IIT JEE MAIN & ADVANCED

PREVIOUS YEAR'S
QUESTIONS BOOKLET
FOR CLASS XIIth
STUDENT'S
 ABOUT EDUCATORS

DR. SHARAD KOTHARI

• MSc., PhD, NET, JRF
• 18 year experience of IIT JEE in Organic Chemistry
• Ex. Senior Faculty of Vibrant Academy, Kota and Bansal Classes, Kota

PIYUSH MAHESHWARI
• BE (Hons.)
• 11 year experience of IIT JEE in InorganicChemistry
• Author of 'Super Problems in Inorganic Chemistry',
• Ex. HOD Bansal Classes, Kota
• Ex. Senior Faculty of Vibrant Academy, Kota and Allen Career Institute, Kota

BRIJESH JINDAL
• BTech Jaipur MNIT
• 11 year experience of IIT JEE in Physical Chemistry
• Ex. Senior Faculty of Vibrant Academy, Kota, Allen Career Institute, Kota and Bansal
Classes, Kota
 INDEX
S.NO. TOPIC
er ts r ts
PAGE NO.
e 01-39
1
E x
CHEMICAL KINETICS p Exp
r y
t(JEE ADVANCED)
EXERCISE (JEE MAIN)
try 01-12

m i s mis
C heEXERCISE
Che 13-18

ANSWER KEY 19

HINT & SOLUTIONS 20-39

2 SOLD STATE 40-59

EXERCISE (JEE MAIN)

er ts 40-43

E xp
EXERCISE (JEE ADVANCED)
r ts
44-47

ANSWER KEY ry pe
i st Ex 48-49

h e mSOLUTIONS try
C
HINT &

mis 50-59

THERMOCHEMISTRY h e
C ts
3 60-74
er
xp
EXERCISE (JEE MAIN) 60-64

E
try 67
EXERCISE (JEE ADVANCED) 65-66

mis
ANSWER KEY

ts Che
e r
xp
HINT & SOLUTIONS 68-74

E
tryADVANCED)
4 RADIOACTIVITY 75-85
EXERCISEs(JEE
i
m KEY ts
75-79

Ch e er
xp
ANSWER 80-81

ry E
HINT & SOLUTIONS
ist 82-85

em
Ch s
5 THERMODYNAMIC 86-105
er t
p
EXERCISE (JEE MAIN) 86-91
x
E92-95
EXERCISE (JEE ADVANCED)
stry
ts mi
ANSWER KEY
er Che 96

HINT & SOLUTIONS

Exp 97-105

str y
m i
Che
6
r ts
STATE OF MATTER (IDEAL GAS)
r ts 106-123
e 106-109
EXERCISE (JEE MAIN)pe p
E x Ex
st r y ADVANCED) stry
m i
EXERCISE (JEE
mi 110-113

CheANSWER KEY
Che 114

HINT & SOLUTIONS 115-123

7 STATE OF MATTER (REAL GAS) 124-132

EXERCISE (JEE MAIN) 124-125

er ts
xp
EXERCISE (JEE ADVANCED) 126-128

y E er ts
tr p
ANSWER KEY 129

m is Ex
h e
HINT & SOLUTIONS
stry 130-132
CATOMIC STRUCTURE mi
8
Ch e 133-159

er ts
xp
EXERCISE (JEE MAIN) 133-140

E
try 146
EXERCISE (JEE ADVANCED) 141-145

mis
ANSWER KEY

ts Che
e r
xp
HINT & SOLUTIONS 147-159

ry E
9
is t
ELECTRO CHEMISTRY 160-209

e m r ts
ChEXERCISE (JEE ADVANCED)
EXERCISE (JEE MAIN) 160-172

xpe
ry E 173-182

ist
m
ANSWER KEY 183

Che ts
HINT & SOLUTIONS
r
184-209

p e
E x
y
10 IONIC EQUILIBRIUM 210-242

is r
t 210-219
ts m
EXERCISE (JEE MAIN)

er Che
xp
EXERCISE (JEE ADVANCED)
E
220-223

ANSWER KEY y
istr 224

h e
HINT mSOLUTIONS
& 225-242
C
11 LIQUID SOLTIONS
r ts r ts 243-272
e 243-252
EXERCISE (JEE MAIN)pe p
E x Ex
st r y ADVANCED) stry
m i
EXERCISE (JEE
mi 253-256

CheANSWER KEY
Che 257

HINT & SOLUTIONS 258-272

12 SURFACE CHEMISTRY 273-281

EXERCISE (JEE MAIN) 282-281

er ts
xp
EXERCISE (JEE ADVANCED) 282-284

y E er ts
tr p
ANSWER KEY 285

m is Ex
h e
HINT & SOLUTIONS
stry 286-290
C mi
Ch e
er ts
Exp
istry
hem
er ts C
Exp
istry
hem r ts
C xpe
ry E
ist
em
Ch er ts
Exp
stry
ts mi
er Che
Exp
stry
mi
Che
 Chemical Kinetics

EXERCISE # (JEE-MAIN)
1.
s
 2HI the true relationship is –
t
For the reaction H2 + I2 
r r ts[AIEEE-2002]
deHI 1pde
x =p =x
 2  2     2  2   
E dt dt E 2 dt
d H d I  d H d I HI
(1) – =–
y r2dyI 1 d HI
= (2)

2ds
r
 Ht  = – 2d I = d HI
dt dt dt
2d  His t
– i
(3)m
 2   
(4) m =
  2   

Che dt e
2 2

Ch
=
dt dt dt dt 2 dt

2. A chemical reaction 2A + 2B + C –– product follows the rate equation : r  [A] [B]2 then
order of reaction is - [AIEEE-2002]
(1) 0 (2) 1 (3) 2 (4) 3
3. The rate constant of first & second order reaction is respectively - [AIEEE-2002]
–1 –1
(1) time , mole . litre . time
e r ts (2) mole litre , time
–1 –1 –1 –1

E xp
(3) mole–1 . litre . time–1, time–1 (4) sec , litre
r t s
–1 –1

In the equationtkt
s r y x p e
4.
m i = ln C – ln C , the curve
0 between
y
tt
E
and ln C is - [AIEEE-2002] t

h e
(1) a straight line (2) a parabola
CConsider following two reactions – mis tr
(3) a hyperbola (4) none of these
5.
A h
e
d C  
e r ts
xp
A —— Product —— – = k [A]° 1

E
dt

try
d B  
B —— Product —— –
dt
= k [B] 2
is
mas - [AIEEE-2002]
h e –1

(2) M secrt, s (3) sec , M C

k and k are expressed in terms of molarity (mol L ) and time (sec)
1 2

e
–1 –1 –1 –1 –1 –1 –1 –1 –1

p
(1) sec , M sec M sec sec (4) M sec , sec

E x metal surface like tungsten. This follows ........ order reaction -

6. 2

s t r y
H gas is adsorbed on the

m i sFirst
[AIEEE-2002]

h(1)eThird (2) Second (3) Zero

C In respect of the equation k = Ae in chemical kinetics, e r t
(4)
7.
E x p which one of the following
–Ea/RT

t ry
i(2)s R is Rydberg's constant
statement is correct ? [AIEEE-2003]

m
Che (4) A is adsorption factor
(1) E is energy of activation
a
(3) k is equilibrium constant
e r ts
8. For the reaction system: 2NO(g)+O (g)2NO (g) volume is suddenly reduced to half
E x pits value
by increasing the pressure on it. If the reaction is of first order with respectyto O and second
2 2

i s tr [AIEEE-2003] 2

ts value m
order with respect to NO, the rate of reaction will –

e r C h e
(2) Increase to four timesxofp
(1) Increase to eight times of its initial

(3) Diminish to r
E its initial value
y of its initial value
is t one-fourth

e m
(4) Diminish to one-eight of its initial value
h
C
1
 Chemical Kinetics
9. The rate law for a reaction between substances A and B is given by Rate = k [A]n [B]m. On
doubling the concentration of A and halving the concentration of B, the ratio of the new rate to

e r t s
the earlier rate of the reaction will be as :
e r t s [AIEEE-2003]

(1) (n – m)
E x p (2) 2(n – m)
1
E
(3)  m  n x p (4) (m + n)

s t ry s t
2
r y
i
mrate equation for the reaction 2A+B heC m i
C
10.
heThe
C
is found to be : rate= k[A][B]. The correct
statement in relation to this reaction is that the [AIEEE–2004]
(1) rate of formation of C is twice the rate of disappearance of A.
(2) Half life is a constant
(3) unit of k must be s–1

s
(4) value of k is independent of the initial concentrations of A and B

In a first order reaction, thep e r t

11.
E x t s M is
concentration of the reactant, decreases from 0.8 M to 0.4 M in 15
r
tr y
minutes. The time taken
s p
for the concentration to change from 0.1 M
x e 0.025

m i E
yminutes (4) 60 minutes
[JEE MAIN-2004]

h e
CThe half-life of a radioisotope is four hours.
(1) 7.5 minutes (2) 15 minutes
s t r
i If the initial mass of the isotope was 200 g, the
(3) 30

e m
Ch is [JEE MAIN-2004] ts
12.
mass remaining after 24 hours undecayed
p e r
(1) 3.125 g (2) 2.084 g (3) 1.042 g (4) 4.167 g
E x
Consider an endothermic reaction X  Y with the activation energies
is trEyand E for the
m
13. b f
backward and forward reactions, respectively. In general
s C h e [AIEEE-2005]
(1) E > E
b f
e r t
(2) E < E
b f
E xp between E and E
(4) E = E try
(3) there is no definite relation b f

m
b
is
f

s
14. h Ae
C (1) first order reaction e r t
preaction
reaction involving two different reactant can never be - [AIEEE-2005]

E x
(2) unimolecular

t r y
is
(3) biomolecular reaction (4) second order reaction

e m
firsth s
15. t can be taken as the time taken for the concentration of a reactant to drop to 3/4 of its initial
value. If the rate constant for a C t
1/4
order reaction is k, then t can be written as–
e r
xp
1/4

(4) 0.69/k E
[AIEEE-2005]
(1) 0.29/k (2) 0.10/k (3) 0.75/k
s tr y
Rate of reaction can be expressed by Arhenius equation as k = Aei
16.
e r ts h e m –E/RT
. In this equation, E
represents
E p
x colliding molecules will not react C [AIEEE-2005]

yof the reacting molecule at a temperature, T

(1) the energy below which

i s t r
(2) the total energy

e mof these
(3) The fraction of molecules with energy greater than the activation energy of the reaction
h
C (4) None
2
 Chemical Kinetics
17. The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr
 NOBr2 (g)
s s
NO(g) + Br2(g)  [AIEEE 2006]
r t r t
erespect to NO(g) is :
xprateedetermining step, the order of the reaction p
NOBr (g) + NO(g)  2NOBr(g)
x
2
If the second step E
r y
is the
r y E(4) 3
with
(1) 0
is t (2) 1 (3) 2
is t
18. he
m h e m to the concentration of carbon monoxide.
C C
A reaction was found to be second order with respect
If the concentration of carbon monoxide is doubled, with everything else kept the same, the rate
of reaction will - [AIEEE-2006]
(1) triple (2) increase by a factor of 4
(3) double (4) remain unchanged

19.
e r ts  2AB are 180 kJ
The energies of activation for forward and reverse reactions for A2 + B2 
–1
E
–1
x p The presence of a catalyst lowers t s
r change of the reaction
mol and 200 kJ mol respectively. the activation energy of
both (forward andyreverse) reactions by 100 kJ mol . The enthalpy e
s t r
(A + B i 2AB) in the presence of catalyst will be (inE
–1

kJx
p
m
–1

e r
(3)t280y mol ) – [AIEEE-2007]

C(1)h300
2 2
(2) 120
m i s (4) –20

C h e the floor of a room. Its half-life period is 30 days. If the s

20. A radioactive element gets spilled over
initial velocity is ten times the permissible value, after how many days will it be safep to e rt
E x enter

try
the room ? [JEE MAIN-2007]
(4) 10sdays
(1) 100 days (2) 1000 days (3) 300 days
m i
s will generate an C h e
21.
(1)  - particle emission pe
r t
Which of the following nuclear reactions isotope ? [JEE MAIN-2007]

E x (2) Neutron particle emission

t r y
(3) Positron emission (4)  - Particle emission

m is
22. Ch
e e r ttosthe rate of appearance of
p
1
For a reaction
2
E x
A  2B, rate of disappearance of ‘A’ is related

tr y
i(2)s – d[A]  1 d[B]
‘B’ by the expression. [JEE MAIN-2008]

(1) –
d[A] 1 d[B]

he m s
dt 2 dt
C dt 4 dt
e r t
(3) –
d[A] d[B]
 (4) –
d[A]
4
d[B]
E xp
dt dt dt dt
s t r y
t s m iThe time required for the
23. The half life period of a first order chemical reaction is 6.93 e
er reaction will be (log 2C=h0.301) :–
minutes.

E p
completion of 99% of thexchemical [AIEEE-2009]
(1) 46.06 minutesy
is t r (2) 460.6 minutes

m
Che
(3) 230.3 minutes (4) 23.03 minutes

3
 Chemical Kinetics
24. Consider the reaction:
Cl2(aq) + H2S(aq)  S(s) + 2H+(aq) + 2Cl–(aq)

e r t s
The rate equation for this reaction is
er ts
E x p rate = k[Cl2][H2S] xp
E [AIEEE-2010]
s r y
t+ H S  H + Cl + Cl + HS (slow) istry
Which of these mechanisms is/are consistent with this rate equation ?
i
m Cl + HS  H + Cl + S(fast) hem
– –

e
+ +
A. Cl
h
2 2

C B.
+
C – +

H2S  H+ + HS– (fast equilibrium)

–

Cl2 + HS–  2Cl– + H+ + S(slow)

(1) A only (2) B only (3) Both A and B (4) Neither A nor B

25.
r ts
The time for half life period of a certain reaction A Products is 1 hour, when the initial
e
E xp r ts
concentration fo the reactant 'A' is 2.0 mol L–1, How much time does it take for its

tr y e
concentration to come from 0.50 to 0.25 mol L–1 if it is a zero order reaction ? [AIEEE-2010]
s x p
m
(1) 1 h i (2) 4 h (3) 0.5 h
y E (4) 0.25 h

h e s tr
26. CThe rate of a chemical reaction doubles m i 10°C rise of temperature. If the temperature is
C e
h increases by about :-
for every
[AIEEE-2011] s
raised by 50°C, the rate of the reaction
e r t
(1) 32 times (2) 64 times (3) 10 times (4) 24 times
E xp
27. A reactant (A) forms two products :
is try[AIEEE-2011]
k
h em
A  B, Activation Energy Ea
t s C
1

r
1

k
xp
A  C, Activation Energy
1
e Ea
If Ea = 2 Ea , then kEand k are related as :-
2

s t r y 1 1 2

m
(1) k  2ki (2) k  k e
Ea 2 / RT
(3) k  k e
Ea1 / RT

s
(4) k  Ak e
Ea 2 / RT Ea1 / RT

e t
e
h r
1 2 1 2 2 1 1 2

e
C For a first order reaction (A)  prodicts the concentrationxofpA changes from 0.1 M to 0.025 M
28.
r y E
in 40 minutes.
m iofsAtis 0.01 M is :
h e
The rate of reaction when the concentration
C
[JEE MAIN-2012]
ts
–5 –4
e r
xp
(1) 1.73 × 10 M/min (2) 3.47 × 10 M/min

E
–5 –4

y
(3) 3.47 × 10 M/min (4) 1.73 × 10 M/min

i s t r
The rate of a reaction doubles whensits temperature changes from m
29.
energy of such a reaction will e
t
ber: (R = 8.314 JK mol C
e
hlog 2 = 0.301)
300 K to 310 K. Activation

E x p and –1 –1

s
(1) 53.6 kJimol tr y [JEE MAIN-2013]

m
–1 –1

e kJ mol
(2) 48.6 kJ mol

C(3)h58.5
–1 –1
(4) 60.5 kJ mol
4
 Chemical Kinetics
30. For the non-stoichiometre reaction 2A + B  C + D, the following kinetic data were obtained
in three separate experiments, all at 298 K. [JEE-MAIN 2014]

er ts er ts
Exp Initial
concentration
Initial

Ex
concentrationp Initial rate of
formation of C

stry (A) (B)

stry (mol L– S–)

mi mi
Che 0.1M
e
0.1M

Ch
1.2×10–3

0.1M 0.2M 1.2×10–3

0.2M 0.1M 2.4×10–3

dc dc dc dc
= k[A] [B]2 = k[A]2 [B]
ts
(1) (2) = k[A] (3) = k [A] [B] (4)
r
dt dt dt dt
e
xpare rare due to :-
y E e r t s
r
31. Higher order (>3) reactions [JEE-MAIN-(Offline)2015]
(1) shifting oft
is equilibrium
E x p
towards reactants due to elastic collision
(2) lossm y
h e of active species on collision
C(3) low probability of simultaneous collision s tr
iof all the reacting species
e m
Ch energy as more molecules are involved.
(4) increase in entropy and activation
e r ts
E xp
try
32. The reaction
2N O (g)  4NO (g) + O (g)
2 5 2 2
i s
monly N O was found to
s h e
C exerted by the gases after 60
follows first order kinetics. The pressure of a vessel containing
t
2 5

e r
xp remains constant) [JEE-MAIN-(Online)2015]
increase from 50 mm Hg to 87.5 mm Hg in 30 min. The pressure

(1) 106.25 nmr

E
min. will be (Assume temperature
y (2) 116.25 nm Hg (3) 125 mm Hg
i s t Hg (4) 150 mm Hg

h e m r t s
33. C For the equilibrium, A(g)  B(g), H is –40 kJ/mol. Ifp
x e
2 y
E the ratio of the activation energies

of the forward (E ) and reverse (E ) reactions s istrthen : – [JEE-MAIN-(Online)2015]

f
m i 3
b

(1) E = 60 kJ/mol; E = 100 kJ/mol

C he (2) E = 30 kJ/mol; E = 70 kJ/mol r t s
e
f b f b

(3) E = 80 kJ/mol; E = 120 kJ/mol

f b (4) E = 70kJ/mol; E = 30 kJ/mol
f
E
b
xp
s t r y
t s m i the concentration of
e
34. Decomposition of H O follows a first order reaction. In fifty minutes
r M in one such decomposition.
h
2 2

2 2
H O reaches 0.05 M,E p
H O decreases from 0.5 to 0.125 e C
thexrate of formation of O will be :–
When the concentration of

rymin
2 2 2 [JEE-MAIN-(Offline)2016]
(1) 1.34 × 10stmol
i
–2 –1 –2 –1
(2) 6.93 × 10 mol min

h e m× 10 mol min
(3) 6.93 –4 –1
(4) 2.66 L min at STP –1

C
5
 Chemical Kinetics
35. The reaction of ozone with oxygen atoms in the presence of chlorine atoms can occur by a two
step process shown below : [JEE-MAIN-(Online)2016]

e r t s
O3(g) + Cl(g)  O2(g) + ClO(g) ......(i)
e r ts
ki = 5.2 × 10xLp
E mol s 9 –1 –1
E x p
ClO(g) +t r y s tr y
is  O (g) + Cl (g)
i
O×(g) 
2

hekm 10
= 2.6 × 10 L mol s –1 –1
....(ii)
hem
C O (g) + O(g)  2O (g) is :
C The closest rate constant for the overall reaction
ii

3 2
10 –1 –1 10 –1 –1
(1) 3.1 × 10 L mol s (2) 2.6 × 10 L mol s
–1 –1
9
(3) 5.2 × 10 L mol s (4) 1.4 × 1020 L mol–1s–1

tAs+ B  Product
36. The rate law for the reaction below is given by the expression k[A] [B]

p e r
If the concentration ofEBx s value of A at 0.1 mole,
is increased from 0.1 to 0.3 mole, keepingtthe
y
trwill be : p e r
is
the rate constant
(1) 3k m (3) k y E x[JEE-MAIN-(Online)2016]

C h e (2) 9k
i st r (4) k/3

h m
e pre-exponential factors. Activation energy of R s
37. 1
C
Two reactions R and R have identical
exceeds that of R by 10 kJ mol . If k and k are rate constants for reactions R and r
2
–1
e Rt
1

xp
2 1 1 1 2

E
–1
respectively at 300 K, then ln(k /k ) is equal to : (R = 8.314 J mol )
y
2

r
1

is t
[JEE-MAIN-(Offline)2017]
(1) 6 (2) 4 (3) 8
h e m(4) 12

r t s C
e on increasing the temperature from 300 to 310 K. By how
38.
x p
The rate of a reaction A doubles
E of reaction B should be increased from 300 K so that rate doubles if
r y
much, the temperature
activation s t of the reaction B is twice to that of reaction A: [JEE MAIN 2017 (Online)]
mK i energy
s19.67 K
Ch(1)e2.45 (2) 4.92 K (3) 9.84 K
e r t
(4)

E xp
39.
i s t ry changes from 300 to 310 K. The
The rate of a reaction quadruples when the temperature
activation energy of this reaction is:
e m [JEE MAIN 2017 (Online)]
(Assume Ea and A are independent Chof temperature In 2 = 0.693; R = 8.314 J mol K ) erts –1 –1

(4) 26.8 kJ mol xp

E
–1 –1 –1 –1
(1) 107.2 kJ mol (2) 53.6 kJ mol (3) 214.4 kJ mol

s r y
tAfter 50 minutes, the
s 50 mmHg to 87.5 mmHg.
tfrom i
mThe pressure of the gaseous
40. 2 5

e r
N O decomposes to NO and O and follows first order kinetics.
2 2

h e
xatpconstant temperature will be:C [JEE MAIN 2018 (Online)]
pressure inside the vessel increases
E
try (2) 175.0 mmHg (3) 106.25 mmHg (4) 136.25 mmHg
mixture after 100 minutes

is
(1) 116.25 mmHg
m
C h e
6
 Chemical Kinetics

1th
41. For a first order reaction, A  P, t½ (half-life) is 10 days. The time required forconversion

s s
4

e r t
of A (in days) is : (ln 2 = 0.693, ln 3 = 1.1)
er t
[JEE MAIN 2018 (Online)]
(1) 5
x p
E occurs in 100 second and 75% of therreaction
(2) 4.1 (3) 3.2
x p
E occurs in 200 second, the
(4) 2.5

s t y
If 50% of arreaction
s y
t [JEE MAIN 2018 (Online)]
i i
42.

he m
order of this reaction is:
h m
(3)eZero
C
43.
(1) 1 (2) 2
C (4) 3
At 518º C, the rate of decomposition of a sample of gaseous acetaldehyde, initially at a pressure
of 363 Torr, was 1.00 Torr s–1 when 5% had reacted and 0.5 Torr s–1 when 33% had reacted.
The order of the reaction is : [JEE-MAIN-(Offline)2018]
(1) 0 (2) 2 (3) 3 (4) 1
44.
r ts
The following results were obtained during kinetic studies of the reaction :
e
Experiment [A] (in E
xp
2A + B  Products
mol L–1) [B] (in mol L–1) Initial Rate ofr s (in mol L–1 min–1)
[JEE MAIN -2019(JAN.)]
t
s r
t0.10y x p e reaction

(II) em
(I) i 0.20
E
y 6.93×10
6.93×10-3

h
C(III)
0.10 0.25
i st r -3

0.20
e m
0.30
h half of A is :
1.386×10-2

C
The time (in minutes) required to consume
e r ts
(1) 10 (2) 5 (3) 100 (4) 1
E x p
45. 
For the reaction, 2A + B products, when the concentrations of A and B both
st ry were doubled,
–1 –1
m i L s . When the
–1 –1

emol L s to 0.6 mol L s .

the rate of the reaction increased from 0.3 mol L s to 2.4 mol

t s C
concentration of A alone is doubled, the rate increased from 0.3
r h –1 –1 –1 –1

(1) Total order of theE x p e [JEE MAIN -2019(JAN.)]

y reaction is 4
r with respect to B is 1
(2) Order thetreaction
s
m i s
h e
(3) Order of the reaction with respect to B is 2
C (4) Order of the reaction with respect to A is 2 e r t
E x p
t ry
is
46. Consider the given plots for a reaction obeying Arrhenius equation (0ºC < T < 300ºC) : (k and

m
Che
E are rate constant and activation energy, respectively)
a [JEE MAIN -2019(JAN.)]

e r ts
E xp
s t ry
ts m i
Choose the correct option : er
C h e
E x p
(3) I is wrong t
s y
r II is right
(1) I is right but II is wrong (2) Both I and II are wrong

m i but (4) Both I and II are correct

C h e
7
 Chemical Kinetics
d[A]
47. 
For an elementary chemical reaction, A 2 1
 k
 2A , the expression for is:
k
dt
s s
–1

r t
ek [A ]–k [A] (3) 2k [A ]–k [A] xpe r t [JEE MAIN -2019(JAN.)]
1 2
E x
(1) 2k [A ]–2k [A] (2)
–1 p 2
1 2 –1
2

E 1 2 –1
2
(4) k1[A2]+k–1[A]2

s t r y s r
t 1y
If m
i m i
48.
C he h e
a reaction follows the Arrhenius equation, the
C
plot lnk vs
(RT)
gives straight line with a

gradient (–y) unit. The energy required to activate the reactant is : [JEE MAIN -2019(JAN.)]
y
(1) unit (2) yR unit (3) y unit (4) –y unit
R

49.
r ts
The reaction 2X  B is a zeroth order reaction. If the initial concentration of X is 0.2 M, the
e
E xp r t s
half life is 6 h. When the initial concentration of X is 0.5 M, the time required to reach its final

s tr y
concentration of 0.2 M will be :-
xp e [JEE MAIN -2019(JAN.)]
(1) 18.0 h
m i (2) 9.0 h (3) 7.2 h
E (4) 12.0 h

h e
50. CDecomposition of X exhibits a rate constantiof s ryg/year. How many years are required for
t0.05
h e m
C ts
the decomposition of 5 g of X into 2.5 g ? [JEE MAIN -2019(JAN.)]
e r
xp
(1) 25 (2) 40 (3) 50 (4) 20

For a reaction consider the plot of ln k versus 1/T given in the figure. If the r
E
yconstant of this
51.
s t
i MAIN -2019(JAN.)]
rate
m
–5 –1
reaction at 400 K is 10 s , then the rate constant at 500 K is :
s C h e [JEE

e r t
E x p
s t r y
m i s10 s
Ch e e r t
xp
–6 –1 –4 –1 –4 –1 –4 –1
(1) 10 s (2) 4×10 s (3) 2×10 s (4)
E
52. For the reaction 2A + B  C, the values of s
i tryrate at different reactant concentrations are
initial
given in the table below. The rate lawe
h mthe reaction is :
C Initial Rate (mol L s )
for [JEE MAIN -2019(APR.)]
e r ts
–1
[A] (mol L ) [B] (mol ) –1 –1 –1

Ex p
0.05 0.05 0.045
s tr y
t s m i
0.10 0.05
e r 0.72
0.090
C h e
0.20 0.10
x p
E(2) Rate = k[A] [B] (3) Rate = k[A] [B] (4) Rate = k[A][B]
s tr y
i
2 2 2 2
(1) Rate = k[A][B]

h e m
C
8
 Chemical Kinetics
k1 k2
53. For a reaction scheme A   B  C, [JEE MAIN -2019(APR.)]

r t s r t s
If the rate of formation of B is set to be zero then the concentration of B is given by:
e k  e
E x p E x p
tr y   –
tr y
1
(1) k k [A]
1 2 (2) [A] (3) (k k1) [A] (4)
2 (k + k ) [A] 1 2

is  k  2
i s
m of a reactant R with time for two
mgiven plots represent the variation of theheconcentration
54.
C heThe
C
different reactions (i) and (ii). The respective orders of the reactions are :
[JEE MAIN -2019(APR.)]

(i) (ii)

ln [R]
e r t s [R]

E p
x1, 1 time time
t s1, 0
tr y p e r
s x
(1) 0, 1 (2) (3) 0, 2 (4)
i
mthe given plot of enthalpy of the following E
yreaction between A and B.
55.
C h e
Consider
i st r
A + B C + e Dm
Identify the incorrect statement.C
h [JEE MAIN -2019(APR)]
r ts
xp e
E
is try
h em
e r t s C
E xp
s tr yA and B from C has highest enthalpy of activation.
m i
(1) Formation of
s
Ch e e r t
xp
–1
(2) Activation enthalpy to form C is 5kJ mol less than that to form D.
E
try
(3) D is kinetically stable product.

m i s
e
(4) C is the thermodynamically stable product.
h
C wound grows as N’(t) = N exp(l), where the timeet isrtins
xp
56. A bacterial infection in an internal 0

hours. A dose of antibiotic, taken orally, needs 1 hour to reach the wound. Once
ry E it reaches

i s tMAIN -2019(APR.)]
ts dt m
dN
r e
2
–
h
there, the bacterial population goes down as = 5N . [JEE

x p e C
r y E N

is t
0
What will be the plot of vs. t after 1 hour?
N
m
Che
9
 Chemical Kinetics

(1)
er ts (2)
er ts
Exp Exp
stry stry
m i mi
Che(3) Ch e
(4)

57. For the reaction of H2 with I2, the rate constant is 2.5×10–4 dm3 mol–1 s–1 at 327ºC and 1.0 dm3

r ts
mol–1 s–1 at 527ºC. The activation energy for the reaction, in kJ mol–1 is :
e
(R = 8.314 J K mol ) p
–1

E x –1

r t s72
[JEE MAIN -2019(APR.)]

s tr y x p e
i
(1) 150 (2) 59 (3) 166 (4)

e m r y E
h
58. CIn the following reaction; xA  yB i st
em [JEE MAIN -2019(APR.)]
 d[B]  Ch t s
log 
 d[A] 
  0.3010 e r
xp
10  log  
10
 dt   dt 
E
‘A’ and ‘B’ respectively can be:
is try
(2) C H and C H m
(1) C H and C H
2 4 4 8
s C h
2
e 2 6 6

e r t
p
(3) N O and NO
2 4 2 (4) n-Butane and Iso-butane

E x
s t r y
59.
i
NO required
m
for a reaction is produced by the decomposition of N O in CCl as per the
+sO (g)
2 2 5 4

h e e
2 N O (g)  4 NO (g)
C The initial concentration of N O is 3.00 mol L and it isx2.75 r t
p mol L after 30 minutes. The
equation, 2 5 2 2

E –1 –1

try
2 5

rate of formation of NO is: 2

i s
m (2) 2.083 × 10 mol L min
[JEE MAIN -2019(APR.)]
–2
(1) 1.667 × 10 mol L min
C
–1
h e –1 –3 –1

ts
–1

e r
xp
–3 –1 –1 –3 –1 –1
(3) 4.167 × 10 mol L min (4) 8.333 × 10 mol L min

r y E
s t
i (T) occurs 10 times
t s m
6

rThe charge in the activation e

60. The rate of a certain biochemical reaction at physiological temperature

x p
faster with enzyme than without. e C henergy upon adding enzyme is :
r y E
(1) + 6RT is
t [Jee Main (Jan. 2020)]

e m (2) –6(2.303)RT (3) +6(2.303)RT (4) –6RT

Ch
10
 Chemical Kinetics
1
61. Consider the following plots of rate constant versus for four different reactions. Which of
T

er ts er ts
the following orders is corrects for the activation energies of these reactions ?

