJ mol–1
n = number of electrons
F = Faracday constant = 96500 C/mol
= 17.37 × 1000 J mol–1
º
17.37 × 1000 = – 3 × 96500 × Ecell
17.37 × 1000
º
Ecell =
3 × 96500
º
Ecell = –0.06 = – 6 × 10–2
91. Molar and activity, λm is defined as the conducting power of all the ion produced by dissolving
one gram mole of on electrolyte in solution, it is a function of the ionic strength of a solution.
The molar conductivity of both weak and strong electrolytes increases with decrease in
concentration Molar conductivity is the conductivity affered by one mole of ions.
Increased dilution results in the dissociation of more electrolytes into ions and effectively
increasing the number of active ions in the solution. These active ions impart more
conductivity.
CH3COOH
Λ/Scm–2mol–1
KCl
C1/2/mol1/2L1/2
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92. For 1 mol of ClO3− , 6 F charge required but current efficiency is only 60%. So, to obtain 1 mol
10g
ClO3− , Now, moles of KClO3 =
122
10
∴ Charge = × 10F
122
∴ Current using = 2 A
Applying, W=Z×l×t
10 2
∴ = × 2 × 3600 ⇒ t = 11 hrs
122 96500
Hence, the correct answer is (11).
93. Given, cell is Cu(s)|Cu2+(C1M)||Cu2+(C2M)|Cu(s)
Gibbs free energy, DG = – nFEcell
∆G is negative, if Ecell is positive, two half reaction are as follows for given cell reaction
At anode Cu(s) → Cu2+(C1) + 2e–
At cathode Cu2+(C2) + 2e– → Cu(s)
Total cell reaction
Cu2+(C2) → Cu2+(C1) ; Ccell
º
=0
2.303RT C
Ecell = 0 – log 1
nF C2
C1
Ecell > 0 ; if < 1 ⇒ C1 < C2
C2
C2 = 2 C1 is correct
94. The half cel reactions are :
(1) Cu2+ + 2e– Cu; Eº = 0.34 V
+ –
(2) Cu + e Cu; Eº = 0.522 V
2+ – +
(3) Cu + e Cu ; Eº = x
As we know, QGº = – nFE
∴ To obtaine the Eº of required equation, subtract ∆Gº of equation (2) from ∆Gº of (1) as
∆Gº of (3) = ∆Gº of (1) – ∆Gº (1) as
Or – 1× F × x = (–2 × F × 0.34) – (–1 × F × 0.522)
∴ x = 2 × 0.34 – 0.522 = 0.68 – 0.522 = 0.158 V
95. According to Kohlrausch’s law,
Limiting molar conductivity of an electrolyte is the sum of the individual contributions of the
cation and the anion of the electrolyte. Therefore, for option(a).
λ mº (Na + ) + λ mº (Br − ) − λ mº (Na + ) − λ mº (Cl− )
= λmº (K + ) + λmº (Br – ) − λmº (K + ) − λ mº (Cl− )
Or λmº (Br − ) − λmº (Cl− ) = λ mº (Br − ) − λ mº (Cl− )
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∴ LHS = RHS
∴ The LHS of option (a) = λmº (Br − ) − λmº (Cl− ) and also RHS of that = λmº (Br − ) − λmº (Cl− )
LHS = RHS
For option(b),
λ mº (K + ) + λ mº (Cl− ) − λ mº (Na + ) − λ mº (Cl− )