Exp Exp
stry log k a
stry
i d c
i
Chem bCh
em
1/T [Jee Main (Jan. 2020)]
(1) Ea > Ec > Ed > Eb (2) Eb > Ea > Ed > Ec
(3) Ec > Ea > Ed > Eb (4) Eb > Ed > Ec > Ea

62. For following reactions

e r ts
A  700K
 Product
E xp r t s
s tr y x p e
i
A  Product
E
500K

mfound that the E is decreased by 30kJ/molrinythe presence of catalyst. If the rate remains
caatalyst

h e
Cunchanged, the activation energy for catalysed
It was a
i streaction is (Assume pre exponential factor is
h em
same) C e
[Jee Main (Jan. 2020)]r ts
(4) 198 kJ/mol xp
(1) 105 kJ/mol (2) 75 kJ/mol (3) 135 kJ/mol
y E
The results given in the below table were obtained during kinetic studies ofis trfollowing reaction:
63.
h e m the

ts Initial rate/ molC min

2A + B  C + D
Experiment [A]/molL e[B]/molL r
xp 0.1
–1 –1 –1 –1

ry E –3

t 0.1
I 0.1 6.00 × 10
II is
m s
–2

Ch e
0.2 2.40 × 10
e r t
xp
–2
III 0.2 0.1 1.20 × 10

r y E –2
IV X 0.2
i s t 7.20 × 10
V 0.3 Y
e m –1
2.88 × 10

Ch : e r ts
X and Y in the given table are respectively
(4) 0.4, 0.4 Ex
[Jee-Main (Sep) 2020]
p
(1) 0.4, 0.3 (2) 0.3, 0.3 (3) 0.3, 0.4
s t r y
t s m i
e
r a single step reaction Ch [Jee-Main (Sep) 2020]
64. It is true that :

p e
xis a multistep reaction
(1) A first order reaction is always

ry E
i s t
(2) A zero order reaction

e m order reaction is a single reaction

(3) A second order reaction is always a multistep reaction
h
C (4) A zero
11
 Chemical Kinetics
3
65. For the reaction 2A + 3B + C  3P, which statement is correct? [Jee-Main (Sep) 2020]
2

er ts er ts
p p
dn A dn B dn C dn A 3 dn B 3 dn C

x
  
E x
y E4 dn
(1) (2)

y
dt dt dt dt 2 dt 4 dt
dn st2rdn
(3) i 
dn 2 r
ist 
dn 3 dn
e m 
e m
A B C A B C
(4)

Ch dt 3 dt 3 dt
Ch dt 3 dt 4 dt

66. A flask contains a mixture of compounds A and B. Both compounds decompose by first-order
kinetics. The half-lives for A and B are 300 s and 180 s, respectively. If the concentration of A
and B are equal initially, the time required for the initially, the time required for the

e r ts
concentration of A to be four times that of B (in s) is : (Use In 2 = 0.693)

E xp r ts
try (2) 900 e (4) 300
[Jee-Main (Sep) 2020]
(1) 180
is (3) 120
E x p
Thee m constant (k) of a reaction is measured r
h in the given figure. The activation energy aty
t of the reaction in kJ mol is : (R is constant)
67.
Cplotted
rate
m i s different temperature (T), and the data are

e
–1

10 C
h r ts
x p e
E
ln k
i s try
m
5

s C h e
0er
t
E xp 10 1 2 3 4 5

s tr y 3

m i T
s
Ch(1)e2R t
[Jee-Main (Sep) 2020]

e r
(2) 1/R (3) 2/R
E xp (4) R

i s try
h e m
C e r ts
E xp
s t r y
t s m i
e r C h e
E x p
s tr y
m i
C h e
12
 Chemical Kinetics

EXERCISE # JEE ADVANCED

1.
e r ts
Which of the following statement(s) is (are) correct
e r ts [JEE 1999]

E x p
(A) A plot of log Kp versus 1/T is linear
E x p
s y
tofrlog P versus 1/T is linear at constant volume.
(B) A plot of log [X] versus time is linear for a first order
s tr y
reaction, X  P

i
(C) A plot
m i
mA plot of P versus 1/V is linear at constanthetemperature.
Che(D)
C
2. The rate constant for an isomerisation reaction A  B is 4.5 × 10–3 min–1. If the initial
concentration of A is 1 M. Calculate the rate of the reaction after 1 h. [JEE 1999]

3. The rate constant for the reaction

e r s
tO  4NO + O
[JEE 2000]

pis 2.4 × 10 mol litre sec , then thetsconcentration of N O (in

2N
is 3.0 × 10 sec if thex
2 5 2 2
–5

mol litre ) is ry
E–1
rate –5

e r
–1 –1
2 5

(A) 1.4mi
–1
st (C) 0.004 E
p
x (D) 0.8
e tr y
CAhhydrogenation
(B) 1.2
i s
mat 500 K. If the same reaction is carried out in the
reaction is carried e
4.
presence of a catalyst at the C
h out
r ts
xp e
same rate, the temperature required is 400 K. Calculate the

E
–1

try [JEE 2000]

activation energy of the reaction if the catalyst lowers the activation barrier by 20 kJmol .

is
mAB for the photochemical
s C h e
5.
e r t
If I is the intensity of absorbed light and C is the concentration of
process
E xratepof formation of AB is directly proportional to
s t y
AB + hv AB, the
r [JEE 2001]
(A) C
m i (B) I (C) I 2

s
(D) Cl

h e e r t
C The rate of a first order reaction is 0.04 mole litre s atx10pminutes and 0.03 mol litre s at
–1 –1 –1 –1
6.

r y E
is t
20 minutes after initiation. Find the half life of the reaction. [JEE 2001]

Consider the chemical reaction, Nh

m
(g)e+ 3H (g) 2NH (g). The rate of this reaction can bes
7.
C 2 2 3

e r t
E x p
expressed in term of time derivative of concentration of N (g), H (g) or NH (g). Identify
2 2 the
3

s try [JEE 2002]

i
correct relationship amongst the rate expressions.
2
e r
(A) Rate = – d[N ]/dt = – 1/3 d[H ]/dt
t 2s = 1/2d[NH ]/dt
h e m
3

(B) Rate = – d[N ]/dt = – 3p

E2
x d[H ]/dt = 2d[NH ]/dt
2 C 3

(C) Rate = d[N r

s y
t ]/dt = – d[H ]/dt = d[NH ]/dt
i
]/dt
2 = 1/3 d[H ]/dt =1/2d[NH ]/dt
2 3

h e m
(D) Rate = – d[N 2 2 3

C
13
 Chemical Kinetics
8. In a first order reaction the concentration of reactant decreases from 800 mol/dm 3 to 50
mol/dm3 in 2 × 104 sec. The rate constant of reaction in sec–1 is [JEE 2003]
(A) 2 × 10 4

e r t s
(B) 3.45 × 10 –5
(C) 1.386 × 10 –4

er t s
(D) 2 × 10 –4

E xp x p
E the concentration of X
The reaction, y follows first order kinetics. In y
9.
is r X Product
t 0.1 M to 0.025 M. Then the rate of reaction
i s r
twhen concentration of X is 0.01 M
40 minutes

he m
changes from
h e m
C (A) 1.73 × 10–4 M min–1 C (B) 3.47 × 10–5 M min–1
[JEE 2004]

(C) 3.47 × 10–4 M min–1 (D) 1.73 × 10–5 M min–1

10. For the given reactions, A + B Products, following data were obtained. [JEE-2004]
[A0] [B0] R0(mol L–1 s–1)

er ts
xp
1. 0.1 0.2 0.05
2. 0.2
y
0.2
E 0.10
er ts
3.
istr
0.1 0.1 0.05
Exp
(a)
h e m ry
Write the rate law expression
t
C(b) Find the rate constant
mis
Ch e s
11. 2X(g) 3Y(g) + 2Z(g)
er t [JEE 2005]
Time (in Min) 0 100 200
Exp
Partial pressure of X 800 400
ist ry
200
(in mm of Hg)
hem
e r ts
Assuming ideal gas condition. Calculate C
(a) Order of reaction xp
r E
y75% completion of reaction (d) Total pressure when P = 700 mm.
(b) Rate constant

is
(c) Time taken t for
m s
X

h e e r t
12. C Which of the following statement is incorrect about order of p
E x reaction? [JEE 2005]

r y
ist
(A) Order of reaction is determined experimentally
m
Chonestoichiometric coefficients ts
(B) It is the sum of power of concentration terms in the rate law expression

e r
xp
(C) It does not necessarily depend
(D) Order of the reaction can not have fractional value.
r y E
is t
13. Consider a reaction aG + bH  r ts When concentratione
e eight times. However, Cwhen
Products. ofm
h concentration of G is doubled
both the reactants G and H is
x p
E of H fixed, the rate is doubled. The overall order of the reaction is :
doubled, the rate increases by

s tr y
keeping the concentration

m i
C(A)he0
[JEE 2007]
(B) 1 (C) 2 (D) 3

14
 Chemical Kinetics
14. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance
becomes half in 40 seconds and 20 seconds through first order and zero order kinetics,

er ts k 
er ts
Exp  k0 
E p
respectively. Ratio  1  of the rate constants for first order (k1) and zero order (k0) of the
x
stry stry
i i
reactions is [JEE 2008]

hem –1
(A) 0.5 mol dm 3
(B) 1.0 mol dm –3

em
(C) 1.5 mol dm
h
–3 –1
(D) 2.0 mol dm3

C
15. C
For a first order reaction AP, the temperature (T) dependent rate constant (k) was found to
1
follow the equation log k = – (2000) + 6.0 . The pre-exponential factor A and the activation
T
Ea , respectively, are [JEE-2009]
6 –1 –1 –1 –1

ts
(A) 1.0 × 10 s and 9.2 kJ mol (B) 6.0 s and 16.6 kJ mol
6 –1
(C) 1.0 × 10 s and 16.6 kJ mol
p e
–1
r (D) 1.0 × 106 s–1 and 38.3 kJ mol–1

E inxthe reaction R  P was measured as a function

r t s of time and the
16.
y
tisrobtained :
The concentration of R
s x p e
m i
following data
y E
C h e i st r
m
[R] (molar) 1.0 0.75 0.40 0.10

Ch e
t(min) 0 0.05 0.12 0.18
e r ts
E xp2010]
tarerygiven below. The
The order of the reaction is. [JEE

m is
17.
s C h e
Plots showing the variation of the rate constant (k) with temperature (T)

e r t
plot that follows Arrhenius equation is – [JEE 2010]

E x p
k
s t r y k
(A)
m i (B)
s
Ch e e r t
T
E xp T

i s try
h e m
C ts
k k
(C) (D)
e r
E xp
s t r y
i
T T

18. For the first order reaction

r t s
e (g) + O (g) h e m [JEE 2011]

(A) the concentration E

2 5
x p
2N O (g) 4NO 2 2 C
ry of the reactant decreases exponentially with time

them
ist of the reaction decreases with increasing temperature.
(B) the half-life
(C) e
C(D)h the reaction proceeds to 99.6% completion in eight half-life duration.
half-life of the reaction depends on the initial concentration of the reactant.

15
 Chemical Kinetics
19. An organic compound undergoes first-order decomposition. The time taken for its decomposition

s s
to 1/8 and 1/10 of its initial concentration are t1/8 and t1/10 respectively. What is the value of

er t er t
[t1/8 ]
× 10 ?
E xp Exp
t1/10
s r y
t2 = 0.3) stry
m i
(take log
mi [JEE 2012]
e e
10

h
C the reaction :
20. In Ch [JEE 2013]
P + Q  R + S

[Q]0

[Q]
e r ts
E xp r ts
s y
trfor 75% reaction of P is twice the time
time
x e
p for 50% reaction of P. The
i
m of Q varies with reaction time astrshown E
y in the figure. The overall order of the
e
the time taken taken

C h i s
m
concentration
e
Ch (C) 0 ts
reaction is -
e r
xp
(A) 2 (B) 3 (D) 1
E
For the elementary reaction M  N, the rate of disappearance of M increases is tryby a factor of 8
mrespect to M is
21.
upon doubling the concentration of M. The order of the reactione
r ts C h with

(B)p
x3 e [JEE 2014]
(A) 4

r E (C) 2
y as a function of time in the reaction
(D) 1

i s t
22.
m
The % yield of ammonia
t s
[JEE 2015]

ChNat e(P,(g) T+ 3H 2NH (g), H < 0

e r


xp
2 2 (g)
 3

E
try
1 ) is given below -

m i s
h e ts
% yeild

T1
C e r
E xp
s try
If this reaction is conducted at (P, T s
t
time
m i as a function of
e r 2 2 1

C e
), with T > T , the % yield of
h
ammonia
time is represented by –
E x p
s t r y
m i
C h e
16
 Chemical Kinetics

T2 T1

s s
% yeild
T1

% yeild
t t
T2
(A)
per (B)
per
Ex Ex
stry stry
m i time
mi time

e e
T1
h h
T2

C C
% yeild

T2

% yeild
T1

(C) (D)

time time

e r ts 

xp
23. In dilute aqueous H2SO4, the complex diaquodioxalatoferrate(II) is oxidized by MnO4 . For
this reaction, the ratioE
y e r t s of [ MnO ] is.


tr
+

p
of the rate of change of [H ] to the rate of change
s x
4

m i y E [JEE 2015]
h e s t r
24. CAccording to the Arrhenius equation, i
e m
himplies a fast reaction
[JEE 2016]

C
(A) A high activation energy usually
e roft
s
xp
(B) Rate constant increase with increase in temperature. This is due to a greater number
collisions whose energy exceeds the activation energy
y E
rdependence
(C) Higher the magnitude of activation energy, stronger is the temperature
i st of the
rate constant
(D) The pre-exponential factor is asmeasure of the rate at which h e m
e r t C collisions occur, irrespective of

xp
their energy.

r E
yreaction, the steric factor P was experimentally determined to be 4.5. The
25.
s t
i among the following is(are)
In a bimolecular

e m r t s
Ch(A)
correct option(s) [JEE 2017]

x p
The activation energy of the reaction is unaffected by the value e of the steric factor
r
(B) Experimentally determined value of frequency factor
y E is higher than that predicted by
Arrhenius equation
i st
h e m unless an effective catalyst is used
(C) Since P = 4.5, the reaction will not proceed
s
(D) The value of frequency C factor predicted by Arrhenius equation is higher than that
e r t
determined experimentally
E xp
For a first order reaction A(g)  2B(g) + C(g) at constant volume and s t r y
26.
at the beginning (t = 0) and at timettsare P and P , respectively.eInitially,
m i only A is present with
300 K, the total pressure

concentration [A] , and t p is e

r 0 t
C hpressure of A to reach 1/3 of its
x
E option(s) is (are)
0 the time required for the partial
1/3
rd

r y
tall these gases behave as ideal gases)
initial value. The correct
s
m
(Assume thati [JEE 2018]

C h e
17
 Chemical Kinetics

er ts er ts
Exp Exp
(A)
stry (B)
stry
m i m i
Che Che

(C) (D)

er ts
Consider the kinetic datax
E p in the following table for the reactiontAs + B + C Product.
r
27. given

s t r y x p e
m i y E
Che m i s tr
h e
C e r ts
E xp
is t ry
The rate of the reaction for [A] =0.15 mol dm , [B] = 0.25 mol dm
is found to be Y × 10 mol dm s s. The value of Y is ______ h e
–3
m –3
and [C] = 0.15 mol dm –3
–5

r t –3 –1
C
e2N O (g)  2N O (g) + O (g) is started in a closed cylinder
[JEE 2019]

E xp 

y
28. The decomposition reaction
r
2 5 2 4 2

inside theis
t
under isothermal isochoric condition at an initial pressure of 1atm. After Y×10 s, the pressure 3

h e m ideal gas behavior, the value of Y is _____ r ts

cylinder is found to be 1.45 atm. If the rate constant of the reaction is 5×10 s , –4 –1

C assuming
x p e [JEE 2019]

r y E
ist
29. Which of the following plots is(are) correct for the given reaction? [JEE 2020]
([P] is the initial concentration of P)
0

he m
CH 3
C CH 3

e r ts
HC 3 Br + NaOH HC OH + NaBr3
E xp
CH CH
s t r y
i
3 3
P
r t s Q
e m
p e [Q] Ch
x
initial rate

rat
e

r y E ln
 [P] 
 
t
t
s
(A) (B) (C) [P] (D)
i
1/2 0  [P]  0

h e m [P] [P] time time

C
0 0

18
 Chemical Kinetics

ANSWER KEY

er ts EXERCISE # (JEE-MAIN)
r
e 7.ts
1. 3 2.
xp 4
2 E 10.
1 3. 4. 1 5. 4
x
1y E13.
p
6. 3 1
8. 1 9.
s ry
t 1 17. 3
4 11. 3 12.
s r
t 1 20. 1 21.
2 14. 2
i i
15.

C
22. he1
2
m 16.
23. 4 24. 1
18. 2
25. Ch
4
em26. 1 27. 2 28.
19. 2
2
29. 1 30. 2 31. 3 32. 1 33. 3 34. 3 35. 3
36. 3 37. 2 38. 2 39. 1 40. 3 41. 2 42. 1
43. 2 44. 2 45. 3 46. 4 47. 1 48. 3 49. 1
50. 3 51. 4
r t
52.s53. 24 54. 4 55. 2 56. 3
59. pe
57. 3 58. 1
x
E 2 67. 1
1 60. 2 61. 3
r ts
62. 2 63. 3
3ry 66. e
64. 2 65.
ist E xp
hem try
C EXERCISE
m
# is
JEE ADVANCED
e
Ch 3. D
1. ABD 2. (3.435 × 10 M/min) –3

e r ts
24.14 min y E
xpA
tr
4. 100 KJmol–1 r = k [A]= k [A]0e–kt 5. B 6. 7.
8. C 9. C
m is
(a) R0 = K [A]0 (b) 0.5 sec–1
s C h e
t
10.
1 800
p e1r
k=
2  10 4
ln
E x=
2  10 4
ln 4 = 1.386× 10–4

y
50

st r
(b) i6.93 × 10 min , (c) 200, (d) 950 mm
(a) 1,m
Che 1 0.1 1 0.1 1 ts
–3 –1
11.
er
k= ln = ln = ln 4
E xp
ry
40 0.025 40 0.025 40

is t
r = k[X] =
1

em
ln 4 0.01=3.47 × 10 M/minute
h
–4

AC 15.
ts
40
er
xp AD
12. D 13. D 14. D 16. Zero 17. A 18. ABD
BCD E25.
19. 9 20. D 21. B 22. B 23. 8 24.
str y
ts m i
e
26. AD 27. 6.75
29. 28. 2.30 A

per Ch
Ex
istry
hem
C
19
 Chemical Kinetics

HINT AND SOLTUIONS

EXERCISE # (JEE-MAIN)

er t s e r t s
1.
H + I  2HI Exp
(3)
x p
E in the same time interval.
2

s tr y
2

s r y
t1 [HI]
i
When 1 mole of H and 1 mole of I reacts,
2

mthe rate may be expressed as t hem

2 moles
i
of HI
2 are formed

CheThus
 [H
C
] 

[I
t
]

2 t
2 2

The negative sign signifies a decrease in concentration of the reactant with increase of time.
H2 + I2  2HI

2. (4)
Order is the sum of the power of the concentrations terms in rate law expression. R = [A].[B]2

e r ts
Thus, order of reaction = 1 + 2 = 3.

E xp r ts
y e
3. (1)
 mol istr xp
E
1 n

 m y
1
k= 
h
C(3) e L 
 time , where n = order

is t r
e m
Chorder reaction ts
6.

e r
xp
Surface catalysed reaction are zero
7. (1)
ry E
In Arrhenius equation, k = Ae –Ea/RT

ist
E = energy of activation. he
k = rate constant, A = frequency factor
T = temperature, R = gas constant, s
m
r
This equation can be used forecalculation
a
C
t of energy of activation.
E xp
8. (1)
r = K[NO]s[O tr y
m i 2
] 1

s
e t
2

h
C V
1
e r
xp
P P = 2P
E
f i

9. (2)
istry
Rate = k [A] [B] n m

h e m s
C t
1
On doubling the concentration of A and halving the concentration of B
p e r
x
n m

E
Rate = k [2A] [B/2]
2

 2     2 str
1
n m
y m

i
k[2A] [B/2] n n m
Ratio between new and earlier rate

e r t s k [A] [B]
h e
2
m
n m

10. (4)
2 A + B  C, rate E x p C
y
r constant) is always independent of the concentration of reactant and it
= k [A] [B]
The value ofskt(velocity
i
m of temperature only.
C h e
is a function

20
 Chemical Kinetics
13. (2)
H = a.f – a,b > 0
a,f > a,b
er ts er ts
Ex p Exp
17. (3)
r y
t  NOBr (g) s t ry
NO(g)i+sBr (g)  i
he 2

h
2
e m
m (g) + NO(g)  2NOBr(g) [rate determining
C NOBr 2 C
Rate of the reaction (r) = k [NOBr2] [NO]
step]

where [NOBr2] = Kc [NO] [Br2]

r = k. KC [NO] [Br2] [NO]
r = k' [NO]2 [Br2].

r ts
The order of the reaction with respect to NO(g) = 2.
e
E x p t snumber of molecules of
r
18. (2)

s y
tr in the balanced stoichiometric equation. x e
pThus, a reaction involving two
i
Generally, molecularity of simple reactions is equal to the sum of the

e mreactants can never be unimolecular. try

reactants involved E
C h
different
is
he m
19. (1)
C e r ts
xispcorrect.
–1
H = E – E = 180 – 200 = – 20 kJ mol


E
R b

try
–1
The correct answer for this question should be –20kJ mol . But no option given
Hence we can ignore sign and select option
m is
s C h e
20. (1)
e r t
K=
ln2
days
E xp
-1

1 ist 30
30
ry
t= m s
Ch e ln 10 = ×ln10 = 100 days
e r t
p
K ln 2

E x
21. (2)
s t ry
A 1

m i
X   X n
e
A 1

h ts
Z 0

C
Z

e r
22. (2)
E xp
 d[B]
s try
i
d[A]
–2 
dt 2 dt
e r t s h e m
E x p C
23. (4)
r y
t = lnist
1 100
99%

h e mK 1
C
21
 Chemical Kinetics
ln 2 1
k=  min–1
6.93 10

er ts
t99% = 10ln100 = 20 ln 10 = 46.06 min
er ts
Exp Exp
s r y
t [A] stry
i i
24. (1)

he m
From mechanism
hem
C r = K[Cl ][H S]
From mechanism [B]
2 2
C
r = K[Cl2][HS]
[H  ][HS ]
Keq =

ts
[H 2S]
r = K1[Cl2][H2S][H+]–1 e r
E xp r ts
str y xpe
25. (4)
A m
i y E
h
C 1 e product
istr
For zero order reaction
e m
t 
1/2
Ch of reactant
a = initial concentration
n 1
er ts
xp
a
t1/2  a
E
(t1/ 2 )1 a1

1

2
istry
m
;
(t1/ 2 )2 a 2 (t1/ 2 )2 0.50
s Che
0.5
er t
p
t1/2 = = 0.25 h.
2
Ex
s try
m i
ts
26. (1)

hr =er (T.C.) r
C t i
T/10

xpe
E
try
= ri×(2)50/10 = 32 ri

mis
27. (2)
Che ts
er
K1 = A1e Ea1 / RT
Exp
K2 = A2e Ea2 / RT
stry
ts mi
K1
e
A (E  E )/ RTr Che
xp
= 1 e a2 a1
K2 A2
y E
e tr
s
m i
K = K A
Ea1 / RT

e
1 2

Ch
22
 Chemical Kinetics
28. (2)

s s
[A]0
[A]t =
2n
er t er t
Ex
n = 2 so t = 40 min p Exp
2y y
75%

ln r
t = 2×st = 40
i K istr
m m
75%

e
Ch ln 2 Che
K= min–1
20
ln 2
r = K[A] = ×0.01
20
= 3.47×10–4 M/min

e r ts
29. (1)
Ex p ts
E ry
 st   
 1 1
per
log
K
m i 2 a

Ex
h e
K 2.030R
1  T T
stry 2 1

C  2 ; T = 310 K and T = 300 K mi

K
he
2

ts
2 1
K 1
C er
 log 2 
E  1 1  a
  
Exp
try
2.303  8.134  310 300 
 Ea  53598.6J / mol = 53.6 KJ/mol
mis
s Che
Ans is (1)
er t
E x p
30. (2)
=t
1.2 × 10 is
r y
–3

m
x y

ts
K (0.1) (0.1)

Ch1.2e× 10 = K (0.1) (0.2) er

–3 x y

2.4 × 10–3 = K (0.2)x (0.1)y

Exp
R = K [A]1 [B]0
istry
hem
C er ts
31. (3)
Exp
More than 3 molecules can’t colloid simultaneously.
stry
ts mi
e r Che
x(g)p+ O (g)
32. (1)

y0 E
2N O (g)  4NO
t = 0 50 str
2 5 2 2

m i 0

C h e
t = 30 50 – 2x 4x x

23
 Chemical Kinetics
  87.5 = 50 + 3x
  
s s
3x = 37.5 x = 12.5
 
e r t
PN2 O5 after 30 min = 50 – 25 = 25
er t
E x p E x p
 
s ry
t = 30 min.
ry
t 60 min, (two half lives), P remaining i=s50t = 12.5 torr.
1/2

m i m 4
heHence after
he
C = 37.5 torr.
N2 O5

C  Hence decrease in P = 50 – 12.5 N2 O5

  PNO2 = 2 × 37.5 = 75 torr

37.5
PO2 = = 18.75 torr

ts
2
 
er
xp
Ptotal = 12.5 + 75 + 18.75= 106.25 torr.

y E er ts
33. (3)
is tr Exp
H e
h m– E try
s
=E
C –40 = 2x – 3x i
af ab

e m
 E = 80 kJ/mol
af Ch er ts
 E = 120 kJ/mol
ab
E xp
is try
34. (3)
h e m
In 50 minutes, concentration ofrHtO
e s becomes
1
C
of initial.
xp
2 2
4

r E
yminutes
2 × t = 50 minutes
=t25
1/2
t s

m i .6931/2

s
Ch e er t
xp
 k= per minute

E
25

try
.693
s
–3

i
r =
H 2 O2 × 0.05 = 1.386 × 10
m
25
2H O  2H O + O
Ch e ts
r
2 2 2 2
1
r  r ; r = 0.693 × 10
xp e
–3

E
O2 H 2 O2 O2

y
2
r = 6.93 × 10 mol/minute × litre–4

is tr
s m
O2

er t he
x p C
isE
35. (3)

t r y
is
Ki < Kii so Step-(i) RDS

m
Che
24
 Chemical Kinetics
36. (3)
r1 = K[A][B] ......(1)
r2 = K[A]×3[B]
er ts ......(2)
er ts
r2 = 3r1
Exp Exp
s try stry
37.
Km
(2)
i mi
he
C K = A.e
1 = A.e –a2/RT

–a1/RT
Che
1
a1 – a2 = 10 kJ/mol
K 2 e Ea 2 /RT
  Ea1 /RT
= e(Ea1  Ea 2 )
K1 e
K 
ln  2  =
10 103
=4
er ts
 K1  8.314  300
E xp r ts
str y xpe
38. (2) i
m (E a)  1 1  y E
h e tr
C  K  R  T T 
ln
K 
2
 A

mis
h e
1  C ts
1 A 1 2

(E a)  1
er
xp
ln 2 = A
  
R  300 310 
E
(E a) A

10
istry
m
ln2 = .......(1)
R 300  310
s Che
(E a) A

10
er t 2(E a) B  1

1
 
p
=
R
Ex
300  310 R  300 T2 
T = 304.92
s try
i
2

39. h(1)em r ts
C xpe
Ea  1 1  E
try
ln4 =   
R  300 310 
is
m= 107.2 kJ/mol
/e
2  0.693  8.314  300  310
a =
C h
kJ mol
r ts
10  1000
xpe
ry E
40. (3)
ist
ts m
1
N2O5(g)  2NO2(g) +
er O2(g)
Che
0 xp
2
t = 0 50
E
ry 2x
0

–s
t = t 50 i xt
x

h e m 2
Ct =  0 100 50
25
 Chemical Kinetics

 3x 
P =  Po   – Po = 87.5 – 50 1.5x = 37.5 x = 25
 2 

e r ts er ts
p p
If Po = 50 and x = 25, t = 50 min is t1/2

E x Ex
y y
At t = 100 min
r
P = P i+st = 50 + 1.5 × 37.5= 106.25 mm hg
3x
istr
he m t
2
o

h em
C
41. (2)
C
ln 2 ln 2
t1/2 = K= days–1
K 10
1 1 1 4
  ln = 4.1 days
ts
t= ln
K 3/ 4 K 3
e r
E xp r ts
42. (1)
A tr A
y pe
 is E x
A 
h em2 4

t
 o t o

t r y
CSame % is reacted is in same time interval.
m s
i it is 1 order
e
st
So
C h r ts
43. (2)
xpe
E
try
r = K[acetaldehyde]n
1 = K×[363 × 0.95]n – (1)
mis
0.5 = K ×[365 × 0.67]n
s
– (2)
Che
 0.95 
er t n
n
p
n
  (2)  2 = 1  n = 2
x
2=  2

ry E
 0.67 

ist
r =ekm ts
44. (2)
h
C [A] [B]
x y
e r
E
When double the conc. of A. rate is also doubled, So orderxpw.r.t. A is 1. But by changing the
i s t ryzero.
conc. of B rate does not change so order w.r.t. B is
R = k[A] 1

h e m s
–3
6.93 × 10 = k × 0.1 C e r t
xp
–2

E
K = 6.93 × 10
k
s t r y
k
i
A

s m
r

t
2

e r –2

Ch e
p
k = 2 × 3.93 × 10
0.693 x
A

t 
2tr y E = 5 min
is 10
1 –2
6.93
m
2

Che
26
 Chemical Kinetics
45. (3)
2A + B  product

er ts
R.O.R = k[A]x [B]y
er ts
Exp
0.3 = k[A]x [B]y ....(1)
Exp
stry x
2.4 = k[2A] [2B] y
....(2)
stry
mi x y
mi
e e
0.6 = k[2A] [B] ....(3)

Ch Solving the above equations, use get,

Ch
x = 1 and y = 2
i.e. order w.r.t A is 1
and order w.r.t B is 2

46. (4)
e r ts
xp
k = Ae–Ea/RT

y E t
value of Ea, lower will be rate constant forrthe
e sreaction.
r temperature rate constant alwaysxispincreases.
tincreasing
Graph(I): Higher is the
s
Graph(II): iOn
e m ry E
C(1)h is t
47.
h e m
Rate of formation of A = 2 k [AC ]
er ts
xp
1 2

E
2
Rate of disappearance of A = k [A]

try
–1

 Net rate of formation of A = 2 k [A ] – 2k [A]

is
2
1 2 –1

h e m
48. (3)
e r t s C
K = Ae –Ea/RT

E x p
lnK = lnA - ry
t
Ea

m is RT s
hy =eC – mx
C slope = –Ea = –y e r t
E xp
i stry
m
Ea = y

C h e ts
49. (1)
p er
For zero order :
Ex
s tr y
i
C 0.2 1
k= o
 k=  k=
2 t 1

e r t s
26 60
h e m
2

E x p C
C – C ry
Now,
i st o
= tt
 t=
0.5 – 0.2
× 60 = 18 hrs

h e m k 1

C
27
 Chemical Kinetics
50. (3)
[A]o 5

er ts
For zero order reaction t 1 =
2K
=
2  0.05
= 50 years
er ts
p p
2

Ex Ex
51. (4)
r y
st E   1  stry
m ln ki= lnA – mi
Che e
a

–E a
R T
Ch
 = –4606
R

 k 2  Ea  1 1 
ln    – 
 k1  R  T1 T2 

er ts
k
Exp
2.303 log  2–5   4606 
1
–
1 
r
 400 500 ts
 k = 10 ist
ry
 10 
xpe
e m2
–4

ry E
h
C(4) ist
e m
Ch ts
52.

er
xp
m n
Let Rate = k[A] [B]
E
try
On putting given data
0.045 = k (0.5)m (0.05)n …(1)
mis
s Che
t
m n
…(2)
r
0.090 = k (0.10) (0.05)
0.720 = k (0.20) (0.10) pe
x
m n
…(3)

r y E
On solving
i s t
h e m
m = 1, n = 2
r ts
C xpe
ry E
t
53. (2)

m i s
A  B  C
e
K1 K2

h
C = K [A] – k [B] r ts
Net, rate of formation of B =
d[B]
xpe
E
1 2
dt

stry
As,
d[B]

ts
=0
mi
dt
K [A] – K [B] = 0 per Che
 
E x
K y
1 2

[B] =str[A]
 
m i 1

Ch e K 2

28
 Chemical Kinetics
54. (4)
For zero order reaction

er ts
Ct = Co –kt
er ts
E x p Exp
st ry stry
miC /[R] t

mi
Che time
Che
For Ist order reaction
Ct = Coe–kt
lnCt = lnCo – kt

lnCt/[lnR]
e r ts
E xp r ts
str y time
x p e
(2) em
i y E
55.
h
CActivation energy to from C is 5kJ/molem s t r
i than that of to from D
h e greater
(Ea) = 15 kJ/mole
C C er ts
(Ea) = 10 kJ/mole
D
Exp
istry
56. (3)
hem
N0
 e– t
er ts C
N
Exp
before 1 Hour ry
N mi
st
ChNe
0
Will decrease
er ts
Exp
try
N

s
dN
N   –5dt
mi
e
2

h ts
N0

C er
xp
1 1
  5t
N N0
ry E
ist
ts m
N0
 1  5t N 0
N
er Che
E xp
N ry
N 0
After 1Hr. Will increase.
is t
h e m
C
29
 Chemical Kinetics
57. (3)

In
k 2 Ea  1 1 
 
e r
R  T1 T2 t s er ts
p p
k1
x
 EEa  1 Ex
 1 y
 2.5is
r 
1 
t  8.314  600 800  stry
In 
m 10
 =  4 
mi
CheEa = 166 KJ
Che
58. (1)
xA  yB

–
1 d[A]
=+
1 d[B]
e r ts
x dt y dt
E x p ts
r y per
yst
d[A] d[B]
x
x
–
dt
m
=
i dt
y E
C h e istr
m
Taking log both the side,
 xhe
 –d[A] 
log 
 d[B] 
 = log  C
 + log  
er ts
 dt   dt   y
Exp
 
x
log   = 0.3010 = log2    A is C H & B iss
x 2
i ry
CtH
m
2 4 4 8
 y
s
y 1

C h e
er t
59. (1) x
E+ Op
r
2N O t4NOy
0m
is
ts
2 5 2(g) 2(g)

t =e
Ch
3M
er
t = 30 2.75 M
Exp
[N O ] 0.25
istry
=
m
2 5
t 30
1 [N OC
he ts
–  (N O )
er
xp
1 2 ] 5 2
× = ×
2 t 4 t
ry E
[N O 2 ] 0.25
2 = 1.667 × 10–2 mol L–1 min–1 ist
ts m
=
t 30
e r Che
E xp
y (in presence of catalyst)
60. (2)
Sol. K = A e str
m i  Ea '/ RT

Kh=eA e
2

C
 E a / RT
1 (in absence of catalyst)

30
 Chemical Kinetics


 Ea '  Ea 
K2
e RT

s s
K1

er t er t
6
10 = e


E p
 Ea ' Ea 
x RT
Exp
=is
ry
t 10 stry
Ea
m –ln 6

mi
Che RT
Che
Ea = – 6 × 2.303 × RT
61. (3)
Sol. For reaction Ea is more than change with temp will be more.
Magnitude of slop : c > a > d > b

er ts
Exp r ts
y
62. (2)

str xpe
i
–Ea/R×700

E
Sol. K = Ae

h e m –[Ea–30]/R×500
try
C E  E  30 is
=Ae

e m
Ch ts
a a
700 500
er
5E = 7E – 210
E xp
try
a a

E = 105
a

m is
Activation energy for catalysed reaction = 105–30 = 75 kJ
s Ch e
e r t
E xp
y
63. (3)

ist
Sol. From rate law r
h e m r ts
r = 
1 d[A] d[B]
C 2 dt dt 
xp e
E
r = K[A] [B] x y

is try
–3

h e m
ts
x y
6 × 10 = K(0.1) (0.1) ……(1)
–2 C er
xp
x y
2.4 × 10 = K(0.1) (0.2) ……(2)
–2
1.2 × 10 = K(0.2) (0.1) ……(3) x y

ry E
is t
(3) ÷ (1)  x = 1

e r ts he m
(2) ÷ (3)  x = 2
x p C
So, order with respectE
s r y
t to B = 2
to A = 1
Order withirespect
h e m
C(4) ÷ (3)
31
 Chemical Kinetics
2
 x   0.2  7.2 10
2

 
    2
 0.2   0.1  1.2 10

er ts er ts
x=
6  0.2
Exp Exp
s
4
try stry
x = 0.3iM
m mi
Che(5) ÷ (4)
Che
2.88 101
2
 y 
  
 0.2  7.2 102
y2 = 4 × 0.22
y = 0.4 M
e r ts
E xp r t s
64. (2)
s y
tr reaction order is equal to molecularity
x p e
i
mSo zero order reaction cannot be elementary E
yreaction. It is always multistep reaction.
e r
Sol. Since for elementary and molecularity of reaction cannot

C h is t
m
be zero.

h e
65. (3)
C e r ts
Sol. For reaction : 2A + 3B + C  3P
3
E xp
2
is try
–
1 dn

1 dnA

2 dn

1 dnB C P

h e m
2 dt 3 dt 3 dt
er t s
3 dt
C
dn
A 2 dn

3 dtEx
4 dn B
p C

dt 3 dt
s t r y
m i s
66. h
C e e r t
xp
(2)
st
Sol. For 1 order reaction
ry E
i st
t =
ln 2 1

h e m
ts
1/2
k k
C e r
k =
ln 2
,k =
ln 2
E xp
y
A B

r
300 180

i s t
Initially A and B are equal.
After time t : [A] = [B] × 4 er ts h e m
[A] e = [B] e E × 4 x p t t
C
ry
–kat –kBt

t
0 0

em is
e
– kAt

C h e
4
– kBt

32
 Chemical Kinetics
e –[k A – k B ]t  4

er s
[kB–kA] × t = ln 4 = 2 ln 2
t er ts
t=
Exp
2  ln 2

2  ln 2
= 900 sec.
Exp
stry k B – k A ln 2 – ln 2

stry
mi 180 300
mi
Che Che
67. (1)
Sol. K = A e–a/RT
Ea 1
lnk = ln A – 
R T

er
Ea 103 ts
xp
lnk = ln A – 

 Ea ry
E
103  R T
er ts
slope = ist 
.0  10
Exp
h e m1000  R 5  0
try
C 
mis
e
Ea
= –2
1000  R
Ch r ts
Ea = 2R × 10 (J mol) 3

xpe
E
try
= 2R (kJ mol–1)

mis
s Che
er t
Exp
stry
mi
Che er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
33
 Chemical Kinetics

EXERCISE # JEE ADVANCED

2. (3.435 × 10–3 M/min)
er ts er ts
xp Exp
100 KJmol y E y
tkr[A] e r
–1
4.
is ist
he m
r = k [A]= 0
–kt

hem
C C
5. (B)
r = k [A]  2.4 × 10–5 = 3 × 10–5 × [A]  [A] = 0.8 M

ts
6. 24.14 min

p e r
x
– E / RT
According to arrhenius equation K = Ae a

y E e r t s
trthe reaction in presence of catalyst = x E– 20xkJpmol
–1

s
Let E of the reaction in absence of catalyst = x kJ mol
i
a

e m
Therefore
h
E of
t r ythus be written as
–1

s
a

CThe Arrhenius equations in the two

m i
conditions can
h e
–
x
KC
–
x  20

er ts
xp
R 500 R 400
K = Ae ....(i) = ...(ii)
Ae

Dividing equation (i) by (ii), we get

ry E
ist
x  20
m
x x 20
x
e
–
–1

R400
– e 500R = e
h
= or x = 100 kJ mol

er ts 500 400
C
7. (A)
xp
e E
r = k [A]= k [A]y
r
–kt

ist (1)
0

0.04 m
Che
= k [A] e 0
 k 10

er ts
0.03 = k [A]0 e  k  20 (2)
Exp
istry
m
From equation (1) and (2)

Che ts
1 4
t1/2 =
.693
er
xp
k= ln

E
10 3 k

stry
ts mi
9. (C)
er Che
For a chemical reaction, xp
r y E
i t  2NH (g)
N (g)s+ 3H (g)
m
2 2 3

C h e
34
 Chemical Kinetics
Concentration of N2 and H2 are decreased so negative sign is represented in expression, while

s s
concentration of NH3 is increased. So +ve sign is represented in expression. Also, from
r t er t
pe x
same time 3 molesEofxH is consumed and 2 moles of NH is formed.
E p
stoichiometry it can be said that the time during which 1 mole of N2 will be consumed in the

s t ry 2

st r y 3

m i m i
10. he
C (a) R = K [A] (b) 0.5 sec
0 0
C h e
–1

1 800 1
k= ln = ln 4 = 1.386× 10–4
2  10 4
50 2  10 4

11. (a) 1, (b) 6.93 × 10–3 min–1 , (c) 200, (d) 950 mm

k=
1
ln
0.1
=
1
ln
0.1 1
e r
= ln 4 ts
xp
40 0.025 40 0.025 40
E
lnr4y 0.01=3.47 × 10 M/minute er ts
r = k[X] = t
is
1

Exp–4

h e m 40
t ry
C m is
h e
12. (D)
C er ts
2X(g)  3Y(g) + 2Z(g)
Exp
t=0 800 – –
istry
t=t 800 – 2x 3x 2x
hem
Pt = (800 + 3x) r t s C
emin the partial pressure of X decreases from 800 to 400 so t 100
from given data in timex100
E p
r y
1/2

min. Also intnext

m is of initial concentration so reaction must I order with respect
100 min Px decreases from 400 to 200 so again t = 100 min. Since half life
s to X.
1/2

Chis e
independent
e r
st
t
n2
E xp
try
–3 –1
Rate constant K = = 6.93 × 10 min .
t
is
Time taken for 75% completion = 2 ×et m
1/ 2

h
Now when Px = 700 = 800 – 2xCso x = 50 mm of Hg
= 200 min. 1/2

r ts
xp e
r y E
t
so total pressure = 800 + 3x = 950 mm of Hg

s m i s
e r t h e
13. (D)
Order of reaction can E
x p C
s t r y have any value zero, positive ,negative or any fractional value

m i
C h e
35
 Chemical Kinetics
14. (A)
aG + bH  products

e r t s er ts
x p
Rate = k[G]x [H]y
E(Let initial conc. are [G] & [H] ) ry Exp
ry x

t [2H] = K2 .2 R
R = K [G] [H]
s
y

st
i i
0 0 0 0

m so 2 = 8  x + y = 3 hem
x y x y

e
8R = K[2G]
h
0 0

C x+y
C
15. (D)
From Arrhenius equation
K = Ae–Ea/RT

e r ts Ea

xp
nk = nA –

y E
RT
er ts
=t
2.303 log Kis r log A – xp
E
Ea
m
2.303

h e RT
stry
C log K = Ea × 1 + log A mi....... (A)
2.303R T
Che er ts
log K = – (2000)
1
Exp
try
+6 ........(B)
T

mis
e
On comparing equation (A) and (B)
Ea
r ts Ch
= –2000
x p e
E
2.303R

st r y 6

i
Ea = 2.303 × 8.314 × 2000 = 38.29 kJ and log A = 6A = 10

h e m r t s
16. C Zero xp e
ry E
C  C 1  0.75 0.25
is t
m
0
K= = = =5
t 0.05 0.05
C h e ts
er
xp
0.75  0.40 0.35
E
K= = =5
0.07 0.07

stry
ts
So, reaction must be of zero order.
mi
er Che
Exp
18. (ABD)
C = C e str
y
t
m
0
i –Kt

C h e
36
 Chemical Kinetics
1
t1/2  , K on increasing T.
K

er ts er ts
C Exp p
After eight half lives,

Ex
t
C=
s r2y
o

stry
i i
8

hem C
hem
C C –
C
o
o 8
 2
% completion =  100 = 99.6%
C0

19. 9
 C 

ts
Kt1/8 = In  O  = In 8
 CO / 8 
e r
 C  xp s
E r t
Kt = In 
1/10
 tr 
s y O
= In 10
xpe
i
C / 10

tm
E
O

h e ×10 = 9 str
y
C t i
In 8 log 8
 10 =
1/8
 10 =
m
then
In 10 log 10

Ch e
ts
1/10

er
Exp
21. (B)
istry
M  N
hem
r = K [M]x
er ts C
xp
as [M] is doubled, rate increases by a factor of 8.
E
i.e.
stry8 r = K [2M]x

mi 8 = (2)x

Che x=3
e r ts
E xp
trywill increase, so % yield will also increase
22. B

m is
Initially on increasing temperature rate of reaction

h
with time. But at equilibrium % yield
C e at high temperature (T ) would be less than at T as
ts
r
2 1
reaction is exothermic.
x p e
r y E
23. 8
8H + MnO + [Fe(H O) (C O ) ]  Mn + Fe + 4CO + 6H iO st
+ 
4

e r t s 2 2 2

h e
4 2
m 2– 2+ 3+
2 2

rate of change of [H ] p
E x 
C
y
=8
r


is t
rate of change of [MnO ] 4

m
Che
37
 Chemical Kinetics
24. (BCD)

s s
(A) High activation energy means lower value of k and slow reaction.

e r t er t
E x p Exp
(B) On increasing temperature energy of particles increases hence greater number of collisions

s r y
occurs whose energy
t= Ae
exceeds the activation energy.
stry
i
m dk E
– E a / RT

m i
e e
K

Ch k a C h
dT RT 2
dk E
 a2
dT RT
(C) Rate of increase of k with temperature is higher when Ea has a large value

e r ts
xp
(D) A =Frequency factor = No of collisions per unit time per unit volume.

y E e r ts
25. AD
is tr E x p
(A) Eam y
h e is independent on stearic factor
C(B) k = P.Z.e is t r
m
– E a /RT

h e
C ts
– E a / RT

According to collision theory, P value is generally less than unity but for some reactionsePris
k = Ae

E xp from
trthey experimentally
greater than one and for such reactions, observed rate is greater than rate predicted
Arrhenius equation. For a reaction with P value greater than 1, implies s
i that
m by Arrhenius equations
h e
determined value of frequency factor (A) is higher than that predicted
s C
e r t
and such reactions proceeds rapidly without the use of a catalyst.  (A) and (C).

E x p
26. (A,D)
Aist ry
 2B + C
0m
t =e t s
(g) (g) (g)

h
Ct=t P –x
P 0 0
e r
xp
0
0 2x x
E
i
t
s try
Total pressure at t time P = P – x + 2x + x = P + 2x = 0 0

h e m
2C ts
P –P

e r
t 0
x=

 P – P  3P  P E x p
 P –x=P –   = t

s t r y0 0 t

i
0 0
 2  2
 ts e m
1 e
t= p ln 
r P   kt = ln  C2Ph 


E xk  3P – P 2  0 0

 3P  P 
try ln(3P – P ) = ln(2P ) – kt
0 t 0 t

m is
e
0 t 0

C h
38
 Chemical Kinetics
P0
At t  t1 ; PA =
3
t s ts
3

p e r
1  P  ln 3
per

x
t 1  ln  0  = = constant
Edepends on initial concentration of reactant.
k  P0 / 3 
Ex
y y
k
r r
3

Value of ktdoesn't
is is t
he m h e m
C
27. 6.75 C
From the given data rate of reaction is obtained as :
r = k[A]1[B]0[C]1
From experiment–1 : r = k[0.2][0.1] = 6 × 10–5
So, k = 3 × 10–3 s–1

e r ts
r = 3 × 10–3 × 0.15 × 0.15 = 6.75 × 10–5 mol dm–3s–1

28. 2.30
1 d(N O ) E
xp r ts
Rate = –
2istdtr
y = k[N O ] 2 5

xpe 1

E
2 5

h e m– d(N O ) = 2k[N O ] = k [N O ] try

C is
2 5 1 1 1

m
2 5 2 5
dt
e
k = 2k = 2 × 5 × 10 = 10hsec
C ts
1 –4 –3 –1

er
xp

2N O (g)   2N O (g) + O (g)
E
2 5 2 4 2

try
t=0 1 0 0
P
mis
e
t 1–P P

r ts
2
Ch
e
P
Ptotal after time ' t ' 1   1.45 atm
x
Eatmp 2

Ptr y
P =0.9
k’ =  nis
m ts
1

Ch e t P
er
p
t

–3 1 1 1
Ex
ry
10 = n  n 10
y  10 0.1 y 10
st
3 3

mi
y = n10 = 2.303
C h e ts
er
29. (A)
Exp
Sol. Since given reaction follows SN1 mechanism
stry
ts
 reaction is 1st order
mi
er Che
xp
0.693
 t1 
E
try
2 k

mis
Che
39
 Solid State

EXERCISE # (JEE-MAIN)
1. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3rd of

e r t s e r ts
x(2)pX Y xpX Y
tetrahedral voids. The formula of the compound will be: [AIEEE-08]
(1) X Y
ry
4
E 3 2 3 (3) X Y
ry E (4)
2 3 4

s t s t
i and in body centered packed structure
i of free space in cubic close packed structure
e m e m
Ch Ch
2. Percentages
are respectively: [AIEEE-10]
(1) 48% and 26% (2) 30% and 26% (3) 26% and 32% (4) 32% and 48%

ts
3. The edge length of a face centered cubic cell of an ionic substance is 508 pm. If the radius of

p e r
the cation is 110 pm, the radius of the anion is: [AIEEE-10]
(2)x288 pm
E t s618 pm
(1) 144 pm
tr y (3) 398 pm
p e r (4)

m i s E x
h enumber of atoms per unit cell in B.C.C. & t
s ry is respectively:
4.
C(1) 8, 10
The
i
m (3) 1, 2
F.C.C. [AIEEE-02]

h e
ts
(2) 2, 4 (4) 1, 3
C e r
E x?p
5. How many unit cells are present in a cube-shaped ideal crystal of NaCl of mass 1.00g
21 21 y
(2) 1.71 × 10 unit cells istr [AIEEE-03]
m
(1) 1.28 × 10 unit cells
21
s
21

C h e
t
(3) 2.57 × 10 unit cells (4) 5.14 × 10 unit cells
e r
What type of crystalE
xp
6.
s r
t Cly defect is indicated in the diagram below? [AIEEE-04]

m
+
i – + – +
s
–

ChCle t Na
Na Na Cl Na Cl
e r
xNap
– – + +
Cl Na
+ – –

r y E + –

iNast
Na Cl Cl Cl

m
– + – + +

Che (2) Schottky defect

Cl Na Cl Na
(1) Frenkel defect
e r ts
(3) Interstitial defect (4) Frenkel and Schottky defects
E xp
s t r y
s
An ionic compound has a unit celltconsisting m i of a cube and B ions on
7.
e
er The empirical formulaCofhthis compound would be–
of A ions at the corners

E p
the centres of the faces ofxthe cube.

s t r y
m i [AIEEE-05]

C h e
(1) A B 2 (2) AB (3) A B 3 (4) AB3

40
 Solid State
8. Lattice energy of an ionic compound depends upon: [AIEEE-05]

s s
(1) Size of the ion only (2) Charge on the ion only

e r t e r t
E x p
(3) Charge on the ion and size of the ion (4) Packing of ions only
E x p
s r y
t of atoms present in a face-centred cubiciunit
s r y
tcell of a metal is (r is atomic radius):
9.
m i
Total volume
m
C he Ch e [AIEEE-06]
24 3 12 3 16 3 20 3
(1) r (2) r (3) r (4) r
3 3 3 3

10. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm.

e r t
Atomic radius of the lithium will be: s [AIEEE-12]
(1) 152 pm
E x p
(2) 75 pm (3) 300 pm
t s
(4) 240 pm

tr y p e r
Among theis E x
11.
m
hDensity
following the incorrect statement is:
y
e of crystals remains unaffected dueistotrFrenkel defect
[Jee-Main (online)-12]

C(1)
(2) In BCC unit cell the void space ise m
C h 32%
r ts
(3) Electrical conductivity of semiconductors
e
and metals increases with increase in temperature
xp
(4) Density of crystals decreases due to Schottky defect
E
i stry
12.
h
A solid has 'bcc' structure. If the distance of nearest approach
e m between two atoms is
e r
1.73 Å, the edge length of the cellt s
is: C [Jee-Main (online)-12]

E xp216 pm
y
(1) 314.20 pm (2) (3) 200 pm (4) 1.41 pm

s t r
i chloride crystallizes in a body centred cubic lattice with sedge length of unit cell of
e m r t
Ch390 pm. If the size of chloride ion is180 pm, the size of ammonium
e
13. Ammonium

E xp ion would be:

i stry [Jee-Main (online)-12]
(2) 174 pm em (3) 142 pm
(1) 158 pm
C h (4) 126 pm
r t s
x e
p crystal
E
14. The radius of a calcium ion is 94 pm and of the oxide ion is 146 pm. The possible
structure of calcium oxide will be:
s t r y (online)-12]
[Jee-Main
(2) Tetrahedrals m (4)iTrigonal
(1) Octahedral
e r t (3) Pyramidal
e
hM O. Metal M, is present as M
15.
E x
Experimentally it was found p C
that a metal oxide has formula 2+

y
0.98
3+

i s t r
and M in its oxide. 3+
Fraction of the metal which exists as M would be:

h e m [Jee-Main (offline)-13]
C(1) 7.01% (2) 4.08% (3) 6.05% (4) 5.08
41
 Solid State
16. An element having an atomic radius of 0.14 nm crystallizes in an fcc unit cell. What is the
length of a side of the cell? [Jee-Main (online)-13]
(1) 0.96 nm
e r t s
(2) 0.4 nm (3) 0.24 nm
e r
(4) 0.56 nm ts
E x p E x p
s tr y s tr y
i i
17. Which one of the following statements about packing in solids is incorrect?

e m
(1) Void space in ccp mode of packing is 26%
e m
h is 12
[Jee-Main (online)-13]

Ch (2) Coordination number in hcp mode of C packing

(3) Void space in hcp mode of packing is 32%
(4) Coordination number in bcc mode of packing is 8

18. In a face centred cubic lattice, atoms of A form the corner points and atoms of B form the face

er ts
centred points. If two atoms of A are missing from the corner points, the formula of the ionic

Exp
compound is
r ts [Jee-Main (online)-13]

str
(1) AB2y xpe
(2) AB3 (3) AB4 (4) A2B5

mi y E
19.

Che istr
Copper crystallises in fcc with a unit length of 361pm. What is the radius of copper atom?

m
[AIEEE-2011, Jee-Main (online)-13]

Ch e
ts
(1) 181pm (2) 128pm (3) 157pm (4) 108pm

CsCl crystallises in body centred cubic lattice. If 'a' is its edge length then whichpof thee r
20.
[Jee-MainE
x
following expression is correct :
st r y 3a
(offline)-14]
3
  (3) r  r  3a
m i  
(1) r  r 
Cs Cl
2
a (2) r
Cs 
r
s
3a
Cl Cs
h
Cl
e (4) r
Cs 
r CI 

C points and atoms B at the face

2

In a face centered cubicp e rtatoms A are at the corner

21.
E xB is missing from one of the face centered points, the formula of the
lattice

r yis:
centered points. If atom
s t
(1) AB i
ionic compound [AIEEE-2011, Jee-Main (online)-14]

h e m 2 (2) A B
2 3 (3) A B5 2
r t s
(4) A B
2 5

e
22. C The appearance of colour in solid alkali metal halides is generally
xp due to:Jee-Main (online)-14]
E
ry defect (4) Interstitial position
i s tSchottky [AIEEE-2011,

m
(1) Frenkel defect (2) F-centres (3)

h e
C of sides and angles are respectively[Jee-Main (online)-14] ts
23. In a monoclinic unit cell, the relation
p e r
(2) a  b  c and  =  = 90º  Ex
(1) a  b  c and       90º
(4) a  b  c and  =  =  =t90º
s r y
(3) a = b  c and  =  =  = 90º
t s m i
e e
r per atom presentCinha cubic close packed structure is :-
24.
x p
The total number of octahedral
E
void(s)

s r y
t (2) 2
[Jee-Main (online)-14]
(1) 1
m i (3) 3 (4) 4

C h e
42
 Solid State
25. Sodium metal crystallizes in a body centred cubic lattice with a unit cell edge of 4.29Å. The
radius of sodium atom is approximately: [Jee-Main (offline)-15]
(1) 5.72Å
r
(2) 0.93Å
e ts (3) 1.86Å (4) 3.022Å
e r t s
x p compounds is metallic and ferromagnetic? xp
26.
r y E
Which of the following
r y E [Jee-Main (offline)-16]
i st (3) MnO ist
m m
(1) CrO (2) VO (4) TiO
e e
2 2 2 2

C
27. h A metal crystallises in a face centred C
cubic h
structure. If the edge length of its unit cell is „a‟, the
closest approach between two atoms in metallic crystal will be [Jee-Main (offline)-17]
a
(1) 2 a (2) (3) 2a (4) 2 2 a
2

ts
28. Which of the following compounds is likely to show both Frenkel and Schottky defects in its

e r
xp
crystalline form ? [Jee Main (Jan. 2020)]
(1) AgBr
y E
(2) KBr (3) ZnS
r t
(4) CsCl
e s
A diatomicis
tr E x p
29.
h e m ry of molecules present in 200 g of X is :
molecule X has a body-centred cubic (bcc)
density of the molecule is 6.17 g cm . Thetnumber
2 structure with a cell edge of 300 pm.

C(Avogadro constant (N ) = 6 × 10 molm) i s

–3
The 2

e
23 –1

(2) 2 N Ch
[Jee-Main (Sept.) 2020]
ts
A
(1) 8 N A A (3) 4 N A (4) 40 N A
e r
An element crystallizes in a face-centred cubic (fcc) unit cell with cell edge a.E xpdistance
: ry
30. The
between the centres of two nearest octahedral voids in the crystal lattice ist
i s
m[Jee-Main (Sept.) 2020]
s h e
C (4) 2a
(2) ert
a a
xp2
(1) (3) a
2
r y E
s t
A crystaliis made up of metal ions 'M ' and 'M ' and oxide ions. Oxide ions form a ccp lattice
31.
h e m The cation 'M ' occupies 50% of octahedral voids and thertcation
1 2
s 'M ' occupies 12.5%
structure. 1 e
C of tetrahedral voids of oxide lattice. The oxidation numbersxpof 'M ' and 'M ' are, respectively :
2

r y E 1 2

i s t [Jee-Main (Sept.) 2020]

(1) +2, +4 (2) +3, +1
h e m (3) +1, +3 (4) +4, +2
C e r ts
32. –2 –1
An element with molar mass 2.7 × 10 kg mol forms a cubic unit cell with edge length
E p
x________405

y (Sept.) 2020]
3 –3

r
pm. It its density is 2.7 × 10 kg m , the radius of the element is approximately
–12
× 10 m (to the nearest integer).
is t
[Jee-Main

e r t s h e m
E x p C
s t r y
m i
C h e
43
 Solid State

EXERCISE # (JEE-ADVANCED)
1.
t s t s
A metal cryatallises into two cubic phases, FCC and BCC whose unit cell lengths are 3.5 and
e r e r
p p
3.0 Å respectively. Calculate the ratio of densities of FCC and BCC. [JEE-1999]

The figures givenE

x E x
2.
s r y r
t the unit cell for the corresponding structure y
t and identify these planes
below show the location of atoms in three crystallographic
s
planes in FCC

m i
lattice. Draw
m i in your

C hediagram.
C h e [JEE-2000]

3.
r ts
In a solid “AB” having NaCl structure “A” atoms occupy the corners of the cubic unit cell. If
e
xp s
all the face-centred atoms along one of the axes are removed, then the resultant stoichiometry
of the solid is
y E e r t [JEE-2000]
(A) AB2
is tr (B) A2B (C) A4B3
E x p (D) A3B4

h e mionic solid [MX] with schottky defects, r

t ynumber of positive and negative ions are
4.
Csame. [T/F]
In any
m i s the

e
[JEE-2000]

Chcrystallising in a hcp structure is e r ts

xp
5. The coordination number of a metal [JEE-2000]
(A) 12 (B) 4 (C) 8 (D) 6
E
y corner of the
reach
6. A substance A B crystallises in a FCC lattice in which atoms “A” occupy
cube and atoms “B” occupy the centres of each face of them
x y
is t
composition of the substance A B s
C h e cube. Identify the correct

r t
e (B)
.
x y [JEE-2002]
(A) AB 3

E x p AB
4 3

y
(C) A B (D) composition cannot be specified
r
3

Marbles i t 10 mm each are to be arranged on a flat surface so that their centres lie
ofsdiameter
7.
h e mthe area enclosed by four lines of length each 40 mm. Sketch r t sthe arrangement that will
C give
within
x p e
E
the maximum number of marbles per unit area, that can be enclosed in this manner and
deduce the expression to calculate it.
s tr y [JEE 2003]
i
mwith A : B = 1 : 1. The shortest distance between As
8.
h e
(i) AB crystallizes in a rock salt structure
and B is Y nm. The formulaC t
1/3
e
mass of AB is 6.023 Y amu where Y is any arbitrary constant.
p r
Find the density in kg m . –3
E x
[JEE–2004]
-3

s tr y
i
(ii) If measured density is 20 kg m . Identify the type of point defect.

e t s
r contains cations inCalternatee m
h tetrahedral voids?
9.
x p
Which of the following FCC structure
E
(A) NaCl str
y [JEE 2005]

m i (B) ZnS (C) Na O

2 (D) CaF 2

C h e
44
 Solid State
10. An element crystallises in FCC lattice having edge length 400 pm. Calculate the maximum
diameter which can be placed in interstitial sites without disturbing the structure.

e r t s e r ts [JEE 2005]

x p x p
E is 5 Å which crystallizes
Eunit cell of a metal having atomic weightry75 g/mol
11.
s r
The edge lengthy
t If the density is 2 g/cc then find the radius
of
stof metal atom. (N = 6 × 10 ). Give
m i m i 23

e e
in cubic lattice. A

C h the answer in pm.