= λmº (K + ) + λmº (Br − ) − λmº (Na + ) − λmº (Br − )
Or λmº (K + ) + λmº (Na + ) − λmº (K + ) − λ mº (Na + )
∴ LHS = RHS
Similarly for option (c),
LHS = λmº (Br − ) − λmº (I− )
and RHS = λmº (K + ) − λmº (Na + )
∴ LHS RHS
Thus, the correct answer is (c)
0
96. Give, Ered = 123 V
But as the given half cell reaction is an oxidation reaction, Therefore,
º
Eoxi = −Ered
º
= – 1.23 V ⇒ n = 4
T = 298 K ⇒ pH = 5 ⇒ [H+] = 10–5
By Nerst equation, at 298 K :
0.0591
= Eº −
E logQ [Q Q = Po2 × [H+]4]
n
0.0591
= –1.23 – log1 × (10–5)4
4
1
= –1.23 – 0.0591 log10−20
4
= – 1.23 – 0.0591 × 5 log 10
= –1.23 – (0.0591 × – 5) = 1.23 × 0.295
= –0.935 V ≈ –0.94 V
97. (exact value –2.154
Cel notation
Sn(s) |Sn2+ (aq ; 1 M)| |Pb2+(aq; 1M)) |Pb(s)
Cell reaction :
Sn(s) + Pb2+(aq) Pb(s) + Sn2+(aq)
[Sn2+ ]
Equilibrium constant (K) = ⇒ unknown
[Pb2+ ]
=º
ECell º
ECathode − EºAnode
= (–0.13 V) – (–0.14 V) = 0.01 V
From Nernst equation,
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2.303RT 0.06
=Eº = logK logK
nF n
nEº
∴ =
logK = ;(n 2)
0.06
2 × 0.01 1
= = 0.33 or
0.06 3
K = 100.33 or 101/3 = =
3
= 2.15
10 2.154
The value may range from 2.13 to 2.17
98. Equal quantity of electricity produces same number of equivalent of productcs in electrolysis.
∴ No. of equivalent of O2 produced = No. of equivalents of Ag produced
No. of equivalent of Ag
Mass 108
= = = 1.
Equivalent mass 108
∴ No. of equivalents of O2 formed =1.
For production of O2 from water
2H2O → O2 + 4H+ + 4e–
n-factor = 4
1
∴ 1 equivalent = moles
4
Volume of gas at 273 K and 1 bar pressure
1
= 22.7 × n = 22.7 × - 5.675 L
4
99. Eqn is –
MnO4– + H⊕ + 5e– → Mn+2 + 4H2O
Nernst equation:
[Mn+2 ] 1
8
0.059
E= E 0
− log
[MnO4− ] H+
cell cell
5
(I) Given [H⊕ ] = 1M
0.059 [Mn+2 ]
E= E0 − log
[MnO−4 ]
1
5
(II) Now : [H⊕ ] = 10–4 M
0.059 [Mn+2 ] 1
E2 =
E − 0
log ×
5 [MnO4 ] (10 −4 )8
−
0.059 Mn+2 0.059
=E −
0
log −
+ log10−32
5 [MnO4 ] 5
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0.059
therefore : E1 − E=
2 × 32 = 0.3776 V = 3776 × 10–4
5
x = 3776
2+
101. Zn(s) → Zn(aq.) + 2e–
2Ag(aq.) + 2e– → 2Ag(s)
_______________________________
+ 2+
Zn(s) + 2Ag(aq.) → Zn(aq.) + 2Ag(s)
_______________________________
=
E0cell E0Ag+ / Ag − E0Zn2+ /Zn
= 0.80 – (–0.76)
= 1.56 V
−0.059 [Zn2+ ]
Ecell = 1.56 log
2 [Ag+ ]2
0.059 0.1
= 1.56 − log
2 (0.01)2
0.059
=1.56 − ×3
2
= 1.56 – 0.0885
= 1.4715
= 147.15 × 10–2
m.mol
102. Given concn of KCl =
L
: Conductance (G) = 0.55 mS
: Cell constant = 1.3 cm–1
A
To Calculate : Molar conductivity (λm) of sol.