C h [JEE 2006]

12. Match the crystal system / unit cells mentioned in Column I with their characteristic features
mentioned in Column II. Indicate your answer by darkening the appropriate bubbles of the 4 ×
4 matrix given in the ORS. [JEE 2007]

e r ts
Column I
E x p Column II
t s a = b = c and
tr y
(A) simple cubic and face-centred cubic
e r
(P) have these cell parameters
 =  =  xp
m is E
(B) e r y
thave only two crystallographic angles of 90°
C(C)h cubic and tetragonal s
cubic and rhombohedral (Q) are two crystal systems
i
m (S) belong to same crystal system.
e
(R)
(D) hexagonal and monoclinic
C h r ts
xp e
Paragraph for Question No. 13 to 15
ratomsE
y is described
In hexagonal systems of crystals, a frequently encountered arrangement of
is t
e
as a hexagonal prism. Here, the top and bottom of the cell are regular m hexagons and three atoms
are sandwiched in between them. A space-filling model ofhthis structure, called hexagonal
e r t s C
by six identical spheresx asp
close-packed (HCP), is constituted of a sphere on a flat surface surrounded in the same plane

r E
y each other and represent the second layer. Each one of these three spheres
closely as possible. Three spheres are then placed over the first layer

s t
i spheres of the bottom layer. Finally, the second layer is scovered with a third layer
so that they touch

e m
touches three
r t of every sphere to be „r‟.
Chthat is identical to the bottom layer in relative position. Assume
x p eradius

r y E
13. The number of atoms in this HCP unit cells is
i(C)t
s 12
[JEE 2008]
(A) 4 (B) 6
he m (D) 17

C e r ts
14. The volume of this HCP unit cell is
E x p
[JEE 2008]

r ry
t
64
s
3

i
(A) 24 2r 3 (B)16 2r 3 (C)
12 2r 3 (D)

s m
3 3

e t
rcell is h e
15.
E
The empty space in this HCPx p unit C [JEE 2008]

t r y
is
(A) 74% (B) 47.6 % (C) 32% (D) 26%

m
Che
45
 Solid State
16. The correct statement(s) regarding defects in solid is (are) [JEE 2009]
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion.

r t s
(B) Frenkel defect is a dislocation defect
e e r t s
E x p x p
(C) Trapping of an electron in the lattice leads to the formation of F-center.
E
r y ry
(D) Schottky defects have no effect on the physical properties of solids.
s tcell shown below is
t efficiency of the two-dimensional squareiunit
s
m i m
17.
C heThe packing
C h e [JEE-2010]

e r ts (C) 74.05%
p
(A) 39.27% (B) 68.02% (D) 78.54%

E x r t sis.
18.
s t r y
The number of hexagonal
x p e
faces that present in a truncated octahedron [JEE-2011]

m i y E
19. e M X has cubic close packingis(ccp)
hcompound
CAshown tr arrangement of X. Its unit cell structure is
ofm
p q

below. The empirical formula e

C h the compound is: [JEE-2012]
r ts
xp e
E
s try
M=

m i
e
M=

r t s C h
xp e
r y E
is t
h e m r t s
C (A) MX e
p (D) M X
(C) M X Ex
try
(B) MX 2 2 5 14

The arrangement of X ions around e

–
Am
i s
h
+

ts
20. ion in solid AX is given in the figure (not drawn to
scale). If the radius of X is 250C r
e
– +

xp
pm, the radius of A is - [JEE-2013]

ry E
X-
i s t
e r t s h e m
E x p A+
C
(A) 104 pm st r y
m i (B) 125 pm (C) 183 pm (D) 57 pm

C h e
46
 Solid State
21. If the unit cell of a mineral has cubic close packed (ccp) array of oxygen atoms with m fraction

s s
of octahedral holes occupied by aluminum ions and n fraction of tetrahedral holes occupied by

e r t
magnesium ions m and n respectively, are –
e r t [JEE-2015]

E p 1, 1
x(B) E xp1 , 1
y
1 1 1 1
2 8 ry r
(A) , (C) ,
t t
(D)
is
mCORRECT
4 2 2
m is 4 8

22. he
C The statement(s) for cubic close e
Ch (ccp) three dimensional structure is (are)
packed
[JEE-2016]
(A) The number of the nearest neighbours of an atom present in the topmost layer is 12
(B) The efficiency of atom packing is 74%
(C) The number of octahedral and tetrahedral voids per atom are 1 and 2, respectively
(D) The unit cell edge length is 2 2 times the radius of the atom

e r ts
xp
23. A crystalline solid of a pure substance has a face-centred cubic structure with a cell edge of

E t s
400 pm. If the density of the substance in the crystal is 8 g cm -3, then the number of atoms
y e r
is tr E x p
present in 256 g of the crystal is N × 1024. The value of N is [JEE-2017]

h e m t r y
is the sequential instructions [JEE-2018]
24. Consider an ionic solid MX with NaCl structure. Construct a new structure (Z) whose unit cell
CisNeglect m
constructed from the unit cell of MX following given below.
the charge balance.
C hethe central one r ts
e
(i) Remove all the anions (X) except
(ii) Replace all the face centered cations (M) by anions (X)
E xp
ry
(iii) Remove all the corner cations (M)
(iv) Replace the central anion (X) with cation (M)
i st
 number of anions 
h e m
 number of cationsts C
The value of   in Z is _____.
e r 

E xp of a compound containing cation M and anion X is shown below.

25.
r yto the anion, the cation has smaller ionic radius. Choose the correct
The cubic unit cell structure
s t
m i
When compared
s
Ch e e r t
xp
statement(s). [JEE - 2020]

E
istry
h e m
C e r ts
E xp
s t r y
t s m i
(A) The empirical formula of thee r is MX. C h e
x p compound
(B) The cation M y andE
is t r anion X have different coordination geometries.

e m
(C) The ratio
h
of M-X bond length to the cubic unit cell edge length is 0.866.

C ratio of the ionic radii of cation M to anion X is 0.414.

(D) The
47
 Solid State

ANSWER KEY
s s
EXERCISE # (JEE-MAIN)
r3t r t
1. 1
pe 2
2. 1 3. 4. 2 5. 3
p
6.
e
x 3 14.
2 7. 3
1 Ex10. E
8. 3 9.
s try2 17. 2 11. 1 12.
str
3
y 20. 3 21.
13. 1

mi23. 2 24. 2 mi 2 27. 3 28.

15. 1 16. 18. 3 19. 3 1
22. he 25. h 1 e 26.
C
29.
4
3 30. 1 31. 1 32.
C 143
1

EXERCISE # (JEE-ADVANCED)
1. (1.259)
er ts
Exp r ts
stry xpe
mi y E
2.
Che istr
e m
Ch er ts
E xp
try
3. (D) 4. (T) 5. (A) 6. (A)

m is
e
7. To have maximum number of spheres, the packing must be hcp.
Maximum number of spheres = 25.
r t s C h
xp e
r y E
i s t
h e m r ts
C xp e
E
i stry
h e m
C er ts
E xp
Area of figure = 2 × Area of equilateral triangle of side = 40 mm or 4 cm.ry
i s t
3
e r ts h em
= 2
xp C
2
(4) = 13.856
4
E
ry marbles/cm
is=t1.804
25
 2

h e m
13.856
C
48
 Solid State
8. (i) 5 kg m–3

s s
(ii) There is a huge difference density & observed density. It is only possible if some foreign

e r t er t
E x p
species occupy interstitial space i.e. substitution defect.
Exp
r y
(i) In Rock salt like crystal AB,
st Z  M = 4  6.023y mist
there are 4 AB units per
r
unit
y
cell

midensity =
8y  10  6.023 e
Che a N
Ch 10
3 –27 23
A

1 1
= 5 × 03 g/m3 [ a = 2y 3
nm or 2y 3 10–9 m ]
or 5kg/m3

9. (B) 10.
er ts 11. 216.5 pm
117.1 pm
12. A  P, S
E xp r ts
str y x p e
B  P, Q
C eW m i y E
h
CD  Q, R istr
em
Ch e r ts
Have the cell parameters a = b = c &  =  =  = (p) & are 2 crystal systems (Q)Exp
(A) simple cubic & FCC

is try
m angles of 90° (R).
(C) Cubic & Tetragonal are 2 crystal system. (Q)

s C h e
t
(D) Hexagonal & Monoclinic are 2 crystal system (Q) have 2 crystallographic
e r
A E15.
xp D 16. BC 17. D 18. 8 19. B
13. B 14.
s t r y
m i s
Che t
20. A 21. A 22. BCD 23. 2 24. 3 25. AC

e r
E xp
is try
h e m
C e r ts
Exp
s tr y
t s m i
e r C h e
E x p
s t r y
m i
C h e
49
 Solid State

HINT AND SOLUTIONS

EXERCISE # (JEE-MAIN)

e 2r ts er ts
1.
x p
Number of Atom X =
EY = 4 3
8
Exp
ry
Number oftAtom
stry
is i
e m or X Y em
Ch Ch
X
 Formula of compound is Y 16
4 4 3
3

2. For C.C.P.
% Of free space = 26 %

er ts
For B.C.C.
%x
% Of free space = 32 E
p ts
tr y per
ma is Ex
h e stry
C mi
e
3. (r++ r–) =
2
Ch r ts
110 + r =
508
xpe
E
–
2

 r– =
508
– 110 istry
2
hem
 r– = 144 pm
er ts C
Exp
stry
i
4. (2)

h e m r ts
C x p e
6.022 10
E
23

ry
5. 58.5 gm of Nacl contains unit cells
4
6.022 m
i s t
 1 gm of Nacl should contain
h e
C 58.5  4
10 1 23
21

ts
r
i.e. 2.57 × 10 unit cells

xpe
r y E
6. Schottky defect
is t
i.e.r1ts h e m
8pe
1
7. Number of Atom A = 4 
E1 x C
s ry
t B = 6  2 i.e. 3
m i
Number of Atom

Ch e
Formula of compound is AB 3

50
 Solid State
8. Lattice energy of an ionic compounds depends on  (3)

er s
i.e. charge on the ion & size of the ion.
t e r ts
x p x p
Eis 4  r
E present in a face. centred unit cell ofrmetal
9. Total volume y
s tr of atoms
s t y 4 3

i
m16 r m i 3

C hei.e. 3
C h e
3

10. For B.C.C.

3a

ts
r=
4
p er
3  351
i.e. r =E x r ts
=
4
str y 152 pm

x p e
m i E
yconductivity of semiconductors & metals
11. h e
Cincreases with Increases in temperature.mi
The s t r
only incorrect statement is (3) i.e. electrical

Che er ts
12. For B.C.C
E xp
3a
is try
2 em
The distance of Nearest Approach between atom is equal to

r ts C h
3a
= 1.73
xp e
2
 a = 2Å ort200 r ypm E
m i s s
h e e r t
13. C For NH Cl in B.C.C lattice: xp
E
try
4

 r  r  = 32 a m is
NH 4  Cl

C h e t s
er
xp
3  390
r  180 =
NH 4 
2
ry E
3  390 i s t
 r NH 4 
= – 180
er ts h e m
p C
2
 r
E x
y
= 158 pm
r
NH 4 

ist
h e m
C
51
 Solid State
rCa 2 94
14. For Cao : = = 0.643  By radius radio rule it should be octahedral.
s s
rO 2 146

er t er t
E x p Exp
15. M O0.98

s
1
r y
1trole of oxide stry
i
mof M = 0.98, mole of 0 = 1
Consider
mi
C hemole –2

Che
Let moles of M+3 = x
& moles of M+2 = (0.98 – x)
 By charge bereaving (0.98 – x) 2+ 3x – 2 = 0.
0.04
 x = 0.04  % of M+3 =

e r t s
0.98
 100
i.e. 4.08 %

E x p t s
tr y p e r
a = 2 2 r is  a = 2 2 × 0.14 i.e.
16. For F.C.C

m Ex
h e r y
a = 0.4 mm
s t
CThe only incorrect statement is (3) i.e.. void
m ispace in hcp mode of packing is 32%
Ch e
ts
17.

er
Number of atom A = 6 
1 3
E xp
try
18. i.e.

s
8 4

m i
e
1
Number of atom B = 6  i.e. 3  Formula of compound is AB
2
r t s Ch 4

xp e
19. For F.C.C.
E
a y 361
r = str =
m i i.e. r = 128 pm
s
Ch e 2 2 2 2
e r t
E xp
try
3
20. For CsCl r r =
cs cl
2
a
m i s
C1 h e ts
1
er
xp
21. Number of atom A = 8  i.e.
1
8
 Formula compounds is (AB ) i.e. tr Ay
E
Number of atom B = 5  5/2
is B 2 5

ts metal halide is generally m

2

e r C h e
22.
E x: p
The appearance of colour in solid–alkali due to F–centers.

23.
a b c ist&
ry  =  = 90° a
For monoclinic unit cell

h e m
C
52
 Solid State
24. The total number of octahedral void per atom present in cubic close packed structure is 1.

3a
e r ts

3  4.29
e Å ts
r = 1.86 r
p p
25. For B.C.C. r= r= i.e.

E x 4 4
E x
26.
t r y
CrO2 is magnetic & ferromagnetic both
s s t r y
m i m i
Ch
27. e
The
Ch e
closest approach between 2 atoms in metallic crystal in F.C.C. structure is
a
2
28. AgBr can both schottky and Frenkel defect

Z M
29. Density =
NA  a3

6.17 =
2 M
6 10  (300 10 –10 )3
23
r ts
e 200  N
M = 50

E x p t s
tr y
 Number of molecules in 200 gm. = =4N
p
A
e r
s x
A

Mine
i 50
m between two octahedral voids in fcctr=y 2 E
h
a
C is (Distance between edge centre and body centre)
30. distance

he m
C e r ts
31. –2
O ions form ccp. O  (–8 charge)
4
E x p
try
50
M = 50% of O.V. 
1
100
×4 = 2 : (M ) 1 2

m is
×8 = 1s: (M ) C h e
100 rt
12.5
M = 12.5% of T.V. 
e
2 2 1

So formula is : (M )E xp
y
(M )O
r Both metals must have +8 charge in total.
1 2 2 1 4

This must betneutral.

m is s
Ch e O.N.of M  2 
e r t
xp
1
From given options :  
 M  4  2

ry E
Z M ist
32.  Density =
h e m
N a
C ts
3
A

e r
Z  2.7 10
xp
–2

E
3
2.7 × 10 =
6.02 10  (405 10 )
r y
23 –12 3

is t
s m
Z=4

e r t h e
C
Structure is FCC.

E x p
y
So, a = 2 2R

R =ist
405r 10 –12
–12

m
m = 143 × 10 m

C h e 2 2

53
 Solid State

EXERCISE # (JEE-ADVANCED)
1. (1.259)
e r ts er ts
p p
Z
Density 
E(3)x a3
Ex
=st
r y stry
d mi (3.5) i
3
d. 4

m
F.C.C
= 1.259

Che he
3
2
C
B.C.C

2.

e r ts
E xp r ts
3. (D)
s y
tr A per unit cell =  1  8  4  1  = 3 Expe
Number ofiatoms
h em 2 ry
t
C
8
 m
i s
4·e
1 
Number of atom B per unit cell = h
C  4  ts
12   1
er
 Formula is (A3B4)
Exp
istry
hem
4. (T)
e r ts C
Factual
E x p
s tr y
5. (A)
m i s
h e
3 - consecutive layers of atom in hcp are there.
e
C Atom X is in correct of 12 like atoms, 6 from layer B and x3 from r t
E p to and bottom layer A each.

r y
ist
 C.N. = (6 + 3 + 3) i.e 12

he 1 m s
6. (A)
C e r t
Number of atom of A per unit cell = 8  i.e. 1
E xp
y
8
1
i st r
t
Number of atoms of B per unit cell =
e r s6 
2
h m
i.e. 3  formula is AB
e
3

x p C
E of spheres, the packing must be hcp.
7.
r y
t of spheres = 25.
To have maximum number
s
m i
Maximum number

C h e
54
 Solid State

er ts er ts
Exp Exp
stry stry
mi mi
Che Che

Area of figure = 2 × Area of equilateral triangle of side = 40 mm or 4 cm.

= 2
3 2
(4) = 13.856 
25
e r ts
= 1.804 marbles/cm2
xp
4 13.856

y E e r t s
8. (i) 5 kg m
i s tr
–3

E x p
h e mis a huge difference density & observed
(ii) There
t ry density. It is only possible if some foreign
C species occupy interstitial space i.e. m is defect.
heare 4 AB units per unit cell
substitution

C
(i) In Rock salt like crystal AB, there
e r ts
 density =
Z M
=
4  6.023y
E xp
a N 8y  10  6.023  10
ry
3 –27 23

s t
A

2y 10 m ]m i
e
1 1
3 –9

h
3 3
= 5 × 03 g/m [ a = 2y nm or
or 5kg/m 3

e r t s C
E x p
s t r y
In C.C.P,inumber of tetrahedral voids = 2 × number of atoms.
9. (B)

h m
Asethere are 4S ions at lattice points & they need 4 zn , e r t sare adjusted in alternate
C tetrahedral voids –2

xp
which +2

E
i s try
mof void known as octahedral & Tetrahedral voids. s
10. 117.1 pm

h e t
It r is the radius of void & r isC
In a cubic crystal system, there are 2 types
e r
xp
1 the radius of atom creating these voids, then
2

r 
ry E
 
1
= 0.414
i s t
r 2 octahedral

e r t s h e m
r 
 
1
= 0.225
E x p C
r 2

s r y
t ratio values indicate that octahedral void has larger radius, have for maximum
The above iradius
tetrahedral

h e mof atom to be present in interstitial space

C diameter
55
 Solid State
r1 = 0.414r2

er t
Also in F.C.C., 4r2 =
s 2a
er
2  0.414  ats 0.414  400
xp
 Diameter required (2r1) = 2 × 0.414 r2 =
E Exp =

y y
2 2 2
i.e.
is t r
117.1 pm
istr
11. he
m hem
C 216.5 pm
Z M
C
=
a 3  NA
 a 3  N A 2  (5  10–8 )3  6  1023
Z = = =2

ts
M 75

per
So, it is a B.C.C. unit cell
3  5Ex ts
R=
3a
= y
4 tr 4
 R = 216.5 pm
per
m is Ex
h e stry
CA  P, S m i
12.
h e
B  P, Q
C e r ts
CW
E x p
D  Q, R
i s try
(A) simple cubic & FCC
Have the cell parameters a = b = c s&  =  =  = (p) & are h e msystems (Q)
e r t system. (Q) C 2 crystal

E x
(C) Cubic & Tetragonal arep 2 crystal
(D) Hexagonal &y
is t r Monoclinic are 2 crystal system (Q) have 2 crystallographic angles of 90° (R).

13. h (B)e m r ts
C  1x p
e
Total number of atoms in 1 unit cell = 12    3   2E
 1
6 try 2 
  =6

m is
Che e r ts
xp
14. (A)
2
 4r
r y E
t
C=
3
s m is
(2 r) er
t h e
4 xp C
3
Area of Base = 6  2

r y E
 volumeiof s tHexagon = Area of base × height =  6 3  4r    2  4r  = 24 2 r
m
2 3

C h e  4   3 

56
 Solid State
15. (D)

s s
4 3
 r
er t
Volume of atomin1unit cell

e
6
r t 3 100 = 74%
p p
Packing fraction = 100 =

E x Volume of 1unit cell

Ex 24 2r3

stry
 Empty space = 26%
stry
m i mi
16. he
C (B), (C)
Che
Frenkel defect is a dislocation defect Trapping of an electron in the lattice leads to the
formation of F-centres.

17. (D)
4R = L 2
e r ts
So, L= 2 2 R
E xp r ts
str
 Area of squarey  
2
2

xpe
i
unit cell = 2 2 R = 8R

e m r y E
Ch is t
Rm
hR e
C ts
R
4R=
er
R So, L= L 2 L 2
Exp
try
R r

mis
e
R

r t s Ch
Area of atoms presentein 1 unit cell = R  4·
 R 
p
2

x  = R
2 2

r y E  4 

t
is Packing efficiency =
2R
m
2

h e 100 = 78.54 %
2

e r ts
C
8R

E x p
18. (8)
istry
h e m
C er ts

Exp
stry
ts mi
e r Che
E xpoctahedron is the 14-faced Archimedean solid with 14 total faces :
try hexagons.
Explanation : The truncated

is
6 square & 8 regular
m
C h e
57
 Solid State
The truncated octahedron is formed by removing the six right square pyramids one from each

s s
point of regular octahedron.

e r t er t
Truncated octahedron unfolded in two dimensions.

Ex p Exp
stry stry
19. (B)
i
m  No. of M atoms =  4  1 = 2 hemi
C heSolution
1
4 C
1 1
Number of X atoms = 6  8 = 3 + 1 = 4
2 8
So, empirical formula of compound is (MX2).

e r ts
p void arrangement.
20. (A)

Eisxoctahedral ts
y
The given arrangement
tr r 0.414 × 250 per
r
r em
A
is Ex
h
0.414 A

st ry
C i

X

i.e. r  103.5 pm em
A
Ch er ts
xp
r A
< 0.732  rA < 183 pm.
E
try
rX 

So, the radius of A+ is 104 pm.

mis
s Che
er t
4 xp
21. (A)
In CCP, O ions areE
–2

s t ry charge = – 8
i of Al ions be x
Hence total negative
m
Letenumber
Ch
+3

er ts
+2
& number of Mg ion be y
Exp
 Total position charge = 3x + 2y
i s try
 3x + 2y = 8
h e m
This relation is satisfied only byCx = 2 & y = 1
er ts
Hence number of Al = 2 +3
Exp
& number of Mg+2 = 1
s try
ts i 1
ions = emi.e.
e r
 m i.e. fraction of octahedral holes occupied by Al +3
Ch4
2

E xp 2

tryof tetrahedral holes occupied by Mg

1
i s
+2
and n i.e. fraction ions =

h e m 8

C
58
 Solid State
22. (B), (C), (D)
(a) Nearest neighbor in the top most layer of CCP structure is 9 thus incorrect.
(b)
r t s
e 4  4 r
Packing efficiency is 74% thus correct.
er ts
xp xp
E efficiency = 3 100 = 3 ry100Ei.e. 74 %
4
y  
3 3

% ofrpacking
4 r

ist (2is2tr)
m Number of tetrahedral void per atomh= 2em
3 3
a

Che(c)
C
Number of octahedral void per atom = 1
this correct
(d) In ABC A
2 2 2 r
AC = AB + BC
 (4r) = a + a
2 2

e r s
t a
2
r

p
r
 4r = 2 a Ex ts
r
r
r y p e
 ais=t2 2 r x
C
E
B a

h e m t r y
C(A,C) m i s
h e
The given compound has CsClC ts
25.
r
type structure in which anion x form simple cubic unit celleand
E xp
ry
+
M cation is present in cubic void.

is t
 r r 
a 3
h e m
s
M X
2
e r t C
= 0.866p
r r
2 Ex
M X 3
 
a
s t r yof M = 8
m i
Coordination no. +

s
Ch e –
e r t
p
Coordination no. of X = 8

E x
try
r M

s
And 0.732 < <1
r X
m i

C h e ts
r
Correct Ans. (A), (C)

xp e
r y E
i s t
e r ts h e m
E x p C
s t r y
m i
C h e
59
 Thermochemistry

EXERCISE # (JEE-MAIN)
1.
ts ts
If at 298 K the bond energies of C–H, C–C, C=C and H–H bonds are respectively 414, 347,
e r r
e [AIEEE-2003]
x p
H C = CH (g) + HE(g) H C–CH (g) at 298 K E x p
615 and 435 kJ mol–1, the value of enthalpy change for the reaction :

will bei:-st
2
ry 2 2 3

s try
3

m m i
he (3)e+250 kj
h
C (1) +125 kJ (2) –125 kJ
C (4)–250 kJ

2. The enthalpies of combustion of carbon and carbon monoxide are –393.5 and –283 kJ mol–1
respectively. The enthalpy of formation of carbon monoxide per mole :- [AIEEE-2004]
(1) 110.5 kJ
e t s
(2) 676.5 kJ
r
(3) –676.5 kJ (4) –110.5 kJ

E x p t s are in the ratio of

y e r
trH for the formation of XY is –200 kJEmolxp. The bond dissociation energy of
s
3. If the bond dissociation energies of XY, X and Y (all diatomic molecules)
1 : 1 : 0.5 i
2 2

h e m and f

t r y
–1

C X will be :-
m i s [AIEEE-2005]
(2) 100 kJ mole
2

Ch (3) 800 kJ mol (4) 300 kJ mol erts

–1 –1 –1 –1
(1) 200 kJ mol

E x p
4. The enthalpy changes for the following processes are listed below :
s t r y[AIEEE-2006]
–1
m i
Cl (g)  2Cl(g),
2

s
242.3 kJ mol

C h e
I (g)  2I(g)
t
r 211.3 kJ mol
–1

ICl(g)  I(g) + Cl(g), pe

2 151.0 kJ mol

E x –1

s
I (s)  I (g),
t ry –1

i the standard states for iodine and chlorine are I (s) and Cl s(g), the standard enthalpy
2 2 62.76 kJ mol

e m r t
Chof formation for ICl(g) is :-
Given that
e
2 2

E x p
(1) –16.8 kJ mol –1

t ry–1 –1
(4) –14.6 kJ mol –1

is
(2) +16.8 kJ mol (3) +244.8 kJ mol

m
5. Che( H°) at 298K for methane, CH (g), is –74.8 kJemolrts.
The standard enthlapy of formation –1

xp
f 4

The additional information required to determine the average energy for C–H bond
r E formation
y [AIEEE-2006]
would be:-
i s t
t s
r of carbon and electron
(1) Latent heat of vapourization of methane
e e m
hgain enthalpy of hydrogen
(2) The first four ionizationp
x
E of hydrogen molecule H
energies C
s ry
t energy of H and enthalpy of sublimation of carbon
(3) The dissociation energy
i
2

e m
(4) The dissociation
h
2

C
60
 Thermochemistry
6. Oxidising power of chlorine in aqueous solution can be determined by the parameters indicated
below:
1
er ts1
diss H eg H  hyd H 
er ts
p
Cl2 (g)   Cl(g)   Cl  (g)   Cl  (aq)
p
2
[AIEEE-2008]
2
Ex Ex
stry 1
The energy involved in the conversion of Cl2(g) to Cl– (aq)
stry
mi 2
mi
Che he
(using the data diss H Cl2 = 240 kJ mol–1, eg HCl = –349 kJ mol–1, hyd HCl– = –381 kJ


C
mol–1) will be:-
(1) –610 kJ mol–1 (2) –850 kJ mol–1 (3) +120 kJ mol–1 (4) +152 kJ mol–1

7. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
ts
CH3OH(l) + O2(g) CO2(g) + 2H2O(l)
2
e r
E xp r ts
At 298 K standard Gibb's energies of formation for CH3OH(l), H2O(l) and CO2(g) are –166.2,

s tr y xpe
–237.2 and –394.4 kJ mol–1 respectively. If standard enthalpy of combustion of methanol is

m i
–726 kJ mol–1, efficiency of the fuel cell will be
y E [AIEEE-2009]

Ch e
(1) 90% (2) 97%
is t r
(3) 80% (4) 87%

h e m data :  G H  0 
C ts
0 
8. On the basis of the following thermochemical
er
f (aq)
–
H O(l)  H (aq) + OH (aq) ; H = 57.32 kJ
2
+

E x p
try
1
O (g) H O (l) ; H = –286.20 kJ
H (g) +
2
2
2 2

m is
s
The value of enthalpy of formation of OH ion at 25°C is :-
(3) –22.88 kJC h e
–
[AIEEE-2009]
(1) +228.88 kJ
e r
(2) –343.52tkJ (4) –228.88 kJ
x p
E of formation of NH is –46.0 kJ mol . If the enthalpy of formation of
9.
r y
t is –436 kJ mol and that of N is –712kJ mol , the average bond enthalpy of
The standard enthalphy
H from itssatoms
3
–1

m i –1

s
–1

e t
2 2

hN–H bond in NH is :-
C (1) –1102 kJ mol (2) –964 kJ mol (3) + 352 kJ mol
3

p e r [AIEEE-2010]

x
–1 –1 –1 –1

E
(4) +1056 kJ mol

st ry
10. Consider the reaction :
4NO (g) + O (g)  2N O (g),  H =e m i [AIEEE-2011]

If N O (s) is formed instead of C

2 2
h2 –111kJ.
5 r

r ts
2 5 N O (g) in the above reaction, the  H value will be :-
2 5

xp e r

E
–1
(given, H of sublimation for N O is 54 kJ mol )
r ykJ
2 5
(1) –165 kJ (2) +54 kJ (3) +219 kJ
s t
(4) –219
i
e ts
r NH OH with HCl isC–51.46 h e m –1
11.
E p
The enthalpy of neutralisation of kJ mol and the enthalpy of
x HCl is –55.90 kJ mol . The enthalpy of ionisation of NH OH is:
4
–1

y
neutralisation of NaOH with
r
4

i s t [JEE-MAIN (online) 2012]

e m –1
(1) +107.36 kJ mol (2) –4.44 kJ mol –1
(3) –107.36 kJ mol (4) +4.44 kJ mol –1 –1

Ch
61
 Thermochemistry
12. Given [JEE-MAIN (OnLine) 2013]
Reaction Energy Change (in kJ)

er ts
Li(s) Li(g) 161
er ts
xp
Li(g) Li (g)
E
+
520
Exp
str
1
y F2(g)  F(g)
stry
i i
77
m m
2

Che F(g) + e– F– (g)

– Che
(Electron gain enthalpy)
Li (g) + F (g) LiF(s) –1047
+

1
Li(s) + F2(g)  Li F(s) –617
2
Based on data provided, the value of electron gain enthalpy of fluorine would be :
(1) –300 kJ mol–1 (2) –328 kJ mol–1 (3) –350 kJ mol–1 (4) –228 kJ mol–1

e r t s
13. Given :
1 E
x p tskJ mol
[JEE-MAIN (online) 2013]
H (g) +ryO (g)  H O (l)
t2 p e r
s x
–1
Hº
i
(a) ; = –285.9
E
2 2 2 298K

h e m y = – 241.8 kJ mol
;str Hº
C i
1 –1
O (g)  H O (g)
m
(b) H (g) +
2 2 2 298K
2
e
hof water will be :-
The molar enthalpy of vapourisation
C e r ts
xp
–1 –1 –1 –1
(1) 241. 8 kJ mol (2) 527.7 kJ mol (3) 44.1 kJ mol (4) 22.0 kJ mol

The standard enthalpy of formation ( Hº ) for methane, CH t

E
ry74.9 kJ mol .
i s
–1
14. is–
In order to calculate the average energy given out in the formation m
f 298 4

necessary to know which one of thesfollowing? C h e of a C–H bond from this it is

r t
(1) the dissociation energy ofethe hydrogen molecule, H .
[JEE-MAIN(online) 2014]

E xpof H and enthalpy of sublimation of carbon (graphite).

2

tr
(3) the firstsfour yionisation energies of carbon and electron affinity of hydrogen.
(2) the dissociation energy 2

m i s
Ch e
(4) the first four ionisation energies of carbon.
e r t
For complete combustion of ethanol, C H OH(l) + 3OE
p (g) + 3H O(l), the amount
x2CO
15.
of heat produced as measured in bombst
2

i
5
ry is 1364.47 kJ mol at 25ºC.
(g)2 2 2
–1

m  H, for the raction will be :-

calorimeter,

h e
Assuming ideality the Enthalpy of combustion,
C ts
r
c

e
–1

p
(R = 8.314 kJ mol ) [JEE-MAIN 2014]
(1) –1460.50 kj mol –1
(2) – 1350.50 kJ mol –1
E x
(3) – 1366.95 kJ mol –1
(4) – 1361.95 kJ mol –1

s t r y
t s m i
e r and ethane are 360CkJ/mol h e
p
16. The heat of atomisation of methane and 620 kJ/mol, respectively.

E x light capable of breaking the C–C bond is :

try= 6.02 × 10 , h = 6.62 × 10 J s)
The longest wavelength of
s
(Avogadroinumber 23 –34

m× 10 nm (2) 1.49 × 10 nm (3) 2.49 × 10 nm (4) 2.48 × 10 nm

[JEE-MAIN (Online) 2015]

C h
(1) e
2.48 3 3 4 4

62
 Thermochemistry
17. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol–1,
respectively. The heat of formation (in kJ) of carbon monoxide per mole is :

e r ts er ts
[JEE-MAIN 2016]
(1) 676.5
Ex p (2) – 676.5 (3) –110.5
xp
(4) 110.5
E
Given st ry st r y
18.
i
C m + O (g) CO (g) ; H°m
e
i
Ch e (graphite)
1
2 2
Ch = – 393.5 kJ mol
r
–1

H2(g) + O2(g)  H2O (l) ; rH° = – 285.8 kJ mol–1

2
CO2 (g) + 2H2O (l)  CH4 (g) + 2O2 (g) ; rH° = + 890.3 kJ mol–1
Based on the above thermochemical equations, the value of rH° at 298 K for the reaction
C(graphite) + 2H2(g)  CH4 (g) will be: [JEE-MAIN 2017]
(1) +74.8 kJ mol –1

e r ts
(2) +144.0 kJ mol –1
(3) –74.8 kJ mol –1
(4) –144.0 kJ mol–1

E xp(l) gives CO (g) and H O (l). Givenrtthats heat of combustion of

try volume is – 3263.9 kJ mol at 25ºExC p; heat e of combustion (in kJ mol )
19. The combustion of benzene
s
2 2

i
m at constant pressure will be : (R = 8.314
benzene at constant –1

yJK mol )
–1

h e
of benzene
C(1) – 3267.6 st r
i(3) –452. 6
–1 –1
[JEE-MAIN 2018]
(2) 4152 . 6
em (4) 3260

Ch e r ts
xp
20.
E
i s try
h em
e r ts C
E xp
s tr y
m i s
h e
C Based on the above thermochemical equations, find out which e r t
E xp one of the following algebraic
relationships is correct ?
i s try [JEE-MAIN 2019 (Jan.)]
(2) y = 2z–x em (3) z = x + z
(1) x = y–z
C h (4) x = y + y
r ts
Enthalpy of sublimation of iodine is 24 cal g at 200ºC. If specific heat of I (s) andxIp e
E
–1
21. (vap) are
y
2 2
–1 –1

i s t r
0.055 and 0.031 cal g K respectively, then enthalpy of sublimation of iodine at 250ºC in cal

s m
–1

(2) 22.8 rt
g is: [JEE-MAIN 2019 (Apr.)]

e C h e
xp
(1) 2.85 (3) 11.4 (4) 5.7

E
ry for Br is x kJ/mol and bond enthalpy for Br is y kJ/mol, the
If enthalpy oftatomisation
22.
m is 2(l) 2

e
C(1)his x = y
relation between them :
(2) is x > y (3) does not exist
[Jee Main (Jan. 2020)]
(4) is x < y
63
 Thermochemistry

23. The standard heat of formation   ƒ H0298  of ethane (in kJ/mol), if the heat of combustion of

r t s r ts
ethane, hydrogen and graphite are –1560, –393.5 and –286kJ/mol, respectively is _________.
e eMain (Jan. 2020)]
Exp E x p
[Jee

s r y
t and enthalpy of solution of NaCl are 788
s r y
tkJ mol and 4 kJ mol , respectively.
m i m i
e e
–1 –1
24. Lattice enthalpy
h
C The hydration enthalpy of NaCl is : C h [Jee-Main (Sep) 2020]
(1) 784 kJ mol–1 (2) –780 kJ mol–1 (3) –784 kJ mol–1 (4) 780 kJ mol–1

25. The heat of combustion of ethanol into carbon dioxids and water is –327 kcal at constant

e r ts
xp
pressure. The heat evolved (in cal) at constant volume and 27ºC (if all gases behave ideally) is
–1
E–1
r t s
try e
(R = 2 cal mol K ) ________. [Jee-Main (Sep) 2020]

is Ex p
e m try
Ch m is
h e
C e r ts
E xp
i stry
h e m
e r t s C
E xp
s tr y
m i s
Ch e e r t
E xp
i stry
h e m
C e r ts
E xp
s t ry
ts m i
e r C he
E x p
s tr y
m i
C h e
64
 Thermochemistry

EXERCISE # (JEE-ADVANCED)
1.
r t s r ts
Estimate the average S–F bond enthalpy in SF6. The H°f values of SF6 (g), S(g), and F (g) are
erespectively. e
E x p
–1100 , 275 and 80 kJ/mol
Exp [JEE 1999]

s r y
tthe following is not an endothermic reaction?istry
Whichiof
2.
he m h e m
C (A) Combustion of methane
(B) Decomposition of water
C
(C) Dehydrogenation of ethene to acetylene
(D) Conversion of graphite to diamond [JEE 1999]

3.
e r t s
Diborane is a potential rocket fuel which undergoes combustion according to the reaction,
B H (g) + 3O (g) B Op(s) + 3H O(g)
2 6
E2
xcalculate the enthalpy change for the combustion
2 3

r ts of diborane :
2

s tr3
From the following ydata,
x p e
m i y E
C h e 2B(s) + O (g) B O (s) ;
2
2

is t r
H = –1273
2 kJ 3

m
Che; H = –286 kJ ts
1
H (g) + O (g) H O(l)
r
2 2 2
2
xp e
H O(l) H O(g) ; H = 44 kJ
E
try [JEE 2000]
2 2

2B(s) + 3H (g) B H (g) ; 2 H = 36 kJ

2 6

m is
H° for CO (g), CO(g) and HtO(g) s C h e
r
–l
are – 393.5, –110.5 and –241.8 kJ mo respectively.
e(in kJ) for the reaction
4. f 2 2

E x p
The standard enthalpy change [JEE 2000]

t ry CO (g) + H (g) CO(g) + H O (g) is

(A) 524.1is
2 2 2

h e m (B) 41.2 (C) –262.5

r t s
(D) – 41.2

C Which of the following reactions defines H° ? xp e

5. E
ryH2(g) + 1/2 F2(g)  HF(g)
t1/2
f

(A) C + O (g) CO (g) i s

m (D) CO(g) + 1/2O (g)  CO (g) [JEE 2003]s
(B)
e
(diamond) 2 2

(C) N (g) + 3H (g) 2NH

2 2
C h 3 2 2
r t
xp e
r y E
In a constant volume calorimeter, 3.5 g of a gas with molecular weights28
i t
s m
6. was burnt in excess

e
oxygen at 298.0 K. The temperaturet e
r process. Given that theChheat capacity of the calorimeter is
of the calorimeter was found to increase from 298.0 K to

E x p
298.45 K due to the combustion

try value for the enthalpy of combustion of the gas in kJ mol [JEE
–1 –1

is
2.5 kJ K , the numerical

m
is

Ch e 2009]

65
 Thermochemistry
7. Using the data provided, calculate the multiple bond energy (kJ mol –1) of a C C bond in
C2H2. That energy is (take the bond energy of a C–H bond as 350 kJ mol–1.)

er ts er ts [JEE 2012]

p p
–1
2 C(s) + H (g)  C H (g) H = 225 kJ mol
x x
2 2 2

E2C(g) H = 1410 kJ mol E

r y
2 C(s) 
t s t ry –1

i2sC(s)  2C(g) i kJ mol

m m
–1
H = 1410

Che H (g)  2H(g)

2
e
ChH = 330 kJ mol –1

(A) 1165 (B) 837 (C) 865 (D) 815

8. The standard enthalpies of formation of CO2(g), H2O(l) and glucose(s) at 25ºC are

r t s
–400 kJ/mol, –300 kJ/mol and –1300 kJ/mol, respectively. The standard enthalpy of
e
E x p
combustion per gram of glucose at 25ºC is
t s [JEE (Advanced)2013]
(A) +2900 kJ ry (B) – 2900 kJ
p e r
ist x
(C) –16.11 kJ (D) + 16.11 kJ

m y E
he the reaction(s) from the following options,
9. CChoose i str for which the standard enthalpy of reaction
is equal to the standard enthalpy ofh
e m [JEE (Advanced)2019] s
C formation.
e r t
(A) 2H (g) + O (g)  2H O(l)
2 2 2 (B) 2C(g) + 3H (g)  C H (g)
E2
xp 2 6

s tr y
i
1 3
(C) S (s) + O (g)  SO (g) (D) O (g)  O (g)
m
8 2 2 2 3
8

s
2

C h e
10.
r
Tin is obtained from cassiterite by
the minimum temperaturep
t
(ineK) at which the reduction of cassiterite by coke would take place.
reduction with coke. Use the data given below to determine

x
E(s)) = –581.0 kJ mol ,  H°(CO (g)) = –394.0 kJ mol
r y
t = 56.0 J K mol , S°(Sn(s)) = 52.0 J K mol ,
At 298 K :  H°(SnO
s
–1 –1

S° : (SnOi(s))
f 2 f 2

m s
–1 –1 –1 –1

e t
[JEE (Advanced)2020]
: (C(s)) = 6.0 J K mol , S°(CO (g)) = 210.0 J K mol . er
ChS°Assume
2

xpindependent.
–1 –1 –1 –1
2

E
try
that the enthalpies and the entropies are temperature

m i s
C h e ts
e r
E xp
s tr y
t s m i
e r C h e
E x p
s t r y
m i
C h e
66
 Thermochemistry

ANSWER KEY

er ts EXERCISE # (JEE - MAIN)

er ts
xp x p
E6. (1) 7.
y(3)E 3. y
1. (2) 2.
(4) i9.
tr
s (3) 10. (4)
(3) 4. (1) 5.
i s r
t (2) 13. (3) 14.
(4) (2)
8.
15.
m
Che(3) 16. (2) 17. (3)
11.
18. Ch
em19. (1) 20. (4) 21.
(4)
(3)
12. (2)
(2)
22. (2) 23. –192.50 24. (3) 25. (326400) NTA Ans. (–326400.00)

EXERCISE # (JEE-ADVANCED)

er ts3. –2035kJ mol 4. (B) –1

xp 8. (C)
1. 309.16kJ/mol 2. (A) 5. (B)

y E er ts
tr
6. (9) 7. (D) 9. (CD) 10. 935.00

is Exp
h em t r y
C m is
Ch e
er ts
Exp
istry
hem
er ts C
Exp
stry
mi
Che er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
67
 Thermochemistry

HINT AND SOLTUIONS

EXERCISE # JEE-MAIN
r ts
rH = C – C + H – H – C – C – 2 C – H
e er ts
p p
1.

E x
= 615 + 435 – 347 – 2 × 414= – 125 kJ
Ex
s r y
t s) + O (g)  CO (g) stry
2. i
m= – 393.5
C (graphite,
mi
e e
2 2

h rH
C CO(g) + O (g)  CO (g)
1
2 2
Ch
2
rH = – 283 kJ
– 283 = – 393.5 – Hƒ CO(g)
Hƒ CO(g) = – 110.5 kJ

1 1
er ts
xp
3. X2(g) + Y2(g)  XY(g)
2
y E2
er ts
tr p
1 1
rH =
mis x
X – X + Y – Y – X – Y
E
y
2 2

Ch e 1 1
i
– 200 = × a + × 0.5a – astr
2 2
e m
A= = 800
X–X
Ch er ts
Exp
try
1 1 rH1
4. I2(s) + Cl2(g)   ICl(g)
2 2
mis
 62.76/2 0
s
0

Che
1
I2(g) +
1
er t
Cl2(g) 
rH 2
 ICl(g)
2
Exp2
62.76
rH2 +
stry = rH1
i
2

em 1 1
r ts
rH2 = × 151 + × 242.3 – 211.3 = 196.65 – 211.3 = – 14.65
h
C 2 2
xpe
62.76
E
try
rH1 = – 14.65 + = 16.73 kJ/mol
2
is
C (graphite) + 2H (g)  CH (g) em
Ch ts
5.
r
2 4

xpe
6. rH =
1
× 240 – 349 – 381= – 610 kJ/mol
ry E
2
ist
ts m
7. rGº = – 394.4 – 2 × 237.2 + 166.2

er
= – 702.6 kJ/mol
Che
xp
= W non – PV
E
try
H = – 726 kJ/mol = q

mis
465.4
 100  97%

Che 726

68
 Thermochemistry

8. 57.32 = Hƒ OH– (aq) – Hƒ H2O()

r ts
57.32 = Hƒ OH– (aq) + 286.2
ekJ er ts
E x
–
p
H OH (aq) = – 228.88
Exp
y y
ƒ

i s tr istr
1m
9. he N (g) + H (g)  NH (g)
3
hem
C 2 2
2 2 3
C
– 46 =
3 1
× 436 + × 712 – 3 N – H
2 2

3 N – H = 1056   = 352 kJ mol–1

ts
N–H

p e r
Ex2N O (g) r ts
y e
111
4NO (g) + O (g) 
tr p
10.
rH is x
2 2 2 5

e m 2N O (s) 2×54 ry E
C h ist
m
2 5

ChkJe
er ts
xp
rH + 2 × 54 = – 111rH = – 219
E
istry
11. – 51.46 = – 55.90 + H ion
hem
t s
H ion. = + 4.44 kJ mol–1
e r C
xp
Li(s) + sFtr
y E  LiF(s)
i2
1 617
12. (g) 
m ts
2

e
Ch 161  77 er
Exp
Li(g) F(g) –1047
istry
 520  egH
hem
Li+(g) + F–(g) C er ts
Exp
stry
161 + 520 + 77 + egH F(g) – 1047 = – 617
ts mi
egH F(g) = –328 kJ/mol
e r Che
E xp
s y
trO(g)
13. H O() 
m i H
e
2 2

h
CrH = b – a = – 241.8 + 285.9 = + 44.1 kJ
69
 Thermochemistry
14. C (graphite) + 2H2(g)  CH4(g)

e r s
rH = H sub. C(graphite) + 2 H – H – 4 C – H
t er ts
x p
E(g)  2CO (g) + 3H O() Exp
st r y stry
15.
m
2
i
C H OH()5+ 3O 2

mi 2 2

C heU = – 1364.47 kJ/mol

C h e
H = U + ngRT
1 8.314  298
= – 1364.47 – = – 1366.95 kJ/mol
1000

16. 4 C – H = 360 kJ
er ts
 = 90 kJ/mol Exp s
C–H

r y er t
 + ist = 620 Exp
he m C–C C–H

try
C = 80 kJ/mol = ev / bond mi
80 s
he
C–C

C ts
96.5

er
1240
 =  96.5 nm = 1.493 × 03 nm
Exp
try
80

mis
17. (i) C (graphite) + O2(g)  CO2(g)
s Che
r t
H = – 393.5 kJ mol–1
e
x p
CO(g) + OE(g)  CO (g)
y2
1
(ii)
is t r 2 2

e m r ts
Ch
H = – 283.5 kJ/mol

xpe
1
(iii) C (graphite) + O (g)  CO(g)
ry E
t
2

s
2

m i
(iii) = (i) – (ii)
he
C kJ/mol ts
rH = – 393.5 + 283.5 = –110.0
er
Exp
18. C (graphite) + 2H2(g)  CH4(g)
stry
rH = Hƒ CH4(g)
t s mi
890.3 = H CH (g) – H pe r Che
Ex
ƒ CO (g) – 2 H H O()
4 ƒ 2 ƒ 2

ry
t 393.5 + 2 × 285.8
890.3 = H sCH
i (g) +
=m
ƒ 4

h
rHe
C H CH (g) = – 74.8 kJ/mol
ƒ 4

70
 Thermochemistry

19. C6H6() + 7.5 O2(g)  6CO2(g) + 3H2O()

ng = – 1.5
e r t s er ts
H = U + ngRT xp
E Exp
s r y
t – 1000 = –3267.6 kJ ist
H = –i3263.9
1.5  8.314  298 ry
he m hem
C C
20. (i) C (graphite) + O2(g)  CO2(g)
rHº = x kJ/mol
1
ts
(ii) C (graphite) + O2(g)  CO(g)
2
e r
E xp= y kJ/mol
rHº
r ts
s y
t+r2 O (g)  CO (g) xpe
m
(iii) CO(g) i 1

y E
e r
2 2

C h ist
rHº = 2 kJ/mol
e m
(i) = (ii) + (iii) x = y + z Ch er ts
Exp
try
21. I2(s)  I2(g)
( Cp)r = 0.031 – 0.055 = – 0.024 cal g–1 k–1
mis
s Che
e r t
rH 523 k – rH 473 kx =p
rH 523 k –t y
24r=
E – 0.024 × (523 – 473)

m iks= 22.8 cal g

– 0.024 × 50

Che
rH 523 –1

er ts
Exp
22. [2]
istry
Sol. Br2(l)  2Br(g) , Hatomisation
hem
Hatomisation = Hvap + HBE
C er ts
Therefore x > y
Exp
stry
ts mi
23. [–192.50]
er Che
Sol.
E xp
2C(s) + 3H2(g)  C2H6(g)

try + 3×(–393.5) – (–1560)

Hreaction = HC – HC
s
=i2×(–286)
R P

hem= –192.5 kJ/mole

C
71
 Thermochemistry
24. (3)

s s
+4kJ
t t
Sol. NaCl(s) NaCl(aq)

p r
eH per
+788 kJ
x
E(g) Ex
r y –

ry
+ hyd.

t t
Na (g) + Cl
4 = 788is
m + H
mis
he hyd.

C H = 4 – 788 = –784 kJ / mol

hyd
–1
Che

25. (326400)
NTA Ans. (–326400.00)

e
C2H5OH ( ) + 3O2(g) r ts
 2CO2(g) + 3H2O ( )
xp
Sol.

y E er ts
tr
 n = 2 – 3 = –1

 H =  Ui+s(n ) RT
g

Exp

h
c
e m c g
try
 C H =  U – RT mis
c c

Ch e
  U =  H + RT
er ts
xp
c c

= –327 × 103 + 2 × 300

E
= –326400 cal.
istry
hem
 
r ts
Heat evolved
e C
= 326400 cal.
Exp
s t ry
m i
Ch e er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
72
 Thermochemistry

JEE ADVANCED
1. S(s) +
r t
e 0s 1100
3F2(g)   SF6(g)
er ts
 275  6×80
x p
E SF (g) Exp
st r
S(g) + 6F(g)y stry
i i
6

he m = 275 + 6 × 80 – 6 
– 1100
hem
C
S–F
C
6 S – F = 275 – 6 × 80 + 1100

S – F = 309.16 kJ/mol

e r ts
xp
2. Combination is exothermic reaction

y E er ts
rH = H iBs tOr(s) + 3H H O(g) – H B H (g) Exp
m
3.
y
ƒ ƒ ƒ

e
2 3 2 2 6

h
C44 = H H O(g) + 286
Hƒ B O (s) = – 1273 kJ
ist r
m
2 3

h e
C ts
ƒ

r
2

H H O(g) = – 242 kJ
ƒ
xpe
E
2

try
Hƒ B2H6 = 36 kJ
rH = – 1273 – 3 × 242 – 36= – 2035 kJ/mol
mis
s Che
e r t
rH = H CO(g) + Hxp
4.
r y
ƒ
E+ 393.5 = 41.2 kJ/mol
H O(g) – H CO (g)
ƒ 2 ƒ 2

ist
= – 110.5 – 241.8

h e m r ts
C xpe
5. Refer notes
E
istry
h e m
ts
6. 9 = 2.5 × 0.45 kJ
C er
xp
2.5  0.45
H =   28 = – 9 kJ/mol
3.5
ry E
ist
2C(s) + H (g)  C H (g) rtsH = 225 kJ /mol em
7.
x p e 2 2
C
2
h
330 E  0
try C H (g)
1410
s
2C(g) + i2H(g)
m
e
2 2

C h
73
 Thermochemistry

225 = 1410 + 330 – 2 × C – H – C  C

r t s
225 = 1740 – 2 × 350 – C  C
e er ts
 = 1740 – 700 x p
E – 225 = + 815 kJ Exp
CC

s t ry stry
m i mi
he
8.C C H O (s) + 6O (g)  6CO (g) + 6HC
6 12 6 2
h
O()
e 2 2

rH = – 6 × 400 – 6 × 30 + 1300

= – 2700 kJ/mol

ts
2900
=  kJ (per gram) = – 16.11 kJ
e
180r
Exp r ts
Refer notes stry xpe
9.
m i y E
h e str
10. C(935.00) mi
Sol. SnO + C  Sn + CO Ch
e
er ts
xp
2(s) (s) (s) 2(g)

H0reaction  Hf0 (CO2 (g)) –  Hf0 (SnO2,S) E

istry
= –394.0 – [–581.0]
hem
= 187 KJ
r ts
e(g)) – S (SnO ,(s) – S (Cs)) C
S o

E x
0
p
= S (Sn(s)) + S (CO 0
2
0
2
0

y
reaction

= (52 + 210)t–r(56
m is + 6)
s
h e
= 200 J
C G  H – TS er t
E xp
i s try
m
For reaction to be spontaneous
G° < 0
C h e ts
er
H° – TS° < 0
Exp
187 × 1000 – T × 200 < 0
stry
ts mi
T  935K
er Che
Exp
istry
hem
C
74
 Radioactivity

EXERCISE # (JEE-ADVANCED)
1.
ts ts
The nucleidic ratio 13 H to 11H in a sample of water is 8.0 × 10–18 : 1 Tritium undergoes decay
r r
e g of such a sample
with a half-life period pof e
12.3 years. How many tritium atoms wouldp
E x Ex 10.0

st r y stry
i i
contain 40 years after the original sample is collected. [JEE-1992]

e m e m
2.Ch One of the hazards of nuclear explosion Chis the generation of Sr and its subsequent
90

incorporation in bones. This nucleide has a half-life of 28.1 years. Suppose one microgram was
absorbed by a new-born child, how much 90Sr will remain in his bones after 20 years.
[JEE-1995]

e r ts
Al is a stable isotope xAl
E pis expected to disintegrate by : ts
r(D) proton emission
27 29
3. [JEE-1996]
r y (B)  emission (C) positron emission e
13 13

is
(A)  emission t E x p
m y
ChAce has a half-life of 22.0 year withm i str
227

h e
ts
4. respect to radioactive decay. The decay follows two
parallel paths, one leading to CTh and the other to Fr. The percentage yields of these two r
e
227 227

E xforpeach of
try [JEE-1996]
daughter nucleides are 2.0 and 98.0 respectively. What are the decay constants ()
the separate paths ?
m i s
s C h e
e r t
5.
x p
Write a balanced equation for
E
the reaction of N with -particles.
14
[JEE-1997]

s tr y
m i s
6.
Ch e e r t [JEE-1998]

E xp
i s ry is the correct explanation of the assertion
treason
e m
(A) if both assertion and reason are correct and
h
(B) if both assertion and reason Care correct, but reason in not the correct explanationeofrthets
assertion
E xp
s t r y
(C) if assertion is correct but reason is incorrect

ts m i
e r
(D) if assertion is incorrect but reason is correct
C h e
x p
E is observed during
t r y
is
7. Decrease in atomic number [JEE-1998]

e m
(A) alpha emission (B) beta emission
C(C)h positron emission (D) electron capture
75
 Radioactivity
139 94
8. The number of neutrons accompanying the formation of 54X and 38Sr from the absorption
of slow neutron by 92U235 followed by nuclear fision is
s s
[JEE 1999]
(B) 2 rt (D) 3 ert
(A) 0
x p e (C) 1
xp
r E
y stable isotope of Na. Find the process sbytwhich
r E
y Na can undergo radioactive
i st i
m m
23 24
9. Na is the most
e
Ch decay:
11

Ch e [JEE 2000]
11

(A) ¯ -emission (B) -emission (C) + -emission (D)K-electron capture

10. 64
Cu (half-life = 12.8 hr) decays by  – emission (38%),  + emission (19%) and electron capture

e r ts
(43%). Write the decay product and calculate partial half-lives for each of the decay processes.

E x p ts [JEE 2002]

r y p e r
m istsample emits n b-particles in 2 sec. InynextEx2 sec it emits 0.75 n b-particles, what
Cishtheemean life of the sample? tr
11. A radioactive

m is
e
[JEE 2003]

Ch e r ts
[JEEp
12. Fill in the blanks
E x 2005]
(a) 235
U  n 
1 137
 A  B  _____________
97

is try
m
92 0 52 40

Se 
s
 2 e  _____________
C h e
t
82 0
(b)
r
34 –1

x p e
ry E
t
s procedure is based on the formation of C by neutron
Question No. 13
iThe
to 15 (3 questions) Carbon 14 is used to determine the age of orgainc

e m
material.
r t s 14
capture in the upper
Chatmosphere. x p e
N + n  C y E
tr
14 1 14 1

s
+ H
i
7 0 6 1
14
e m 14

Chdies, the uptake of carbon dioxide by it ceases and theelevel

C is absorbed by living organisms during photosynthesis. The C content is constant in living
organism once the plant or animal r ts
E14
xp
y
of 14C in the dead being falls due to the decay which C undergoes.
C  N + e° 14 14
i s tr
s m
–1

t
6 7
14
e r years. The decay constantC h e
p
The half life period of C is 5770 () can be calculated by using the

following formulay =E

x
tr t
0.693

m i s 1/2

C h e
76
 Radioactivity
The comparison of the – activity of the dead matter with that of carbon still in circulation

e r s er ts
enables measurement of the period of the isolation of the material from the living cycle. The
t
x p xp
method however, ceases to be accurate over periods longer than 30,000 years. The proportion
E matter is 1 : 10 E
r y ry
14 12 12
of C to C in living [JEE 2006]
i s t ist
m
Which of the following option is correct ? he
13. he
m
C (A) In living organisms, circulation of
C [JEE 2006]
14
C from atmosphere is high so the carbon content is
constant in organism
(B) Carbon dating can be used to find out the age of earth crust and rocks

ts
(C) Radioactive absorption due to cosmic radiation is equal to the rate of radioactive decay,
e r
xbepused to determine concentration of rCtinsdead beings.
hence the carbon content remains constant in living organism
E
try e 14

p
(D) Carbon dating cannot

m is x
E of its age?
h e s tr y
C(A) 6 years i(B) 6000 years
14. What should be the age of fossil for meaningful determination [JEE 2006]

e m
(C) 60000 years Ch (D) it can be used to calculate any age erts
E x p
A nuclear explosion has taken place leading to increase in concentration of C yin nearby areas.
trage of the fossil is
14

s
15.

m i
e
14
C concentration is C in nearby areas and C in areas far away. If the
h
1 2

r t s respectively, then C
eincrease at the place where explosion has taken place and
determined to be t and t at the places [JEE 2006]
p
1 2

E x
(A) The age of the fossil will

t –t = ilnst
1 C r y
m s
1

e t
1 2
 C
h e r
C (B) The age of the fossil will decrease at the place where explosion
2

E xp has taken place and

1 C
t – t = ln i s t ry
m
1

e
1 2
 C
h
C to be the same ts
2

e r
xp
(C) The age of fossil will be determined
t C
r y E

t
1 1
(D)
t C
s m i s
t
2 2

e r. The ratio of the atomic

C e
hmass and atomic number of the
16.
E
A positron is emitted fromx p Na 23

y
11

is t r
resulting nuclide is [JEE 2006]
(A) e
h m
C
22/10 (B) 22/11 (C) 23/10 (D) 23/12

77
 Radioactivity
214
17. The total number of a and b particles emitted in the nuclear reaction 238
92 U 
82 Pb is.

er t s e r t s [JEE 2009]

E x p xp
Enuclear fission to Xe and
st y
The numberrof 235

s tr y 142

i i
18. neutrons emitted when U undergoes controlled
92 54

he mis -
90

h e m
C C
Sr
38 [JEE 2010]

19. Bombardment of aluminium by a-particle leads to its artificial disintegration in two ways, (i)
and (ii) as shown. Products X, Y and Z respectively are : [JEE 2011]

er ts
E xp r t s
s tr y x p e
i
m neutron, positron E
y positron, proton
h e
C(C) proton, positron, neutron
(A) proton,
s r
(B)tneutron,
i(D) positron, proton, neutron
e m
Ch e r ts
The periodic table consists of 18 groups. An isotope of copper, on bombardment E xpprotons,
20.

s y , element X
trgroup
with

m
undergoes a nuclear reaction yielding element X as shown below. To which
i
s C h e
t
belongs in the periodic table ? [JEE 2012]
eCur H 
E x p 63
29 6 n    2 H  X
1
1
1
0
1
1

ry
In them isttransmutation s
21.
e nuclear
ChBe  X  Be  Y e r t [JEE-2013]
9 8

E x p
y
4

r
4

(X, Y) is(are)
m i st
(A) (, n)
C
(B) (p, D)
h e (C) (n, D) (D) ( , D)
ts
p e r
E xConsidering
22. 238

s t
A closed vessel with rigid walls contains 1 mol of U and 1 mol of air at 298
r y K.
i
92

complete decay of 238

U to
e r s
P b,tthe
206
ratio of the final pressurem
h e to the initial pressure of the
p C
92 82

system at 298 K is -
E x [JEE-2015]

is try
h e m
C
78
 Radioactivity
23. STATEMENT-1 : The plot of atomic number (y-axis) versus number of neutrons (x-axis) for

s s
stable nuclei shows a curvature towards x-axis from the line of 45° slope as the atomic number
r t r t
is increased. and
STATEMENT-2E :x
pe tox
Proton-proton electrostatic repulsions beginE
pe
s tr y and neutrons in heavier nuclides. stry overcome attractive forces

m i
involving protons i
mis True ; STATEMENT-2 is a correct
[JEE 2008]

Che(A) STATEMENT-1 is True, STATEMENT-2

C h e
explanation for STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct
explanation for STATEMENT-1

ts
(C) STATEMENT-1 is True, STATEMENT-2 is False
e r
xp
(D) STATEMENT-1 is False, STATEMENT-2 is True

y E e r t s
is tr E xp
m y
Che
24. In the decay sequence, [JEE-2019]

i s tr
h e m
C emitted by the respective isotopes. The correct option(s)
e r ts
xp
x , x , x and x are particles/radiation
1 2 3 4

E
try
is(are) :
(A) x will deflect towards negatively charged plate
1
m is
(B) x is  

s C h e
r t
2

(C) x is –ray
xp e
E
3

tr y
(D) Z is an isotope
s
of uranium

m i s
h e e r t
25. C U is known to undergo radioactive decay to form Pb by
238

E xpemitting alpha and beta particles.