1 k
→ Since λ=
m × .....(1)
1000 m
mol
→ Molarity = 5 × 10–3
L
1.3
→ Conductivity = G × =
0.55 mS × 1 m
−1
A
100
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= 55 × 1.3 mSm–1
1 55 × 1.3 mSm2
eqn (1) λ= ×
1000 5 mol
m
1000
mSm2
⇒ λm = 14.3
mol
1
103. =
κ ·G ∗
R
For same conductivity cell, G∗ is constant and hence κ.R. = consant
∴ 0.14 × 4.19 = κ × 1.03
0.14 × 4.19
Or, κ of HCl solution =
1.03
= 0.5695 Sm–1
= 56.95 × 10–2 Sm–1 ≈ 57 × 10–2 Sm–1
0 0
E1 E2
Fe3+ Fe3+ Fe
104. F30
E10 + 2E02 =
3E30
=
E10 3E03 − 2E02
= 3 (–0.036) –2(–0.44)
= + 0.772 V
= EFe
E0cell 0
3+
/Fe2 +
+ EI0−=
/I
0.233
2
∆rG = – 2 × 96.5 × 0.233 = –45 kJ
0
105. From Kohlrausch’s law
Λ m∞ (BaSO4 ) = λ m∞ (Ba 2+ ) + λ m∞ (SO2–
4 )
Λ m∞ (BaSO4 ) = λ m∞ (BaCl2 ) + Λ m∞ (H2SO4 ) − 2 Λ m∞ (HCl)
= 280 + 860 – 2 (426)
= 288 Scm2 mol–1
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C HE M IS T RY
MPP
MASTER PRACTICE PROBLEMS
TARGET : JEE(MAIN + ADVANCED)
ST
NO. 03
ELECTROCHEMISTRY
SOLUTIONS
3. Lowest standard reduction potential highest reducing power.
4. Lowest standard reduction potential highest reducing power.
1
9. SO42– + 4e– → S2O32–
2
–4 × Eº × F = 2 × 0.936 F + 2 × 0.576 F
2 × 0.936 + 2 × 0.576
Eº = – = – 0.756 volt
4
10. Mn3+ + e– → Mn2+ 1.5 volt
Mn3+ → MnO2 + e– – 1 volt
2H2O + Mn3+ → MnO2 + 4H+ + e–.
2Mn3+ + 2H2O→ MnO2 + 4H+ + Mn2+.
2Mn3+ → Mn2+ + MnO2, Eº = 1.5 – 1 = 0.5 volt.
∆G = –1 × 0.5 × 96500 = – 48.25 KJ.
11. 2AI2O3 (melt) → 2AI2O3(s) , ∆G1º = – 2 × 16
2AI2O3(s) → 4AI(I) + 3O2(g), ∆G2º = 2 × 1269
3C + 3O2 → 3CO2, ∆G3º = – 3 × 395
2AI2O3 (melt) + 3C → 4AI (I) + 3CO2(g),
∆Gº = ∆G1º + ∆G2º + ∆G3º = – 32 + 2 × 1269 – 3 × 395 = 1321 kJ
∆Gº = – nFEº ⇒ 1321 × 103 = – 12 × Eº × 96500
Eº = – 1.14 volt
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12. H2 → 2H+ + 2e–
0.1M and PH2 = 1 atm
0.0591
Eoxidation = 0 – log ( PH2 )2 = + 0.0591 × 1 = 0.0591 volt
2
14. Cu2+ +2e– → Cu,
pH = 14, [H+] = 10–14 M [OH–] = 1 M ⇒ [Cu2+] × 12 = 1 × 10–19
⇒ [Cu2+] = 1 × 10–19 M
0.0591 1 0.0591
E = 0.34 – log −19 = 0.34 – × 19 = – 0.2214 volt
2 10 2
15. (M → Mn+(0.02M) + ne–) × 2
(2H+ + 2e– → H2) × n
2M + 2nH+ → 2Mn+ + nH2
0.81 = (0.76 + 0) –
0.0591
log
( 0.02) 2
⇒ (0.81 – 0.76) =
0.0591
log 4 × 10–4
2n (1)2n 2n
0.0591
n=– × log 4 × 10–4 = – 0.591 (–4 + 0.6) = 2.