206

Ify
92 82

Ut. r
–6
A rock initially contained 68 × 10 g of
m is 238
92
the number of alpha particles that it would

C h e 18

ts
r
238 206
emit during its radioactive decay of U to Pb in three half-lives is Z × 10 , then what is
e
92 82

the value of Z ?
E xp
[JEE-2020]

s tr y
t s m i
e r C h e
E x p
s t ry
m i
C h e
79
 Radioactivity

ANSWER KEY
EXERCISE # (JEE-ADVANCED)
r ts er ts
pe
Nt = 5.6223 × 106
p
1.
moles of H atomE =x Ex –18

y y
3
10 ×8×10
r
oft H atom = 10 ×8×10 ×6×10 = 4.8×10 str
1

number s
m i 3

m i –18 23 7

e e
1

Ch 40= 12.3 ln 4.8  10 = 5.6×10 Ch

7
5
ln 2 N
 n 2
 20
28.1
2. Wt = 1 × e = 0.610 m gram

3. (B)
er ts

E x p ts 227

r
Th
y
1

4. Ac
r
ist Fr
227

xpe
em 

ry E 223

h
C  = 2 and ln 2  22 mi st
Che ts
1
  100
1  
2 1 2

er
2 ln 2 ln 2
Exp
try
1 =    6.3  104
100 22 11 100

mis
2 =
98
and 1 = 3.087 × 10–2
s Che
2
er t
E x p
s ry
t  F   O  H
m i
N  He
14

 4 18 17 1

ts
5.
e
1 2 9 8 1

h
C (B)
unstable

er
6.
Exp
7. (ACD)
istry
8. (D)
hem
C er ts
xp
9. (A)
10. 64 1
Cu   –1e
0
+ 30Zn64
ry E
st
29

2
Cu  
ts mi
e
0
64
+ 28Ni64
r
+1e

e Ch
29

Cu + e  Ni xp
E
64 0 3 64
–1

y
29 28

n2 r
is=t12.8 hr;
  m
Che

1 2 3

80
 Radioactivity
1 38 n2 12.8
= (t1/2)1 = =  100
1   2   3 100 , 1 38

e r t s er ts
 `2
E
1   2   3x=p 19
(t1/2)2=
n2 12.8
2
=  100
Exp
y y
100 , 19

ist
r istr
hem
 
=
43 3
(t ) =
n2 12.8

= 
h
100
em 1/2 3

C C
1 100 ,
2 3 43 3

11. n= N0[1 – e–2]

1.75 n = N0[1 – e–4]

1.75 =
e ts
(1  e 2  )(1  e 2  )
r = 1 + e–2
xp
2 
1 e

e = 0.75 = ry
E er ts
t4 p
3
s
–2

i
m 1 4 Ex
he stry
C 3
e 2
=
4
  = n
mi
2 3
Ch e
er ts
Exp
try
235 137 97
U + n1  A+ B + 2 n1
s
12. (a) 92 52 40

i
0 0

82
Se  2 e0 + Kr82
hem
s C
(b) 34

t
–1 36

r
xpe(A) 16.
(B) E15.
13. (C) 14.
str y 22. (9) 23. (C) 17. (8) 18. (4) 19. (A)

m i
ts
20. (8) 21. (AB) (A) 24. (ABD) 25. (1.20)

Ch e er
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
81
 Radioactivity

HINT AND SOLUTIONS

6
1. Nt = 5.6223 × 10

e r ts
moles of 1H3 atom = 10 ×8×10–18
er ts
number of H atom x
E =p 3
Exp –18 23 7

y y
10 ×8×10 ×6×10 = 4.8×10
r r
1

12.3 t4.8  10
40= isln
7
ist
he mln 2 N = 5.6×10
h e m 5

C C
 n 2
 20
2. Wt = 1 × e 28.1 = 0.610 m gram

3. (B)
e r ts
n n
E x p ts
  > P
   
P
try
-emission
per
is x
stable

em ry E
Ch ist

m
227

e
Th 1

Ch ts
227
Ac
4.
 223
er
xp
Fr 

E
1 2 ln 2
 22 istry
m
= and
1   2 100 1   2
s Che
2 ln 2
e
ln 2 r t
1 = 
E

x p
100 22 11 100
 6.3  104

s ry
t = 3.087 × 10
 =
98
m i –2

ts
and
e
2 1

h r
2
C xpe
E
5. 14 
N  42 He   18

9 F  8
17
O H
i
1
stry
 unstable 
em
1 1

C h r ts
xpe
E
In Al both neutron and proton are odd in number therefore less stable.try
6. (B)
13
30

s m is
e r t h e
Exp C
ry number increase in all other option it decreases
7. (ACD)

i s
In -emissiontatomic
h e m
C
82
 Radioactivity
8. (D)
+ 0n1  54Xe139 + 38Sr94 + 3 0n1
s s
235
92U

er t er t
Ex p Exp
9. (A)
s ry
t e + Mg stry
m i
Na 
24 0 24
mi
e e
–1 12

h h
11

C n n >  for Na C

P  P stable

1
10. 64
Cu   –1e
0
+ 30Zn64

ts
29

2
Cu  
e r 0
+ 28Ni64
xp
64
+1e

s
29

Cu + e  E r t
64

str y Ni
–1
0 3

xpe 28
64

i
29

e m  = 12.8 hr;
n2
ry E
Ch
   is t
1 2 3

e m
(t ) = Ch ts
 n2 12.8
r
38
 100
e
1
= =
xp
1/2 1
   100 ,  38
E
1 2 3 1

 `2
=
19
(t1/2)2=
n2 12.8
=  100
istry
1   2   3 100 , 2 19
hem
3
e
43
r ts n2 12.8
 100 C
p
= (t1/2)3= =
1   2   3
Ex
100 , 3 43

r y
[1t– e ]
n= Nis
m
–2

ts
11.
e r
0

h
C n = N [1 – e ] e
xp
–4
1.75
E
0

try
(1  e 2  )(1  e 2  )
s
–2
= 1 + e 
1.75 =
1  e 2 
mi
C h e ts
 e–2 = 0.75 =
3
er
4
Exp
4 1 4
stry
e2 =
3
  = n

ts
2 3
mi
er Che
xp
(a) U + n  EA + B + 2 n
y
235 137 97

r
1 1

t
12. 92 52 40

s
0 0

i
m 2 e + Kr
e
82
(b) Se 0 82

h
34
–1

C
36

83
 Radioactivity
15. (A)

s s
1 C1
t1 =

er
n
t 
%C14  er t
Exp fossil

Exp
t = n try
stry
 is % C 
1 C
i
2

m m
2

Che e
14

h
fossil

t1 – t2 =
1 C
n 1
C
 C2

16. (C)
Na  +1e0 + 10Ne23
ts
23

r
11

e
x238p 214 s
17. (8)

y E er t
is tr
Number of -particles = = 6
Exp
h emof -particles = 82 – [92 – 12] = 2 try
4

CNumber
m is
C he r ts
18. (4)
xpe
E
try
92U
235
+ 0n1  142
Xe + 90
Sr + 4 0n1
is
54 38

hem
19. (A)
er ts C
He + Al  Si x +p
E
4 27 30 1
H
y
2 1

r
13 14

s
He + iAl
4 t Si + n 1

m Si + e
27 30

e ts
2 0

r
13 15

Ch e

xp
30 30 0
P
E
15 14 1

i stry
20. (8)
h e m
Cu + H  6 n + He +C
63 1 1 4 1 52
er ts
xp
29 1 2 H + Fe 0 2 1 26

ry E
ist
ts m
21. (AB)

er Che
E x p
(A) 94 Be + 0  0  84 Be + 0n1

try
(B) Be + H  1 2

is
9 8
4 Be + H 1 4 1

m
Che
84
 Radioactivity
22. (9)

s s
238 206
Pb + 82He4 6 –1e0
t t
92U

r r
82

P  1 mol of air
x p e xpe
air +E8 moles of  - particle E
i

P  1 mol of y
str stry
P m9i i
f

he hem
C C
f
=
P i
1

23. (A)

Atomic
e r ts
number
E xp r t s
s tr y x p e
m i y E
h e No. of neutrons

CNote : Neutron increases more than proton s t r

m toi overcome proton-proton repulsion.
Ch e
er ts
24. (ABD)
E xp
x =  ,x = , x = and x =
is try
m
1 2 3 4

s C h e
e r t
25. (1.20)
E x p
 Pby  8   6 
U 
tr
238 206 4 0
92
i s 82 2

mof U present in the rock initially

1

s
e
h mole
C (n ) = 68 10 mole
238

e r t
6

E x p
0
238
is t ry
After 3 half life
h e m
Cn = 7 × n er ts
xp
238
moles of U decayed = (n ) – 0

E
0 3 0
2 8
7  68  10try
s
7
 moles of -particles formed = × n × 8 = 7 × n =
m i s 6

e r t 8
h e 238
0 0

E xp= 7  68 10 × 6 × 10 = C 6

y
 No. of -particles formed 23 18

tr
1.2 × 10

m i s 238

C

h e Z = 1.20

85
 Thermodynamic

EXERCISE-(JEE-MAIN)
s s
1. The internal energy change when a system goes from state A to B is 40 kJ/mole. If the system
r t
e energy ? r t
e[AIEEE-2003]
p p
goes from A to B by a reversible path and returns to state A by an irreversible path what would
be the net change in x
E (2) Zero E x
(1) < 40 kJtry (3) 40 kJ try (4) > 40 kJ
internal

m isthe reaction : N + 3H 2NH carriedmoutisat constant temperature and pressure, if

Che Che
2. Consider 2 2 3

H and U are the enthalpy and internal energy changes for the reaction, which of the
following expressions is true ? [AIEEE-2005]
(1) H = U (2) H = 0 (3) H > U (4) H < U
3. An ideal gas is allowed to expand both adiabatic reversibly and adiabatic irreversibly. If T i is

e r t s
the initial temperature and T f is the final temperature, which of the following statements is
correct :-
xp
E process but T = T for irreversible process t s [AIEEE-2006]

r y p e r
st) x
(1) T > T for reversible
(2) (T ) =i(T
f i f i

m y E
C(3)hTe= T for both reversible and irreversible tr
f rev f irrev

m i sprocesses
e
f i

C h s
oft
(4) (T ) > (T )
r
f irrev f rev

4.
xp of
Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol e
y E
water at 1 bar and 373 K = 41 kJ mol and R = 8.3 J mol K will be)i:-str
water is vapourised at 1 bar pressure and 100°C, (Given : Molar enthalpy of vapourisation
–1 –1 –1

(2) 3.7904 kJ mol em

[AIEEE-2007]
(1) 4.100 kJ mol
r ts
–1

C h –1

(3) 37.904 kJ mol

xp e –1
(4) 41.00 kJ mol –1

5.
r y
The value of enthalpyE change (H) for the reaction
C H OH is+t3O  2CO + 3H O

h e
2
m 5 () 2(g) 2(g) 2

r t s
()

C temperature will be :- –1

xp
at 27°C is –1366.5 kJ mol . The value of internal energy changee for the above reaction at this

y
r kJ E [AIEEE-2011]

i s t–1369.0
m (4) –1361.5 kJ
(1) –1371.5 kJ (2)
(3) –1364.0 kJ
C h e ts
e r
6.
E xp 2012]
The difference between the reaction enthalpy change ( H) and reaction internal energy change r

( U) for the reaction :

s t
[JEE MAIN
r y (online)-
iJ mol K )
r

2C H () + 15O (g)  12CO (g) +s6H O () at 300 K is (R = 8.314 m

t e
–1 –1
6 6

p e r 2 2

C h
2

(1) 0 J mol
E x –1
(2) 2490 J mol –1

s t r y –1 –1

m i
(3) –2490 J mol (4) –7482 J mol

C h e
86
 Thermodynamic
7. Which of the following statements/relationships is not correct in thermodynamic changes ?

(1) q = –nRT n
V2
r t s r t s
(isothermal reversible expansion of an ideal gas)[JEE MAIN (online)- 2014]
e e
p p
V1
x x
Eto internal energy.
(2) For a system atEconstant volume, heat involved merelv changes
r y t r y
(3)m
ist V (isothermal reversible expansion m is
Che w = –nRT ln
V
2

1
Ch e of an ideal gas)

(4) U = 0 (isothermal reversible expansion of a gas)

8. If 100 mole of H2O2 decompose at 1 bar and 300K, the work done (kJ) by one mole of O2(g) as
it expands against 1 bar pressure is : [JeeMain(online) 2016]

ts
 2H2O(l) + O2(g) (R = 8.3 J K mol )–1 –1
2H2O2(l) 

p e r
(2)x249.00 (4)s62.25
(1) 498.00
E (3) 124.50
rt [JEE MAIN–2017]
U is equal tot: ry p e
9.
m is E x
h e st r y
CFor a reaction, A(g)  A(l) ; H = –3RT.mThei correct statement for the reaction is :
(1) Adiabatic work (2) Isothermal work (3) Isochoric work (4) Isobaric work

Che ts
10.

p e r
[Jee Main(online) 2017]
(4) H = U =E 0x
(1) |H| > |U| (2) H = U  0 (3) |H| < |U|
s y work done by
trand
11.
m i
A gas undergoes change from A to state B. In this process, the heat absorbed
the gas is 5J and 8 J, respectively. Now gas is brought back h to e
e r t s C A by another process of during

x p
which 3 J of heat is evolve. In this reverse process of B to A :-
Ewill be done by the surrounding on gas.
[Jee Main(online) 2017]

r y
twork will be done by the surrounding on gas.
(1) 10 J of the work
s
(2) 6 J ofithe
h e mJ of the work will be done by the gas. r t s
C (3) 10
xp e
E
trinyfigure.
(4) 6 J of the work will be done by the gas.

m i s
he
12. An ideal gas undergoes a cyclic process as shown [Jee Main(online) 2018]
U = –5 kJ mol , q = 2 kJC
–1
mol –1

e r ts
xp
BC AB
A
E
–1 –1
W = –5 kJ mol , W = 3 kJ mol B

y
AB CA

Heat absorbed by the system during process CA is :-

i
P
s t r
–1

e r t s –1
h e m C

C
(1) 18 kJ mol (2) +5 kJ mol
p
V

(3) –5 kJ mol –1
E x –1
(4) –18 kJ mol

s t ry
m i
C h e
87
 Thermodynamic
13. Consider the reversible isothermal expansion of an ideal gas in a closed system at two different

s s
temperatures T1 and T2 (T1 < T2). The correct graphical depiction of the dependence of work

er t er t
Exp
done (w) on the final volume (V) is:
Exp [Jee-Main (Jan.) 2019]

stry stry
(1)m
i (2)em
i
Che Ch

ts
(3) (4)

e r
E xp r t s
s tr y p e
i undergoes isothermal compression from E 5 mx to 1 m against a constant external
e m yused to increase the temperature of 1 mole
3 3

r
14. An ideal gas

C h –2
i st
m
pressure of 4 Nm . Heat released in this process is
of Al. If molar heat capacity of Al h e
C is 24 J mol K , the temperature of Al[Jee-Main
–1 –1
s
increases by :
er t
E xp2019]
(Jan.)

3
(4) isKtr
2 y
m
(1) K (2) 2 K (3) 1 K
2
s C h e 3

r t
For a diatomic idealEgas xpin ea closed system, which of the following plots does not correctly
15.

s t r y between various thermodynamic quantities? [Jee-Main (Jan.) 2019]

m i
describe the relation
s
Ch e e r t
(3) y E
xp (4)
tr
(1) (2)

m i s
C h e ts
The combination of plots which does not represent isothermal expansion of an idealx pis:er
16.
r E gas
y (Jan.) 2019]
i s t
[Jee-Main

e r ts h e m
E x p C
s t r y
m i
h e
C and (D) (2) (A) and (D) (3) (A) and (C) (4) (B) and (C)
(1) (B)
88
 Thermodynamic
17. For silver, Cp(J K–1 mol–1) = 23 + 0.01T. If the temperature (T) of 3 moles of silver is raised
from 300 K to 1000 K at 1 atm pressure, the value of H will be close to :

e r t s e r ts
[Jee-Main (Apr.) 2019]
(1) 16 kJ
E x p (2) 13 kJ (3) 62 kJ
x p (4) 21 kJ
Erepresent the first law of
s ry s r y
t gas ? (Assume non-expansion work
t for the given processes involving an iideal
18.
m i
Which one of the following equations does
m
not correctly

C hethermodynamics
is zero)
C h e [Jee-Main (Apr.) 2019]
(1) Cyclic process : U = – w (2) Cyclic process : q = – w
(3) Isochoric process : U = q (4) Isothermal process : q = – w

19. 5 moles of an ideal gas at 100 K are allowed to undergo reversible compression till its

ts
temperature becomes 200 K. If C v = 28 J K–1 mol–1, calculate U and pV for this process.
(R = 8.0 J K–1 mol–1)
e r
xp
[Jee-Main (Apr.) 2019]

y E
(1) U = 14 J; (pV) = 0.8 J
t s
(2) U = 2.8 kJ; (pV) = 0.8 kJ
er
is tr
(3) U = 14 kJ; (pV) = 18 kJ
E x p
(4) U = 14 kJ; (pV) = 4 kJ

h e mthe following, the set of parameters thattrepresents

ry path functions, is :
20.
C(A) q + w
Among
m s
i(C) w
(B) q
(2) (A) and h e (D) H – TS
(1) (B) and (C)
C (D) (3) (A), (B) and (C) (4) (B), (C) and (D)
e r ts
xp
[Jee-Main (Apr.) 2019]

During compression of a spring the work done is 10kJ and 2kJ escaped to r
E
ysurroundings as
21.
i st the
heat. The change in internal energy, U (in kJ) is:
e m
h (4) –12
[Jee-Main (Apr.) 2019]
(1) 8 (2) –8
e r t s (3) 12
C
x p
Ein kJ is:
y
22. An ideal gas is allowed to expand from 1 L to 10 L against a constant external pressure of 1
bar. The workr
i s t done [Jee-Main (Apr.) 2019]

h e m r ts+ 10.0
C (1) –9.0 (2) –0.9 (3) –2.0
xp e (4)

r E
ythe combustion of one mole of heptane (I)
23. The difference between H and U (H–U), when
i s t
e m
is carried out at a temperature T, is equal to :
(2) –4 RT h
[Jee-Main (Apr.) 2019]
(1) 4 RT
C (3) –3 RT (4) 3RT
e r ts
E xp2020)]
24. The true statement amongst the following is:
r y
[Jee Mains
s t
(Jan.

s m i
(1) S is a function of temperature but S is not a function of temperature.
t
e r of temperature. Ch e
(3) Both S and S areE
x p
(2) Both S and S are not functions

s t r y functions of temperature.

m i
(4) S is not a function of temperature but S is a function of temperature.

C h e
89
 Thermodynamic
25. For the reaction; [Jee Main (Jan. 2020)]

A(l)  2B(g)
e r ts er ts
U = 2.1 kcal, S = x
E 20p –1
Exp
y y
cal K at 300 K.

s
Hence iG
r
tin kcal is___________ : istr
he m hem
C C
26. The magnitude of work done by a gas that undergoes a reversible expansion along the path

ABC shown in the figure is _____. [Jee-Main (Jan.) 2020]

er ts Pressure

Exp ts
(Pa) 10
r
stry xpe 8
A B

mi y E 6

Che istr 4 C

e m (2,2) 4 6 8 10 12 Volume
Ch (m3)
e r ts
E xp
For one mole of an ideal gas, which of these statements must be true? ist
ry
27.
h e m
s
(a) U and H each depends only onttemperature
e r C [Jee-Main (Sep) 2020]
E xpz is not equal to 1
ry
(b) Compressibility factor
s t
(c) Cm–i C
h e P, m =R
V, m

er t s
C (d) dU = C dT for any process xp
E
t(a),ry(c) and (d) (4) (c) and (d)
V

(1) (a) and (c)

m s
(2) (b), (c) and (d) i(3)

C h e ts
e r
E xthepvolume.
28.
r y
Five moles of an ideal gas at 1 bar and 298 K is expanded into vacuum to double
st
ts m i
The work done is :
r
e –V ) (3) Zero Ch (4) C (T –T ) e [Jee-Main (Sep) 2020]

(1) –RT ln V /V
E p
(2)x–RT(V
r y
2 1 2 1 V 2 1

i s t
h e m
C
90
 Thermodynamic
29. For a reaction, [Jee-Main (Sep) 2020]

4M(s) + nO2(g)  2M2On(s),

e r t s r t s
e below which
E x p E p
is plotted as a function of temperature. Thextemperature
y y
the free energy change

is r r
t at which :
tis stable could be inferred from the plot as theispoint
he m
the oxide
h e m
C (1) The slope changes from positive to zeroC
(2) The free energy change shows a change from negative to positive value

(3) The slope changes from negative to positive

e r ts
(4) The slope changes from positive to negative

E xp r ts
tr y p e
At constantisvolume, 4 mol of an ideal gas when heatedE x
30.
h e m t r y from 300 K to 500 K changes its
s
Cinternal energy by 5000 J. The molar heatmcapacity
i at constant volume is __________.
Ch e
e r ts
xatp100ºC
[Jee-Main (Sep) 2020]

E
try
31. The internal energy change (in J) when 90 g of water undergoes complete evaporation
i s
m JK mol )
h e
is ________. (Given : H for water at 373 K = 41 kJ/ mol, R = 8.314
vap
s C
–1 –1

e r t
E x p [Jee-Main (Sep) 2020]

s tr y
i
32. For a dimerization reaction

h e m A (g), r t s [Jee-Main (Sep) 2020]

C 2 A(g) 2

x p e
E
at 298 K, U = –20 kJ mol , S = –30 JK moly, then the G will be ________ J.
tr
 –1  –1 –1 

m is
C h e ts
e r
E xp
s t r y
ts m i
e r C h e
E x p
s t ry
m i
C h e
91
 Thermodynamic

EXERCISE-(JEE-ADVANCED)
1.
ts ts
A sample of argon gas at 1 atm pressure and 27°C expands reversibly and adiabatically from
e r e r
12.48 JK mol E
x p xp
1.25 dm3 to 2.50 dm3. Calculate the enthalpy change in this process. C v,m for argon is
E [JEE Adv. 2000]
str y–1 –1

stry
i
m of the following statement is false ? hemi
2.
C heWhich
C
[JEE Adv. 2001]
(A) Work is a state function
(B) Temperature is a state function
(C) Change of state is completely defined when initial and final states are specified.
(D) Work appears at the boundary of the system

e r ts
3.
x p s
One mole of non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K) to
E
y e r=t30.0 Latm. The change in
s tofrthe process in Latm.
(4.0 atm, 5.0 L, 245
i x p
K) with a change in internal energy (U)
E
em r y
t42.3
C(A)h 40.0
enthalpy (H) [JEE Adv. 2002]
i s
m (D) Not defined, because pressure is not constant
e
(B)
(C) 44.0
C h r ts
p
x2002] e
E
tL);ry
4. Two moles of a perfect gas undergoes the following process. [JEE Adv.

m i s
(a) A reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0
(b) A reversible isochoric change of state from (1.0 atm, 40.0hL)e
e r ts C to (0.5 atm, 40.0 L);

xp
(c) A reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L);
(i) Sketch with labelsEeach of the processes on the same P-V diagram.
s t r y
m i total work (w) and the total heat change (q) involvedsin the above processes.
Ch(iii)eWhat will be the values of U, H and S for the overall t?
(ii) Calculate the
e r
E xp process

C value of He is laways but C value of H is tatrlow

s y temperature and moderate temperature
5. vc V

and more than at higher temperature.e

i
m in two or three lines. [JEE Adv. 2003] s
2

C h Explain
r t
e
xppressure
6. One mole of a liquid (1 bar, 100 ml) is taken in an adiabatic container and the
r E
ydecrease by 1 ml.
s t
i [JEE Adv. 2004]
increases steeply to 100 bar. Then at a constant pressure of 100 bar, volume
Find U and H.
e r t s h e m
x p C
Egas is expanded isothermally and reversibly from 1 litre to 10 litre at 300
r y
ist change (in KJ) for the process is :–
7. Two mole of an ideal
K. Them
e enthalpy
C(A)h 11.4 kJ (B) – 11.4 kJ (C) 0 kJ
[JEE Adv. 2004]
(D) 4.8 kJ
92
 Thermodynamic
8. One mole of monoatomic ideal gas expands adiabatically at initial temp. T against a constant
external pressure of 1 atm from one litre to two litre. Find out the final temperature.

er ts
(R = 0.0821 litre. atm K–1 mol–1)
er ts [JEE Adv. 2005]

(A) T
Exp (B)
T
(C) T 
2
Exp (D) T 
2

s t r y 5
 23
1

s try
3  0.0821 3  0.0821
i i
9.
C he m
For the reaction,
2CO(g) + O  2CO (g);  
2 2 = –h
H C
em
560 kJ mol –1

In one litre vesel at 500 K the initial pressure is 70 atm and after the reaction it becomes 40 atm
at constant volume of one litre. Calculate change is internal energy. All the above gases show
significant deviation from ideal behaviour. (1 L atm = 0.1 kJ) [JEE Adv. 2006]

ts
10. The molar heat capacity of a monoatomic gas for which the ratio of pressure and volume is one.
e r
xp
[JEE Adv. 2006]
4
y E 3 5
e r t s
tr p
(A) R (B) R (C) R (D) zero
2
i s 2 2
mthe following, the state function(s) is (are) E x
h e s t ry
11.
C(A) Internal energy
Among
i
m (B) Irreversible expansion work
[JEE Adv. 2009]

h e
(C) Reversible expansion workC (D) Molar enthalpy
e r ts
E xp
12.
(B) elctromotive force istr
Among the following, extensive property is (properties are)
y
[JEE Adv.-2010]

(D) heat capacity em

(A) molar conductivity
(C) resistance
r t s C h
x p e
13.
y
One mole of an ideal E
dashed linestasrshown in the graph below. If the work done along the solid line path is w and
gas is taken from a to b along two paths denoted by the solid and the

m isthe dotted line path is wd, then the integer close to the ratiosw / w is – s

Che
that along
e r t [JEE Adv. 2010] d s

E xp
i s try
4.5
h e m
4.0
C
a

e r ts
xp
3.5
3.0

r y E
P 2.5
ist
s m
(atm) 2.0

e r t h e
C
1.5

E x p
1.0

st r y 0.5
b

m i 0.0

e
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

h
V(lit)

C
93
 Thermodynamic
14. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in
the figure. Which of the following statement(s) is (are) correct ? [JEE Adv. 2012]

er ts er ts
p p
(P1, V1, T1)

Ex Ex
stry stry
isothermal

mi P
mi
Che adiabatic

Che (P2,V2,T2)
(P3,V2,T3)

V
(A) T1 = T2 (B) T3 > T1
(C) wisothermal > wadiabatic (D) Uisothermal > Uadiabatic

e r ts
Paragraph for Question 4 and 5
A fixed mass 'm' of a gas p
inE
x t s [JEE Adv. 2013]
is subjected to transformation of states from K to L to M to N and
r
s tr
back to K as showny the figure.
x p e
m i y E
e r
K L

C h i st
m
Pressure

Ch e N M

e r ts
Volume
E xp
15.
(B) L to M and N to K ist
The pair of isochoric processes among the transformation of states is
ry
(A) K to L and L to M
(D) M to N nd Nh toe
m
(C) L to M and M to N
e r t s C K
16.
xp cooling (B) cooling, heating, cooling, heating
The succeeding operations that
(A) Heating, cooling,Eheating,
enable this transformation of states are

s t r y cooling, heating (D) Cooling, heating, heating, cooling

m i
(C) Heating, cooling,
s
17. h An ideal gas in thermally insulated vessel at internal pressure = Prt
e e
C temperature = T expands irreversibly against zero externalxppressure, as shown in the diagram.
, volume = V and absolute 1 1

r y E of the gas are P , V and T ,

m ist
The final internal pressure, volume and absolute temperature 2 2 2
respectively. For this expansion,
C h e [JEE Adv. 2014]
ts
e r
xp
Pext = 0

r y E
t
Pext = 0 Irreversible

s m is
e r t h e
E x p P1, V1, T1
C P2,V2, T2

s tr y
m i
e
Thermal insulation

C h
(A) q=0 (B) T = T 2 1 (C) P V = P V (D) P V = P V
2 2 1 1 2 2

1 1


94
 Thermodynamic
18. An ideal gas is expanded from (p1 V1 , T1) to (p2,V2,T2) under different conditions. The correct
statement(s) among the following is (are) [JEE Adv. 2017]

er ts er ts
(A) The work done on the gas is maximum when it is compressed irreversibly from (p 2,V2) to

Exp
(p1, V1) against constant pressure p1
Exp
s ry ry
(B) The work done by the gas is less when it is expanded reversibly from V 1 to V2 under
t st
mi i
adiabatic conditions as compared to that when expanded reversibly from V1 to V2 under
m
Che isothermal conditions
Che
(C) the change in internal energy of the gas is (i) zero, if it is expanded reversibly with T 1 = T2 ,
and (ii) positive, if it is expanded reversibly under adiabatic conditions with T 1  T2
(D) If the expansion is carried out freely, it is simultaneously both isothermal both isothermal
as well as adiabatic.

ts
19. A reversible cyclic process for an ideal gas is shown below. Here, P, V, and T are pressure,
er
xp
volume and temperature, respectively. The thermodynamic parameters q, w, H and U are heat,

E r ts
work, enthalpy and internal energy, respectively.
y e
[JEE Adv. 2018]

istr Exp
hem try
C mis
Ch e
er ts
Exp
i stry
The correct option(s) is (are)
–e
= P (V h
m
(A) qAC = UBC and wAB = P2(V2–V1)
(C) H < U and q = e r t s (B) w BC
C
2 V ) and q = H
2 1 BC AC

CA CA
E x p
AC U BC (D) q = H and H > U
BC AC CA CA

s r y
t the P-V work done is given by
20.
m i
In thermodynamics
s
[JEE Adv. 2020]

h e w  –  dVP .
e
C For a system undergoing a particular process, the work donexpis ,
ext r t
r y E
m st – a 
 iRT
he  V – b V 
w  –  dV 
C ts
2

e r
This equation is applicable to a
E xp
(A) System that satisfies the Van der Waals equation of state.
str y
s
(B) Process that is reversible and isothermal.
t m i
(C) Process that is reversible andradiabatic.
e Ch e
E x p
s tr y
(D) Process that is irreversible and at constant pressure.

m i
C h e
95
 Thermodynamic

ANSWER KEY

4ts s
EXERCISE-(JEE-MAIN)
er e r t
p p
1. 2 2. 4 3. 4. 3 5. 3 6. 7. 4 1
x
1 E 10.
x 2 14.
2y E13.
8. 1 9.
try 1 11. 2 12.
str
4
is 1 17. 3
1 m 16. 1 m
i
Che
15. 18.
Ch e 19. 4 20. 1 21. 1

22. 2 23. 2 24. 3 25. –2.70 26. 68 27. 3 28. 3

29. 2 30. 6.25, NTA Ans. (48) 31. (189494.39) NTA Ans. (189494)

32. –13537.57 Answer by NTA (–13538 J)

e r ts
E xp r t s
s y
t2.r A 3. C
EXERCISE-(JEE-ADVANCED)
x p e
m i y E
1.
e
H= –115
h
J
C(ii) –w = q = 620.77J, (iii) H = 0, U =m is tr
4.
h e 0, S = 0
C er ts
5.
xp
Hyderogen molecule is diatomic, has three translational, two rotatinal and one vibrational
E
s t r yof:
degree of freedom. The energy spacing between adjacent levels are in the order

m i
translational , rotational > vibrational
U = 0.1 L atm, H = 9.9 L atm 7. ts C C h e –557 kJ/mol 10. A
6.
p e r 8. C 9.

CD E13. x 2 14. AD 15. B 16. C 17. ABC

11. AD 12.
s t r y
ABDm i BC 20. (ABC or ABCD) s
18.
Ch e 19.
e r t
E xp
i s try
h e m
C er ts
E xp
s t ry
t s m i
e r C h e
E x p
s t r y
m i
C h e
96
 Thermodynamic
HINT AND SOLUTIONS
JEE-MAIN
1.
er ts
U is state function
er ts
Exp
UAB = +40 kJ/mol
Exp
stry
UBA = –40 kJ/mol
stry
2.
ming < 0
mi
C he H = U + ngRT
Che
H < U

3. Tf irrev > Tf rev

ts
4. 
H2O(l)  H2O(g)
er
ng = 1
Exp r ts
s tr y
H = U + ngRT
xpe
m i
41 = U +
1  8.3  373
y E
Ch e 1000
i s tr
U = +37.9041 kJ mol–1
h e m
C er ts
xp
5. C H OH (l) + 3O (g)  2CO (g) + 3H O(l)
E
2 5 2 2 2

try
ng = –1
H = U + ngRT
mis
s
1  8.314  300
Che
–1366.5 = U –
er t 1000

Exp
U = –1366.5 + 2.4942 = –1364.0058 kJ

try
2C6H6(l) + 15O2(g)  12CO2(g) + 6H2O(l)
s
i
6.

hem
ng = –3
r ts
C H = U + ngRT
xpe
E
try
H – U = ngRT
3  8.314  300
mis
= –7482.6 J mol–1
e
=
1000
Ch r ts
xpe
7. For rev. isothermal process
ry E
W = –q = –nRT ln 2
V
ist
V1
r ts em
U = 0
E xp e Ch
s y
t= r–1×8.3×300
8.
m i
W = –ngRT J = –2.49 kJ

Ch e
97
 Thermodynamic
9. For adiabatic process
q = 0, U = W

er ts er ts
10. ng = –1
Exp Exp
t ry
H = U + ngRT
s stry
|U| > i|H|
m mi
C he Che
11. qAB = +5J
WAB = –8J
UAB = qAB + WAB = –3J
UBA = +3J
qBA = –3J
er ts
xp
WBA = UBA – qBA = +6 J

y E er ts
U = U + t
is r + U = 0
U
xp
E
12.
U m
AB BC CA

h e = –5 + 2 = –3 kJ mol –1

stry
C–5 – 3 + U = 0 i
AB

CA

h e m
C ts
–1
U = +8 KJ mol
r
CA

q = U – W = 8 – 3 = +5 kJ mol –1
xpe
E
CA CA CA

istry
14. W = –4×(1 – 5) = +16 J
hem
q = CmT
e r ts C
2xp
16 = 1×24×T T =E K
st r y 3
C ism
i
15.
Ch eP defined at constant P only.
er ts
U = f(T)
Exp
C is defined at constant V only.
V
istry
hem
ts
C and C = f (T)
C
P V

er
Exp
16. For isoT process

stry
PVm = Constant
ts mi
e r Che
PVxp
E U

try
m
P P

m is
C he1/V m P Vm Vm

98
 Thermodynamic
T1 1000
17. H =  nC dT = 
p 3(23  0.01T) dT = 61950 J= 62 kJ
T2 300

r ts er ts
For adiabatic processxpe xp
18.
q=0 y
r  E U = W
ry E
i st ist
19.
he m= 28idealJ kgasmolis given,
5 mole
hem
C 100 K  200 K
C w,m
–1
, –1
R = 8J k mol C
–1 –1

U = ncv,mdT = 5 × 28 × 100
= 14000 J
= 14 kJ
(pv) = P2V2 – P1 V1
= nRT2 – nRT1
e r ts
= 5 × 8 × 100= 4kJ
E xp r ts
str y xpe
i
20. Both work (w) and heat (q) are state function.

e 1m ry E
21.
h
CU = q + w
From st
low of thermodynamics
i st
h e m
q = –2kJ ( Heat rejected into C
w = 10 kJ ( work is done on spring)
er ts
xp
surrounding)
U = –2 + 10 = 8 kJ
E
istry
22. C7 H16(l) + 11O2(g)  7C2(g) + 8H2O(l)
ng =  – 11 = –4
hem
H = U + ngRT
er ts C
H = U = –4RT
x p
r yE
As processsistIrreversible
23.
m i
e
w = –P (dv)
Ch = –1 × 9
ext
er ts
= –9 lit. bar
Exp
istry
24. (3)
hem
C er ts
25. [–2.70]
Exp
Sol. H = U + ngRT
stry
= 2.1 × 1000 + 2 × 2 × 300
ts mi
= 3300 cal
er Che
G = H – TS
Exp
300  20 y
= 3.3 – istr= –2.7 kcal
e m 1000
Ch
99
 Thermodynamic

P B (8, 8)
26. [68] A
Sol. Work done = –  Pdv
e r t s er t s
(2,8)

x p xp
y E D y E
i.e. area under P-V curve.

is r
Total areatunder cure is equal to
i st
(2,2) r C
m m
Cherectangle (PCDQ) Che O Q
(12,2)
(Area of trapezium (ABCD) + Area of

1 (0, 0) P V
=[ (6 + 10) × 6] + [10 × 2]
2
= 48 + 20
= 68 J

er ts
Hence, answer should be [68 J] instead of [48 J] because, origin is changed.

Exp r ts
NTA Ans. (3)tr
s y xpe
27.
Sol. For e mGasi y E
h ideal
C# U = f(T), H = f(T) istr
e m
#Z=1 Ch er ts
# CP – CV = R
Exp
# dU = CV dT
istry
hem
e r ts C
xp
28. (3)
Sol. As the expansion is E
W = zeroistr
y done in vaccum that is in absence of p so
ext

h e m r ts
C (2) xp e
E
try
29.
Sol. If G is negative than Oxide is stable
m i s
C h e ts
er
30. [6.25]
Exp
Sol NTA Ans. (48)
stry
ts mi
U = nCv T
er Che
 5000 = 4 × C × 200
v
Exp
C = 6.25 J molery
t
–1 –1

is
v K

m
Che
100
 Thermodynamic
31. (189494.39)

s s
NTA Ans. (189494)

e r t er t
Sol. H2O(l)  H2O(g)
x p
Eof 90 = 5 moles of H O Exp
s t r y stry
i i
For vapourisation 2

m m
18

CheH = U + ng RT
C he
5 × 41000 = U + 5 × 8.314 × 373
U = 189494.39 J

32. –13537.57 Answer by NTA (–13538 J)

Sol. 2A(g)  A2()
er ts
Exp
Hº = Uº + ngRT
r ts
tr y e
= –20 × 1000 + (–1) × 8.314 × 298
s xp
m i
= –22477.572 J
y E
Che
Hº = Hº – TSº
istr
e m
= –22477.572 – 298 × (–30)
h
C
= –13537.572 J
er ts
= –13538 J
Exp
istry
hem
er ts C
Exp
stry
mi
Che er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
101
 Thermodynamic

JEE ADVANCED
Ti Vi  = TfVf  –1
s s
–1

t t
1.
er
300×(1.25)  –1 = T ×(2.5) 
p
–1

per
x x
f

 1.25  E
T = 300×  ry
r 1

ry E
if
st 2.5  ist
he m hem
C 300 = 188.5 K
=
22 / 3 C
H = nCpT= 0.05×20.8×(188.5 – 300) = –115.41 J

2. Work is path function.

er ts
H = U + P2V2 – V1 P1 = 30 + (5×4 – 3×2) = 30 + 14
xp
3. = +44 L-atm

y E e r t s
ist1r 2 Exp
h e
P
m try
C
1atm
mis
Ch e
ts
4.
0.5atm 3
er
Exp
istry
20 L 40 L V
hem
Wnet = w1 + w2 + w3

e r t s
= –1×20 + 0 + 20 ln2= 20(ln2 –1) = –20×0.307 L-atm C
= –6.14 L-atm

E
q = –w = + 6.14 L-atmx p
s try
for cyclic process H = 0, U= 0, S = 0
m i s
5. h e e r t
C diatomic molecule at hisher temperature vibrational degreexofpfreedom is also considered.
He molecule is monoatomic so it just has three degree of freedom at all temperature but H is
2

ry E
m ist
Che
6. For adiabatic
U = W
e r ts
E xp
W = –PV
s t ry
= 100×10 –3

t s m i
er C h e
= +0.1 bar-L
H = U + P V – P E x p
s y
tr – 1×100) ×10
V
2 2 1 1

m i
= +0.1 + (100×99 –3

=h e
C bar-L
+9.9
102
 Thermodynamic
7. H = nCpT
For isoT T = 0
r ts er ts
For irrev. adiabatic pe p
8.
(V E
x Ex
nC T = –P y
3 ist
r – V)
stry
i
v ext 2 1

e1×m R(T – T) = –1×(2 – 1)

hem
Ch
f
2

Tf = T –
 C
3  0.0821

9. H = U + VP

ts
–560 = U + 1×(40 – 70) × 0.1
–560 = U – 3
e r
U = –557 kJ mol–1 E xp r ts
str y xpe
PV =m K i E
e y
–1
10.
h
CC = 2 R – 2 = 2 R + 2 = 2R mi
3 R 3 R str
Che er ts
11. State function - U, H
Exp
path function - W
istry
hem
12.
r ts
Intesive properties : molar conductivity, EMF
e C
E x p
Extensive properties : Resistance , Heat capacity

y
V 5.5
13.
is tr
Ws = –2.303RT log 2 = –2.303×log
V1 0.5

h e m log 1.1= –4.8 L-atm

= –4.606
r ts
C xpe
3  2 5
Wd = –4× + (–1×1) =      = 
26
E
try
L-atm
 3 2
s
2 3

m i
e
Wd
Ws
= 1.8  2.0
C h r ts
xpe
14. T1 = T 2 > T 3
ry E
T1 > T 3
ist
r ts em
e Ch
W isoT < Wadia (with sign)
U isoT > U adia.
E xp
istry
h e mprocess  vol. constant
15.
CIsochoric

103
 Thermodynamic
16. KL  P constant

er s
V, T 
t er ts
P, T E
xp
LM – V constant
Exp
st r y stry
m i
MN – P
mi
e e
constant

Ch V, T Ch
NK – V constant
P, T

17. For free expansion

er ts
w = 0, q = 0 T = 0
E xp ts
tr y per
P V = P Vis x
T =T
1 2

e m ry E
h t
1 1 2 2

C mis
h e
(P V T )
1 1 1
rev. isoT C er ts
P rev. adiabatic
Exp
18.
istry
hem
e r t s C
E x p
s t r y V

m i s
h e
(A) During irrev. compression maximum work is done on the gas.
e r
C (B) For expansion of ideal gas from same V to same V x|Wp | > |Wt
i

ry Ef isoT adia |

(C) If T = T  T = 0, U = 0
m ist
e
1 2

For rev. adiabatic expansion T C< Th U = –ve r ts

2 1

xpe
ry E
t
(D) For free expansion
is
r ts em
e Ch
Pext = 0 ,w = 0

E xp U = 0 ,q = 0
ry
If it is carried out isothemally

 it ism i st
Ch e adiabatic also

104
 Thermodynamic
19. A-C isochoric process
A-B isoT process

e
B-C isobaric process
r ts er ts
E x p
qAC = UAC= nCv(T2 – T1) = UBC
Exp
st r y V
stry
m i
wAB = –nRT1ln 2
mi
e e
V1

Ch w = –P (V – V ) = P (V – V )
BC 2 1 2 2 2 1
Ch
qBC = HBC = nCP(T2 – T1) = HAC

UCA = nCV(T1 – T2)

HCA < UCA
e r ts
E x p ts
tr y p e r
20.
is
(A, B,C or A,B,C,D)

m(A) : True for Van der Wall’s gas undergoing E x

h e t r y reversible process if irreversible then it
is
Option
C m
he (P = P )
will be false
Option (B) : True, Since it is Creversible. ext in
e r ts
Option (C) : True, Since it is reversible (P = P )
E xp
trypressure is
ext in

is
Option (D) : Given that process is irreversible at constant pressure. If internal
m is constant than it
h e
constant then it is also true. And if only external pressure
will be false. rts C
xp e
r y E
i s t
h e m r t s
C xp e
E
is try
h e m
C e r ts
E xp
s t r y
t s m i
e r C h e
E x p
s t ry
m i
C h e
105
 State of Matter – Ideal Gas

EXERCISE # (JEE-MAIN)
1.
r t s r ts
According to the kinetic theory of gases, in an ideal gas, between two successive collisions a
e e
x p
gas molecule travels
E E x p [AIEEE-2003]

s tr y
(1) In a straight line path
s r y
(2) with an accelerated velocity
t
m i
(3) In a circular path
m i (4) In a wavy path

he
2.C What volume of hydrogen gas, at 273KC
h e
and 1 atm, pressure will be consumed in obtaining
21.6g of elemental boron (atomic mass = 10.8) from the reduction of boron trichloride by
hydrogen ? [AIEEE-2003]
(1) 44.8 L (2) 22.4 L (3) 89.6 L (4) 67.2 L

3.
e r ts
As the temperature is raised from 20°C to 40°C, the average kinetic energy of neon atoms

E xp
changes by factor of which of the following ?
r t s2[AIEEE-2004]

s tr y xp e
i
(1) 1/2 (2) (313 / 293) (3) 313/298 (4)

e m r E
yan empty container at 25°C. The fraction of
4. h
Cthe total pressure exerted by oxygen is -mi
Equal masses of methane and oxygen are s
mixedt in

h e
C ts
[AIEEE-2008]

e r
xp
1 273 1 1
(1) 2/3 (2)  (3) (4)
3 298 3 2
ry E
is t
5. The molecular velocity of any gas is :-
root of temperatureCh
e m [AIEEE-2011]

r t s
to e
(1) inversely proportional to the square
(2) inversely proportionalp
E x absolute temperature

try to square root of temperature

(3) directly proportional to square of temperature

m is
(4) directly proportional
s
h e
C a, v and u represent most probable velocity, average velocity e r t
6.
E x p and root mean square velocity
s t r yThe correct order among the following is
i
respectively of a gas at a particular temperature.

(2) v > u > ah e m [JEE(Main)-2012]

s
(1) a > u > v
C (3) u > v > a (4) u > a > v
e r t
E x p
th of the air in it is expelled.ry
t
2
7. An open vessel at 300 K is heated till
i s Assuming that the

ts the temperature to which mvessel is heated is:

5

e r
volume of the vessel remains constant,
h e
C [JEE(Main-online)-2012]
the

E x p
(1) 750 K
s t ry (2) 400 K (3) 500 K (4) 1500K

m i
Che
106
 State of Matter – Ideal Gas
8. For 1 mol of an ideal gas at constant temperature T, the plot of (log P) against(log V) is a (P :
Pressure, V : Volume) : [JEE(Main-online)-2012]

er ts
(1) Straight line parallel to x-axis
er ts
(2) Curve starting at origin

Exp
(3) Straight line with a negative slope
E xp
(4) Straight line passing through origin

s r y r y
t and root mean square velocity
t among most probable velocity, averageisvelocity
m i m
e e
9. The relationship

C h is respectively :-
C h [JEE(Main-online)-2012]
(1) 2 : 8/  : 3 (2) 2 : 3: 8/  (3) 3: 8/  : 2 (4) 8/  : 3: 2

10. Which one of the following is the wrong assumption of kinetic theory of gases ?
[JEE(Main-online)-2013]

e r ts
(1) All the molecules move in straight line between collision and with same velocity.

E xp
(2) Molecules are separated by great distances compared to their sizes.
r ts
str y x p e
(3) Pressure is the result of elastic collision of molecules with the container's wall.

m i
(4) Momentum and energy always remain conserved.
y E
h e st r
11. CBy how many folds the temperature m of aigas would increase when the root mean square
C ah
e
container of fixed volume is increased from 5 × l0 cm/s to s
velocity of the gas molecules in 4

e r t
xp
4

(4) Six y E
l0 × l0 cm/s ? [JEE(Main-online)-2013]

tr
(1) Four (2) three (3) Two

m is
12.
t s C h
For gaseous state, if most probable speed is denoted by C, average e speed by C and mean square

p e r of molecules the ratios of these speeds are :-

speed by C, then for a large number
E x
ry1.225 : 1.128 : 1
[JEE(Main-offline)-2013]
(1) C : C s: Ct=
(3)eCm
i (2) C : C : C = 1.128 : 1.225 : 1
s: 1.128
Ch : C : C = 1 : 1.128 : 1.225
e r t
(4) C : C : C = 1 : 1.225

E xp
A gaseous compound of nitrogen and hydrogenrcontains
s t y 12.5% (by mass) of hydrogen. The
i is 16. The molecular formula of the compound is:
13.

e m
density of the compound relative to hydrogen
h [JEE(Main-online)-2014] s
C e r t
(1) NH 2 (2) NH3 (3) N H
3 (4) N H
2 4
E xp
s t ry the cylinder
14.
s
The initial volume of a gas cylinder is 750.0 mL. If the pressure of
t m iwill be
gas inside

e r C e
h [JEE(Main-online)-2014]
p
changes from 840.0 mm Hg to 360.0 mm Hg, the final volume the gas
x
E(2) 7.50 L
st r y
i
(1) 1.750 L (3) 3.60 L (4) 4.032 L
m
Che
107
 State of Matter – Ideal Gas
15. The temperature at which oxygen molecules have the same root mean square speed as helium
atoms have at 300 K is : (Atomic masses : He = 4 u, O = 16 u) [JEE(Main-online)-2014]
(1) 1200 K
e r t s
(2) 600 K (3) 300 K
e r
(4) 2400 K ts
x p
E is not an assumption of the kinetic theory x p
Eof gases ?
16. Which of the y
st r following
s t r y
m i m i [JEE-Mains (online)-2015]

Che(1) Gas particles have negligible volume.Che

(2) A gas consists of many identical particles which are in continual motion.
(3) At high pressure, gas particles are difficult to compress.
(4) Collisions of gas particles are perfectly elastic.
17. Initially the root mean square (rms) velocity of N 2 molecules at certain temperature is u. If this

ts
temperature is doubled and all the nitrogen molecules dissociate into nitrogen atoms, then the
er
xp
new rms velocity will be : [JEE(Main-online)-2016]
(1) u/2
y E (2) 4u
er ts (3) 14u (4) 2u
18.
istr xp
Two closed bulbs of equal volume(V) containing an ideal gas initially at pressure pi and
E
hem try
temperature T1 are connected through a narrow tube of negligible volume as shown in the
C mis
figure below. The temperature of one of the bulbs is then raised to T 2. The final pressure pf is :-

Ch e
ts
[JEE-Main-2016]

er
Exp
try
T1 T1 T1 T1

s

i
Pi, V Pi, V Pf, V Pf, V

hem
er ts C
Exp    TT 
(1) 2pi 2pi  T1T2  (2) pi  1 2  (3) 2pi 
 T1 

 T2 
(4) 2pi  
try  T1  T2   T1  T2   T1  T2   T1  T2 

mis
ts
19. An open vessel at 27°C is heated until two fifth of the air (assumed as an ideal gas) in it has

Che er
xp
escaped from the vessel. Assuming that the volume of the vessel remains constant, the

ry E
temperature at which the vessel has been heated is : [JEE-Main-2019 (Jan)]
(1) 500°C (2) 500 K
ist (3) 750° C (4) 750 K
20.
em
The volume of gas A is twice than that of gas B. The compressibility factor of gas A is thrice
Ch
than that of gas B at same temperature. The pressures of the gases for equal number of moles
e r ts
are :
E
[JEE-Main-2019 (Jan.)]
x p
(1) PA = 3PB (2) 3PA = 2PB (3) 2PA = 3PB (4) PA = 2PB
stry
21.
ts m i
0.5 moles of gas A and x moles of gas B exert a pressure of 200 Pa in a container of volume 10

e r : e [JEE-Main-2019 (Jan.)]
, x ish
p2R
m3 at 1000 K. given R is the gas constant in JK–1 mol–1
E x C
4  12 str
2R
y (2) 4  12 4R 4R

i
(1) (3) (4)

m
2R 2R

Che
108
 State of Matter – Ideal Gas
22. Points I,II and III in the following plot respectively correspond to (Vmp :most probable velocity)
[JEE-Main-2019 (Apr.)]

er ts er ts
Exp Exp
stry stry
mi mi
Che Che

er ts
(1) Vmp of O2 (400 K) ; Vmp of N2 (300 K); Vmp of H2 (300 K)

Exp s
(2) Vmp of N2 (300 K) ; Vmp of H2 (300 K); Vmp of O2 (400 K)
r t
stry xpe
(3) Vmp of H2 (300 K) ; Vmp of N2 (400 K); Vmp of O2 (300 K)

mi E
(4) Vmp of N2 (300 K) ; Vmp of O2 (400 K); Vmp of H2 (300 K)
y
23.
Che str
Identify the correct labels of A, B and C in the following graph from the options given below :
i
e m A

Ch ts
B
C
e r
xp
number
E
try
of
molecuels
m i s
t s he
C [IIT MAIN 2020(Jan.)]
Root mean square speed (V e);rmost probable speed (V ); Average speed (V )
speed

(1) A - V ; B – V E
p
; Cx– V
mp mp av
av
y
(3) A – V s;tBr– V ; C – V
rms mp (2) A – V ; B – V ; C – V
mp av rms

i mp av (4) A – V ; B – V ; C – V
mone of the following graphs is not correct for ideal gas ? r[IIT
rms mp rms

s
av
24.
Ch e
Which
e t MAIN 2020(Sep.)]

Ex p
dst r y
d d
m i d

TC h e t s
T 1/T P
p e r
E x
y
I II III IV
d = Density, P = Pressure, T = Temperature
i s t r
(1) IV (2) II
e r t, sHe and O each are enclosed
(3) III
h em (4) I
25.
E p H 2 2
C
x pressure of H is 2 atm, the total pressure
A mixture of one mole each of in a cylinder of volume V at

y
temperature T. If the partial of the gases in the
r (2) 38 atm
2

(1) 14 atm ist

cylinder is: [IIT MAIN 2020(Sep.)]

h e m (3) 22 atm (4) 6 atm

C
109
 State of Matter – Ideal Gas

EXERCISE # (JEE-ADVANCED)

1. r t s
eAlso calculate the partial pressure of He gas e r ts
Calculate the total pressure in a 10 litre cylinder which contains 0.4 g He, 1.6 g oxygen and

E x p E x p
y y
1.4 g of nitrogen at 27ºC. in the cylinder. Assume

is t r
ideal behavious for gases.
is t r [JEE 1997]

he m h e m
C C rA
2. According to Graham's law, at a given temperature the ratio of the rates of diffusion of
rB
gases A and B is given by : [JEE 1998]

ts
1/2 1/2 1/2 1/2
P M  M  P  P M  M P 
(A) A  A 
e r
(B)  A   A  (C) A  B  (D) A  B 

xp
PB  M B   M B   PB  PB  M A  M B  PA 

y E e r t s
is r vessel weighs 50.0 g when empty, 148.0
tglass x pgm when filled with a liquid of
3.
e m
An evacuated
r E
y gas at 760 mm Hg at 300 k . Determine
C h is t
m
density 0.98 g /mL and 50.5 g when filled with an ideal
the molecular weight of the gas. h e
C ts
[JEE 1998]
e r
E xp
4.
t r y
The pressure exerted by 12 g of an ideal gas at temperature t ºC in a vessel of volume V is one

m isvolume, the pressure

e 'V'. [molecular weight of
atmp. When the temperature is increased by 10 degrees at the same
increases by 10%. Calculate thes temperature 't' and volume
r t C h
x p e
gas = 120]

ry E [JEE 1999]

One m
i s t
5.
h e r ts
mole of N gas at 0.8 atm takes 38 sec to diffuse through a pin hole, whereas one mole of
C an unknown compound of Xenon with F at 1.6 atm takesx57pesec to diffuse through the same
2

ry E(At. wt. Xe = 138, F = 19)

i s t
hole. Calculate the molecular formula of the compound.

e m
Ch s
[JEE 1999]

e r t
x p
E If T is the
6.
s r y
The r. m. s. velocity of hydrogen is 7 times the r. m. s. velocity of nitrogen.
t [JEE 2000]
temperature of the gas : i
tT(Ns ) (C) T(H ) < T(Nh)em(D) T(H ) = 7 T(N )
e r C
(A) T(H ) = T(N )
2
E
2
xp
(B) T(H ) >2 2 2 2 2 2

s t r y
m i
Che
110
 State of Matter – Ideal Gas
7. Statement-1 : The pressure of a fixed amount of an ideal gas is proportional to its temperature.

s s
Statement-2 : Frequency of collision and their impact both increase in proportion to the square

e r t e r t
E x p
root of temperature. True / False.
E xp [JEE 2000]

tr
The rootsmean
y varies with density as
ysquare velocity of an ideal gas at constantstpressure
r
8.
m i m i
he
C (A) d 2
(B) d
h
C (C) de 1/2
(D) 1/d
[JEE 2001]
1/2

9. Which one of the following V, T plots represents the behaviour of one mole of an ideal gas at
one atmp? [JEE 2002]

ts
38.8 L 28.6 L

V(L)

per373 K V(L) 373 K


22.4 L 
Ex  
r ts 20.4 L
y e
(A) (B)
r
ist 
273 K

Exp
273 K

h em T(K)

t ry
T(K)

C  

mi
30.6 L
s  
14.2 L

e
V(L) V(L)

h
373 K 373 K

(C) 
22.4 L  C (D)   22.4 L
e r ts
xp
273 K 273 K

 
T(K)   T(K)
r y E
i s t
 of gas molecules is 400 m/sec. Calculate
 velocity 
h e m velocity at the same
 (rms)
ts
10. The average its

e r  C
temperature.

E x p
11.
s tr y velocity of one mole of a monoatomic gas having molar mass M is u .
The root mean square
i between the average kinetic energy (E) of the gas and u s is
rms

e m t
Ch(A) u = 3E (B) u = 2E (C) u = 2Exper(D) u = E
The realation rms [JEE-2004]

r y EM
t
rms rms rms rms

is
2M 3M 3M

m
e and methane under identical condition of pressurets
hhelium
12. C
The ratio of the rate of diffusion of
e r
x p
(D) 0.5 y E
and temperature will be [JEE 2005]
(A) 4 (B) 2 (C) 1
is tr
e r tsspeed of a gas X (molecular
h e m
13. At 400 K, the root mean square (rms)
E C
xpY at 60 K. The molecular weight of the gas Y is [JEE 2009]
weight = 40) is equal to the

s t r y
most probable speed of gas

m i
Che
111
 State of Matter – Ideal Gas
14. To an evacuated vessel with movable piston under external pressure of 1 atm., 0.1 mol of He

s s
and 1.0 mol of an unknown compound (vapour pressure 0.68 atm. at 0°C) are introduced.

e r t er t
Exp Exp
Considering the ideal gas behaviour, the total volume (in litre) of the gases at 0°C is close to

stry str y [JEE 2011]

mi i
m15 & 16
Che C h e
Paragraph for Question
X and Y are two volatile liquids with molar weights of 10g mol –1 and 40g mol–1 respectively.
Two cotton plugs, one soaked in X and the other soaked in Y, are simultaneously placed at the
ends of a tube of length L = 24 cm, as shown in the figure. The tube is filled with an inert gas at

ts
1 atmosphere pressure and a temperature of 300K. Vapours of X and Y react to form a product

e r
xpand assume ideal behaviour for the inert
which is first observed at a distance d cm from the plug soaked in X. Take X and Y to have

y E e r t sgas and the two vapours.

tr p
equal molecular diameters

m i s E x
y
[JEE 2014]

Che m i str
h e
C e r ts
E xp
is try
h e m
15.
e r
The value of d in cm (shown in thetsfigure), as estimated from
C Graham's law, is -
(B)p
(A) 8
E x 12 (C) 16 (D) 20

i s tryvalue of d is found to be smaller than the estimate obtained using Graham's

16.
h e m
The experimental
r ts
C (A) Larger mean free path for X as compared to that of Y xp
law. This is due to -
e
(B) Larger mean free path for Y as compared totthat r y E
m isinert gas as compared to that of X with the inert gas
of X

CofhXewith the inert gas as compared to that of Y with the inert

(C) Increased collision frequency of Y with the
(D) Increased collision frequency
e r t
gass
x p
E mean speed
17.
s
The diffusion coefficient of an ideal gas is proportional to its mean free path
r y
t is increased 2 times
and

tsa gas increased x times thehevalue i

mof x is ? [JEE-2016]
the absolute temperature of an ideal gas increased 4 times and its pressure
e r C
xp
as a result the diffusion cofficient of

r y E
i st
m
Che
112
 State of Matter – Ideal Gas
18. A closed tank has two compartments A and B, both filled with oxygen (assumed to be ideal
gas). The partition separating the two compartments is fixed and is a perfect heat insulator

e r t s er ts
(Figure 1). If the old partition is replaced by a new partition which can slide and conduct heat

Exp Exp
but does NOT allow the gas to leak across (Figure 2), the volume (in m 3) of the compartment A

stry
after the system attains equilibrium is ____.
stry [JEE Adv. 2018]

mi mi
Che 1 m , 5 bar,
3
Che 3
400 K 3 m , 1 bar, 300 K
A B

Figure 1

e r ts
xp
A B

y E e r ts
i str Figure 2
E x p
h e m r y regarding the root mean square speed
of the following statement(s) is (are) tcorrect
19.
C(U ) and average translational kinetic energy
Which
m s
i ( ) of a molecule in a gas at equilibrium ?
rms
e
Ch is increased four times
av
[JEE Adv. 2019] ts
(A)  is doubled when its temperature
av

p er
(B) U is doubled when its temperature is increased four times
E x
(C) U is inversely proportional to the square root of its molecular mass try
rms

rma

m is
t s C h e
(D)  at a given temperature does not depend on its molecular mass
r
av

p e
x speeds of a gas is as per the figure shown below, then the ratio of
E
trythe average, and the root mean square speeds, respectively, is
20. If the distribution of molecular

m i s
the most probable,
s [JEE Adv. 2020]
C h e e r t
E xp
s t r y
m i
e
Fraction of
molecules

Ch e r ts
E x p
s t r y
t s m i
e
speed
e r h
(A) 1 : 1 : 1
E x : 1 : 1.224 (C) 1 : 1.128C: 1.224 (D) 1 : 1.128 : 1
(B) 1p

str y
m i
Che
113
 State of Matter – Ideal Gas

ANSWER KEY

er ts EXERCISE # (JEE-MAIN)
er ts
xp
2. E 4 x
4. E3
p
1. 1
s ry
t 7. 3
3. 3
s r y
t 9. 1
5. 4
6. 3
1m
i 8. 3
4 m
i 10. 1
11.
C 3
16. he 12.
17.
3
4
13.
h
18. C 4
e 14.
19.
1
2
15.
20.
4
3
21. 3 22. 4 23. 2 24. 2 25. 4

er ts
EXERCISE # (JEE-ADVANCED)
0.492 atmp ; 0.246 atmp p
1.
–173°C , 0.82 L y E
x 2. C
r t
3.
s 123
4.
s trare correct 5. XeF
x e
p 9.
6. C
i
6
7.
e m
Both statements 8.
C try
D E C
10.
C4h
434.17 m/sec 11.
is
14.m 7
12. B
13.
e
Ch 17. 4
15. C
16. D 18.
er ts
2.22 or 2.23
19. B,C,D 20. (B or C)
Exp
istry
hem
er ts C
Exp
istry
hem r ts
C xpe
ry E
ist
em
Ch er ts
Exp
stry
ts mi
er Che
Exp
stry
mi
Che
114
 State of Matter – Ideal Gas
HINT & SOLUTIONS

e r ts EXERCISE # JEE-MAIN
er ts
1. (1)
E x p Exp
Sol. Factual
(4) ist
ry stry
m mi
Sol. he e
2.