2 × 0.5
16. (a) Zn + 2Ag+ (aq) Zn2+ (aq) + 2Ag(s)
(b) Eº = 0.8 – (– 0.76) = 1.56 V
0.059 [Zn2+ ] [Ag+ ]2
(c) 1.6 = 1.56– log or 1.356 = log
2 [Ag+ ]2 [Zn2+ ]
[0.1]2 0.01 0.01
or log 2+
= 1.356 or 2+
= 22.7 or [Zn2+] = = 4.4 × 10–4 M
[Zn ] [Zn ] 22.7
17. EºZn / Zn2+ = 0.76 volt EºCu / Cu2+ = – 0.34 volt
CuSO4 + Zn → ZnSO4 + Cu.
0.0591 Zn2+ Zn2+
O = (0.76 + 0.34) – log ⇒ log = 37.22
2 Cu2+ Cu2+
18. Cu2+ + 2e– → Cu
No. of Faraday required = 2 F = 2 × 6.023 × 1023 = 12.04 × 1023
E
19. 0.108 = × 0.5 × 193 E = 108 g/eq.
96500
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WAg E Ag 108 0.5094
20. = = 108
=n n= = 1.92 n = 2.
Wmetal EM n
0.2653
2.977 3 × 1 × 60 × 60
21. = . ⇒ n = 4.
106.4 / n 96500
108
22. 10.8 × 80 × 5 × 10–4 = ×2×t ⇒ t = 193 sec
1 × 96500
0.54
23. Ag+ + e–
→ Ag = 5 × 10–3 mol
108
2H2O + 2e–
→ H2 + 2OH–
–3 –3
nH2 = 2.5 × 10 , VH2 = 22.4 × 2.5 × 10 = 56.0 mL
24. With Ni electrode, cathode reaction, Ni2+ + 2e– → Ni, Anode reaction, Ni → Ni2+ + 2e
No. Change in molarity of solution.
2 × 96500
25. 2HSO4– → S2 O82– + 2e– + 2H+ i= i = 71.48 Amp.
60 × 60 × 0.75
1 4
26. K= × = 2.332 × 10–3 mho cm–1.
245 7
2.33 × 10 –3 × 1000
Λm = = 23.32 mho cm2 mol–1.
0.1
27. RA = 50 Ω RB = 100 Ω
1 1
KA = × & KB = ×
50 A 100 A
when equal volmes one taken the
1 2 1 1
Kresultant = × = × + ×
R1 A 50 A 100 A
2 150 2 × 50 × 100 200
= ⇒ R1 = = = 66.7Ω
R 1 50 × 100 150 3
28. l = 1.5 cm A = 10 cm2 , C = 0.05 M
Effective area A' = 5 cm , R = 50 Ω 2
1 1 1.5 1000 1.5
K= × 1 = × Λm = × = 120 Scm2 mol–1.
R A 50 5 0.05 50 × 5
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29. Λeq = 97.1 Scm2 eq–1, C = 0.1 N
A = 1.5 cm2, l = 0.5 cm
Λeq =
1000 × ( R1 × A) ⇒ 97.1 =
1000
×
1
×
0.5
C 0.1 R 1.5
V 5
R = 34.33 Ω ⇒ i= = = 0.1456 amp
R 34.33
30. C = 0.1 N, K = 1.12 × 10–2 Scm–1, R = 65Ω
1
K= × = cell constant = 1.12 × 10–2 × 65 = 0.728 cm–1
R A A
31. Λºm(NH4CI) = 150 = Λºm(NH4+) + Λºm(CI–)
ΛºOH– = 198, ΛºCI– = 76 , Λm(NH4OH) = 9.6, C = 0.01
Λºm(NH4OH) = 150 – 76 + 198 = 272
Λ m (NH4 OH) 9.6
α= = = 0.0353
Λ ºm (NH4 OH) 272
2
7.36 7.36
32. α= Ka = Cα2 = 0.05 × = 1.77 × 10–5 mol/ lit
390.7 390.7
1000 × 2.28 × 10 −6
33. KAgCI = 2.28 × 10–6 Scm–1, 138.3 =
S
S = 1.65 × 10–5 and Ksp = (S)2 = 2.72 × 10–10 M2.
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