C 2BCl + 3H  2B + 6HCl
3 2
Ch
 21.6 
mole :   =2
 10.8 
n H2 = 3
 Volume of H2 at 273K & 1 atm

e
= 3 × 22.4
r ts
Exp
= 67.2 L
r ts
str y xpe
3. (3)
Sol. K. E m
i y E
h
C e T
istr
(K.E) 313
40 C
e m
Ch
=
ts
(L.E) 293
r
20 C

xpe
E
try
4. (3)
Sol. P n
mis
P
 CH 4 =
w  32
=
2
ts Che
PO2 16  w 1
e r
E xp 1

s t r y
Fraction of total pressure excreted by O is 2
3

(4) mi
Sol.Ch
5.
e er ts
u T
Exp
stry
i
6. (3)
Sol. u > v > a
h e m s
7. (3) C er t
Sol. As, V remains constant
Exp
1
n
stry
T
ts mi
i.e.
er
n1T1 = n2T2
Che
Exp T = 3003 5
3
n1 × 300 = n1  T2  T2 = 500 k

stry 5
2

mi
Che
115
 State of Matter – Ideal Gas
8. (3)

s s
nRT
Sol. As P=
V
r t
e 1 log(P) pe
r t
E x p E x
m =1

r y
log(P) = log(nRT)
st
+ log  
str y
i V
or,m log(P) = log(nRT) – log(V) mi
he
C For, 1 mole ideal gas, Che log(V)

log(P) = log(RT) – log(V)

9. (1)

ts
8
Sol. 2:
er
: 3

xp


y E er ts
Sol. Factualmi
10. (1)
str Exp
h e stry
C(1) mi
Ch e
ts
11.

er
xp
3RT
E
Sol. Urms =

try
m

i.e. Urms  T
mis
ts Che
5 104
er T1

xp
=
10 104
E
T2

1 T
is t ry
4 m
ts
1
=
e
Ch (T = 4T )
T 2

er
Exp
y
2 1

istr
12. (3)
em
2RT Ch er ts
Sol. Umps = C =
m
Exp
stry
VAvg = C =
8RT
&
ts
Urms = C =
3RT
mi
m
e r m
Che
 C : C : C = 1 : 1.128 x
E p
: 1.225

s t r y
m i
Che
116
 State of Matter – Ideal Gas
13. (4)
Sol. Element % (by mass) relation no. of moles Simplest atomic ratio

e r ts 87.5
er ts 6.25
p p
N 87.5 = 6.25 =1
x
E12.5
14
Ex 6.25

s try t
12.5
s ry 12.5
i i
H = 12.5 =2

m formula = NH m
1 6.25

heEmpirical
C Molar mass of compound = 32
2
Che
As, molecular formula = n × empirical formula
32
n= =2  (m.f = N2H4 )
16

14. (1)
e r ts
xp s
Sol. P1V1 = P2V2

y E er t
tr
840 × 750 = 360 × V2

is840  750
Exp
h em
V2 =
360
try
C V2 = 1750 ml 1.750 or
L
mis
Ch e
15. (4)
er ts
Sol.  Urms O =  U rms He
Exp
try
2

3R  T 3R  300
mis
32
=

ts
4
Che
er
xp
T 300
 =
32
E4

i
T=
stry
32  300

hem 4
r ts
C  T = 2400 K
xpe
ry E
16. (3) Factual
ist
em
T
Ch er ts
p
17. Vrms ×
M
Ex
T is doubled
stry
M is lalfed
ts mi
'
Vrms = 4 Vrms
er Che
'
Exp
= 2  try
V =2V
rms rms

m is
Che
117
 State of Matter – Ideal Gas
18. (4)
Sol. (ni)T = (nf)T

e
P1V P1V Pf V Pf V
 rts er ts
p p
=
x
2P V P V y1 E1 
RT1 RT1 RT1 RT2
Ex
= tr  
 T 
stry
RT is R  T T   i
1 f
 P = 2P  
2

T T m
m
f 1

he Che
1 1 2 1 2

C (2)
19.
3
Sol. V1 = V2 , n2 = n1
5
n1T1 = n2T2
n1(300) = n2 (T2)
3
er ts
xp
300 = T2
s
5

y E er t
tr
T2 = 500 K

is Exp
20. (3)
Sol. Vh= em try
CZ = 3Z
A 2V B

mis
A B
h e
Z A
=
P V A
C A

er ts
xp
Z P V
E
B B B

try
PA

3=
PB
×2 2PA = 3PB

mis
ts Che
21. (3)
er
Sol. nA = 0.5
Exp nB = x mole

try
For the container

is
P = 200 Pa
m
Che
V = 10 m3
er ts
xp
T = 1000 K
PV=nRT
ry E
200 × 10 = (0.5 + x) R × 1000
ist
2
em
Ch ts
0.5 + x =
R
per
2
x = – 0.5 
4R
Ex
R 2R
stry
ts mi
22. (4)
er Che
is proportional to xp
E
T
y
Sol. V
r
MPS

t
M

m i s
Ch e
118
 State of Matter – Ideal Gas
23. [2]

s s
2RT
Sol. Vmp =
er t M
er t
Exp Exp
y y
8 RT
V =
ist
avg
r
 M
istr
he m 3RT
hem
C V = rms
M C
24. (2)
PM
Sol. d=
RT
d VS P
e r ts
d= 
 M
P E xp d
r ts
 RT 
try xpe
d V mis E
1 P

h e S

stry
Cd =  PM . 1 i
T

h e m
ts
 
 R  T C er
xp
dV T d
E
S

try
PM
s
d×T=
R 1/T
mi
ts Che
d pe r
Ex
istry
h e m T
r ts
C xpe
25. (4)
ry E
Sol. From PV = nRT
ist
p  mole at constant V and T.
 If 1 mole of H exert 2 atm h em s
2
C er t
 1 mole of He and O2 will also exert 2 atm each.
Exp
 Total pressure = 2 + 2 + 2 = 6 atm
stry
ts mi
er Che
Exp
stry
mi
Che
119
 State of Matter – Ideal Gas
EXERCISE # JEE-ADVANCED
1. nHe =
e
.4
r ts= 0.1
er ts
p p
4

Ex
n O2 = 1.6 = 0.05
Ex
stry 32
stry
mi n N2 = 1.4 = 0.05
mi
Che 28
0.2  0.0821 300 Che
PT =
10
PT = 0.492 atm
0.1
PHe =  0.492
0.2

ts
 PHe = 0.246 atm
e r
2. (C)
E xp r ts
tr y
Sol. According to Graham’s Law,
pe
P  iMs  Ex
 m
12

rheP  M 
r A

A

B

stry
C B B A

mi
Mass of liquid = 148 – 50 = 98gCh
e
3.
er ts
Volume of liquid =
98
= 100 ml = volume of flask
Exp
try
0.98
Mass of gas = 50.5 – 50 = 0.50 g
mis
Using, PV = nRT, we get
ts Che
M=
wRT
=
p r
0.5  0.082  300
e
 M = 123 g mol Ex
PV 1 0.1

ry
–1

For am is t
4.
h e fixed amount of gas at constant volume,
er ts
C1 T
PT
xp
ry E
t
=
1.1 T  10
m is
 T = 100 K or 173°C
12 0.0821h
C e ts
r
nRT 100
Also, V =
P
=
120

1
xpe
 V = 0.82 L
ry E
ist
5.
r ts
For the same amount of gas being diffused,
e hem
r1 t
= 2 = 1
P M2
Exp C
ry
r2 t1 P2 M1
Mt
0.8 is
38 em
57 2

h
=
C
1.6 28

120
 State of Matter – Ideal Gas
 M2 = 252 g mol–1
The formula of compound can be considered to be XeFn

r
 131 + 19n = 252
e ts er ts
n=6
Ex p Exp
stry
 The unknown gas is XeF6.
stry
(C)mi mi
Che U  = 7  U 
6.
Sol. rms H2 rms N 2 Che
T(H2 ) T(N 2 )
=7×
2 28
T( N2 )
 T(H2 ) =

ts
2
 T(H2 )  T(N2 )
p e r
E x r t s
s y
r as u  T
tTrue x p e
i
7. Statement-1: False, Besides amount, pressure also depends on volume.

e m
Statement-2:
r y E
h t
rms

8. C(D) m is
h e
3RT 3P C er ts
xp
Sol. U = rms =

E
m d

try
1/2
1
 Urms   
d
mis
ts Che
e r
xp
9. For an ideal gas , Vm = 22.4 lit at 273 K & 1 atm.
E
In option (C), at the initial point, the volume is 22.4 lit. as required by the ideal gas equation &
y value at both initial & final points.
rsame
V
  have
 T m is t
the

h e er ts
C V 8RT 3RT xp
r y E

t
Avg

s
10. =
U m m
m i
e
rms

Ch ts
8
=
per
x
3
3
ry E
 Urms =
8
 400
ist
r
e s
Ut = 434.17 m/s.
3  3.14
hem
 
Exp

8
 400 rms
C
stry
mi
Che
121
 State of Matter – Ideal Gas

3RT
11. Urms = …….(1)
s s
M

er t er t
The average kinetic energy (E) of the gas is given by the following expression.
3
Exp Exp
y y
E = RT

istr
2
istr
hem
RT = E
2
……(2)
hem
C C
3
Substitute (2) into (1)
2
3 E
Urms = 3
M

ts
2E
r
Urms =
M
xp e
y E er ts
12. (B)
16ist
r xp
rhe
r
=m = 2
ry E
t
He
Sol.
C CH 4 4
mis
(U ) at 400 K = (U ) at 60 K he
13. rms x
Cmps y

er ts

3R  400 2R  60
=
Exp
try
40 my
3  400 2  60 2  60  40
mis
  =
my
 my =
ts 3  400
my = 4
Che
r
40

Partial pressure of He =x1p

e
14.
E – 0.68 = 0.32
n .R ry0.1 0.082  273
V=
P is
He
t = 0.32
T

he
m r t s
e
He

C V = 7 lit.  Volume of container = volume of He.

x p
E
15. (C)
s tryby Y is (24 – d)
Sol. Let distance covered by X is d, then distanceicovered
h e mX & Y s
C t
If r & r are the rate of diffusion of gases
r
x y

r d 40
 d = 16 cm
x p e
E
x
= = =2
ry 24  d 10

s ry
tvalue obtained using
ts collision frequency h i
m the inert gas as compared
16.
e r
The experimental value of d is found to smaller than the
e
estimated
C increases, the molecular speed
to that of X with the E xpgas. ( As, the collision frequency
Graham’s law. This is due to increased of Y with

st r y than expected.)
inert

m i
decreases much more

Che
122
 State of Matter – Ideal Gas
17. (DC) Diffusion coefficient (mean free path)  Umean
Thus (DC)   Umean
=
er
RT
ts 
T
er ts
p p
But
x
E8RT
2 N0 p p
Ex
s ry
t M stry
and
iU
mU  T
= mean
mi
Che mean
Che
(T)3/2
 DC 
p
3/2 3/2
(DC) 2  p  T   p  4T  1
(x) =  1  2  =  1  1  =   (8) = 4
(DC)1  p 2  T1   2p1  T1  2

e r ts
& pT =T
18. Finally, P = P
A
Vy E
x
B

r ts
A B
n
=tr
n is V
A A

xpe
E
So,

h e m5 B B

try
C 400R = V mis
Ch e
A
3 V B

e r ts
xp
300R
E
try
V 5 5 20
 A
= V =  4 = = 2.22
i s
A
V 4 9 9
m
B

The root mean square speed (U t) s C h e

19.
relation with temperature p e r and average translational
rms kinetic energy ( ) has following av

E x and molecular mass

 = RT,t Ury=
3 3RT 1
2 is
av rms and U  rms

he m M M
r t s
C According to the relation given above  gets doubled when
 doesn’t depend on its molecular mass.
av
e
xpthe temperature is increased 2
r y E av
times. Thus option B is incorrect.
is t
e m
Explanation for option (B) : Duehto symmetrical graph given, the average value of velocitiess
20.
C e r t
will be at the middle, symmetrical velocity which is also most probable velocity.
E xp
While calculating rms speed, we have to take average of square of speedstand
s r yits root. In square
of speeds, higher speeds will give more contribution so the value willibe more than the average
e r ts h e m
E x p
value. But we cannot calculate rms speed by given C
data as
3RT
is valid for Maxwell’s

distribution. try
M

m isfor option (C) : According to Maxwell’s distribution of speed

Che
Explanation

123
 State of Matter – Real Gas

EXERCISE # (JEE-MAIN)
Q.1
er ts
When does a gas deviate the most from it's ideal behaviour ?
er ts [JEE-MAIN(ONLINE)-2015]

Exp
(1) At high pressure and low temperature
Exp
stry
(2) At high pressure and high temperature
stry
mi (3) At low pressure and low temperature
mi
Che (4) At low pressure and high temperature
Che
Q.2 If Z is the compressibility factor, Van Der Waals' equation at low pressure can be written as :
[JEE-MAIN-2014]
Pb Pb Pb a
(1) Z = 1 – (4) Z = 1 –
ts
(2) Z = 1 + (3) Z = 1 +
r
RT RT RT Vm RT

xp e
y E e r t s
Pb st
r
Q.3 The compressibility factor
p
for a real gas at high pressure is :-
x (4) 1 + Pb
[AIEEE-2012]

(1) 1 –mi E
y
PT

C h e RT
(2) 1 +
Pb
i st r
(3) 1
RT

h e m
C for gases. Chlorine is more easily liquefied than ethane
Q.4 'a' and 'b' are Van Der Waals' constants
er t s
because
E xp
[AIEEE-2011]
(1) a for Cl < a for C H but b for Cl > b for C H
2 2 6 2 2 6

is try
(2) a for Cl > a for C H but b for Cl < b for C H
2 2 6 2 2

h
6
em
(4) a and b for Cl < a and b e
2
ts
forrC H
(3) a and b for Cl > a and b for C H 2 6
C
E xp2 2 6

Q.5 In van deris tryequation of state of the gas law, the constant 'b' is a measure of : [AIEEE-04]
m s
Waals'

h(1)eintermolecular
C (2) intermolecular attractions e r t
xp
repulsions

ry E
(3) volume occupied by the molecules
i s t
e m
Ch
(4) intermolecular collisions per unit volume

er t s
E
Q.6 Consider the van der Waals constants, a and b, for the following gases. [JEE-MAIN-2019]
xp
Gas At Ne Kr Xe
s tr y
–2

ts 5.0 m i
e
6

1.7r 1.0
a/(atm dm mol ) 1.3 0.2 5.1 4.1
–2 3 –1
p e C h
tox
b/(10 dm mol 3.2
Which gas is expectedE
s tr y (2) Krhave the highest critical temperature ?
(1) Xe
m i (3) Ne (4) Ar

C h e
124
 State of Matter – Real Gas
Q.7 At a given temperature T, gases Ne, Ar, Xe and Kr are found to deviate from ideal gas
behaviour. Their equation of state is given as
RT
e r ts e r t s
P=
Vb
at T.
E x p E x p
s r y
t factor) v p? s tr y
i i
Here, b is the Vander Waals constant. Which gas will exhibit steepest increase in the plot of Z

e m
(compression
e m [JEE-MAIN-2019]

Ch (1) Kr Ch(3) Xe
s

(2) Ar (4) Ne

Q.8 Consider the following table :

Gas a/(k Pa dm6 mol–1) b/(dm3 mol–1)
A 642.32 0.05196
B 155.21
e r ts
0.04136
C 431.91
E x p 0.05196
t s [JEE-MAIN-2019]
155.21 y
trder Waals constants. The correct statement p e r
s x
D 0.4382
a and b areivan E
h e mC will occupy lesser volume than gas A;tgas
r yB will be more compressible than gas D
about the gases is :
(1) Gas s
C(2) Gas C will occupy more volume thanmgasiA; gas B will be more compressible than gas D
h e
(3) Gas C will occupy lesser volume than gas A; gas B will be lesser compressible than gas Drts
C
x p e
y E
(4) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D

is trof gas A is thrice

h e
Q.9 The volume of gas A is twice than that of gas B. The compressibilitym factor

e r ts The pressures of Cthe gases for equal number of moles

than that of gas B at same temperature.
are :
E x p [JEE-Main-2019]
(1) P = 3P
s tr y (2) 3P = 2P (3) 2P = 3P (4) P = 2P
i energy curve for the H molecule as a function of inter nuclear
A B A B A B A B

m s
rt [Jee-Main (Sep) 2020]
CheEnergy
Q.10 The potential 2 distance is :

p e
EnergyEx
s t r y
m i
Ch (2)e ts
(1)
p er
Internuclear Internuclear
E x
distance distance
s tr y
Energy
ts
Energy
m i
e r C h e
E x p
(3)
t r y (4)

m is Internuclear Internuclear

C h e distance distance

125
 State of Matter – Real Gas

EXERCISE # (JEE-ADVANCED)

e r ts e r t s
Q.1
 xB
p
One way of writing the equation for state for real gases is,
E x p [JEE 1997]

PV =y RT E y

s t r 1
 V  ..... where B is
ian approximate expression for 'B' in termsm
a
is t
constant.
r
e m e
Ch Ch
Derive of van der Waals' constants 'a' & 'b'.

Q.2 Using Vander Waals equation, calculate the constant "a" when 2 moles of a gas confined in a 4
litre flask exerts a pressure of 11.0 atm at a temperature of 300 K. The value of "b" is 0.05 litre
mol–1. [JEE 1998]

e r ts
ppressure (B) low temperature andtshigh pressure
Q.3 A gas will approach ideal behaviour at : [JEE 1999]
(A) low temperature andx
r E
y high temperature (D) high temperature
low
e rand high pressure .
is t
(C) low pressure and
E x p
m y
hecompressibility of a gas is less than unityisattSTP.
r Therefore,
Q.4 CThe
m [JEE 2000]
(A) V > 22.4 L
m m
CheL (C) V = 22.4 L (D) V = 44.8 L erts
(B) V < 22.4 m m

E xpat 0° C
rya gas molecule is
Q.5 The compression factor (compressibility factor) for one mole of a van der Waals' gas
and 100 atmosphere pressure is found to be 0.5. Assuming that the volumetof
m i s
negligible, calculate the van der Waals' constant 'a'.
ts C h e [JEE 2001]

e r
E
Q.6 The density of the vapour
xp aofsmall
a substance at 1 atm pressure and 500 K is 0.36 Kg m . –3

r y
ist Determine
The vapour effuses through hole at a rate of 1.33 times faster than oxygen under the

(i)e
h m
same condition.
r t s of the vapour and
[JEE 2002]
mol. wt.; (ii) molar volume;
e
C (iv) which forces among the gas molecules are dominating,xthepattractive or the repulsive
(iii) compression factor (z)

ry E
Q.7 Positive deviation from ideal behaviour takesis
t
e m
h and PV > 1
place because of [JEE 2003]
s
Catoms e r t
p
(A) molecular attraction between
nRT
E x
PV
s t r y
(B) molecular attraction between atoms and <1
i
PV ts m
nRT

(C) finite size of atoms and er> 1 C h e

E xpnRT
s t r y and PV < 1
m i
(D) finite size of atoms

Ch e nRT

126
 State of Matter – Real Gas
Q.8 For a real gas obeying van der Waals' equation a graph is plotted between PV m (y-axis) and
P(x-axis) where Vm is molar volume. Find y-intercept of the graph. [JEE 2004]

r ts
ethe variation of Z er ts
x p
Q.9 The given graph represents
E = PV ) versus P, for three real ry E xp
st r y
(compressibility factor
st
i
mA, B and C. Identify the only INCORRECT
nRT
m i
C hegases
C h e statement. [JEE 2006]

Z
A

s
C

(A) for the gas A, a = 0 andp e r t 0

P(atm)

(B) for the gas B, b = E

x t s
its dependence on P is linear at all pressure
r
(C) for theis
y
trC, which is typical real gas for whichEneitherx e
p a nor b = 0. By knowing the
0 and its dependence on P is linear at all pressure

mand the point of intersection, with Z = 1,tra and

gas

h e
minima
s y b can be calculated.
C(D) At high pressure, the slope is positivemfori all real gases A, B and C.
h e
C e r ts
xpin the
Q.10 Match gases under specific conditions listed in Column I with their properties / laws in Column
II. Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given
r E
y [JEE 2007]
ORS.
i s t
Column I
Hydrogen gas (P = 200 atm,sT = 273 K) e m factor  1
Column II
h
(A)
Hydrogen gas (P ~ 0,e Tr
t (P)
CAttractive forces are dominant
Compressibility

xTp= 273 K)
(B) = 273 K) (Q)
(C)
y
CO (P = 1 atm,
Real t
2 E
r with very large molar volume (S) P (V– nb) = nRT
(R) PV = nRT
(D)
m is gas
s
h e
C (A) behaves similar to an ideal gas in the limit of large molar e r t
Q.11 A gas described by van der Waals' equation
x p
E volumes
[JEE 2008]

s t r y
m i
(B) behaves similar to an ideal gas in the limit of large pressures

h e
(C) is characterised by van der Waals' coefficients
C
that are dependent on the identity of the gas
t s
but are independent of the temperature
p e r
E x
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally

s r y
tin the Vander Waals'
ts
Q.12 The term that corrects for the attractive forces present in a real gas
m i
e r h e
an C
equation is [JEE 2009]

E xpan2 2
(A) nb
s r y (B) (C) – (D) – nb
tof a van der Waals' gas when b = 0 and T = 300 K, the PV vs. 1/V plot is shown
2 2

i
V V

e m
Q.13 For one mole
h
C The value of the van der Waals' constant a (atm. litre mol ) is
2 –2
below.
127
 State of Matter – Real Gas
[JEE 2012]

PV(litre-atm mol–1)
s s
24.6

er t er t
Exp 23.1
xp
[Graph not to scale]
E
stry 21.6
stry
mi 20.1
mi
Che Che

0 2.0 3.0
1
(mol litre–1)

e r ts V
(A) 1.0
E x p
(B) 4.5
s (C) 1.5
(D) 3.0
t
r y
Q.14 One mole ofsatmonoatomic real gas satisfies the equationx e r
p b) = RT where b is a constant.
i E
m of interatomic potential V(r) andtrinteratomic
y
P(V–

C h e
The relationship
is
distance r for the gas is given by-

m [JEE 2015]

Che e r ts
V(r)
E xp
V(r)

0
is try 0

m
(A) r (B) r

ts C h e
e r
E xp
V(r)
i s try V(r)

(C) m
h e 0 (D)
e r t s 0
C r
xp
r

r y E
i s t
e m
Ch e r ts
E x p
s t r y
ts m i
e r C h e
E xp
s tr y
m i
Che
128
 State of Matter – Real Gas

ANSWER KEY

er ts EXERCISE # (JEE-MAIN)
er ts
xp
2. E 4 x
4. E2
p
1. 1
s ry
t 7. 3
3. 4
s r y
t 9. 3
5. 3
6. 2
mi 8. 2
mi 10. 3

C he Ch e
EXERCISE # (JEE-ADVANCED)
 a 
1. B = b  2. 6.52 atm L2 mol–2 3. C 4. B
 RT 
1.256 atm L2 mol–2 (i) 18 g/mol , (ii) 50 L mol–1 , (iii) 1.218 , (iv) repulsive
8. rtsRT
5. 6.
7. C
e
xp (D)R
9. D
10.
y E
(AP,S; (B)R; (C)P,Q; 11.
er ts
A,C,D 12. B

is tr Exp
m
13. C 14. C

h e stry
C mi
Ch e
er ts
Exp
istry
hem
er ts C
Exp
istry
hem r ts
C xpe
ry E
ist
em
Ch er ts
Exp
stry
ts mi
er Che
Exp
stry
mi
Che
129
 State of Matter – Real Gas
HINT AND SOLUTIONS

s s
EXERCISE # JEE-MAIN
r t er t
xp ae xp
4.
r y E b
Ease of liquification 
ry E
i s t ist
heTm 
a
hem
C C
6. C
b

RT
7. P=
Vb
PV – Pb = RT

Z=
Pb
e r ts
xp s
RT
 b 
y E e r t
Z= 
i
 RT  tr
 P
s E x p
h e m t r y
s
b is maximum for Xe
C m i
h e
8. 
C
Gas A and C have same value
ts
of 'b' but different value of 'a' so gas having higher value
of 'a' have more force of attraction so molecules will be more closer hence occupyeless r
E xp
y lesser value
volume.
Gas B and D have same value of 'a' but different value of 'b' so gas r

is t having
of 'b' will be more compressible.
h e m
e r ts C
10. For H gas when molecules
2

E p decreases when molecules approaches too close with each other

xenergy come closer to each other then first attraction among them

y and potential energy increases.

trdominates
dominates so potential
s
m i
then repulsion
s
Ch e e r t
E xp
st r y
m i
Ch e t s
p e r
E x
s t r y
ts m i
e r C h e
E xp
s tr y
m i
Che
130
 State of Matter – Real Gas
EXERCISE # JEE-ADVANCED

1.
er ts
According to the van der Waals equation,
er ts
Exp
P  (a)
(V – b) = RT Exp
stry v2
stry
mi RT a
mi
Che or P=
Vb V
 2
Che
RTV a
or Pv = 
Vb V
1
 b a  b a
or Pv = RT 1     RT 1   
 V V  V V

r ts
Neglecting higher powers of b / V
e
xp
 b a   1 a 
or PV = RT 1  
y E
 V VRT 
 = RT 1   b 
 V ts

RT 
er
is tr Exp
m
Comparing with the given form of the equation. We get

h e a
s try
C B=b–
m i
e
RT

Chof gas is, er ts

2. Vander Waal’s equation for n moles
E x p
try
 n 
2

  –
v 
[v nb] = nRT.
s
P a
i
2

Given, v = 4L, P = 11 atm, T = 300 K, b = 0.05 litre/mol 
h e m
 n=2
e r ts C
Thus, 11  a  [4 E
 2  2
xp = 2 × 0.082 × 300
4ry
– 2(0.05)]

is t 
2

h e matm litre mol

a = 6.46 2 –2

r t s
C We know that, compressibility factor, Z = PV / RT xp e
5.
ry E
i s t
m
0.5 = 100 *V/0.082 *273
 V = 0.1117 L
C h e t s
Note :- Further when volume of a gas molecule is negligible, van der Waal’s equation p e r
E x becomes
2
(P + a / V ) (V – 0) = RT
s tr y
Or PV = RT – a/V or a = RTV – PV s
t m i
r e
2

x p e C h
E
Substituting the values

s t r y * 173) – (100 * 0.1119 * 0.1119)

i L mol
A = (0.082 * 0.1119

m
Che
2 –2
= 1.253 atm

131
 State of Matter – Real Gas
 a 
8.  P  2  (Vm – b) = RT

s s
Vm 

er t er t
PVm – Pb –
a
Expab
 2 = RT
Exp
s r y
t x=0
Vm Vm
stry
i
m i.e. P = 0 mi
e e
at y intercept,

Ch Ch
 Vm  
So the equation becomes
PVm – Pb = RT
PVm = Pb + RT
er ts
y=mx+c
Exp ts
c is the y intercepty
tr per
m i s Ex

h e c = RT
stry
C mi
Ch e s
14. Since a = 0
e r t
E x p
Hence, only repulsive forces are present which are contributive only at very close distance.
Thus, the potential energy will increase abruptly.
is try
h e m
e r ts C
E xp
is try
h e m r t s
C xp e
ry E
is t
e m
Ch e r ts
E x p
s tr y
ts m i
e r C h e
E xp
s tr y
m i
Che
132
 Atomic Structure

EXERCISE # (JEE-MAIN)
1.
e r s r s
An atom has a mass of 0.02 kg and uncertainty in its velocity is 9.218 × 10 –6 m/s then
t t
e [AIEEE 2002]
x p
uncertainty in position i s (h = 6.626 × 10–34 Js)
(1) 2.86× 10 mE (2) 2.86 × 10 cm (3) 1.5 × 10 m E(4) 3.9 × 10 m x p
tH-ryatom in the ground state is –13.6 eV, Hence y in the second excited state is-
–28 –32 –27 –10

s
Energyiof i st r
m m
2. energy

Che Ch e [AIEEE 2002]

(1) –6.8 eV (2) –3.4 eV (3) –1.51 eV (4) –4.3 eV
–5
3. Uncertainty in position of a particle of 25 g in space is 10 m. Hence uncertainty in velocity
(ms–1) is (Planck's constant h = 6.6 × 10–34 Js) [AIEEE-2002]
–28 –34 –34 –24
(1) 2.1 × 10 (2) 2.1 × 10 (3) 0.5 × 10 (4) 5.0 × 20

4.
e r ts
The orbital angular momentum for an electron revolving in an orbit is given by     1 .
h

xp will be given by
.
s
2

y E e r t
tr (2) + 1 . 2 p (4) h
This momentum for an s-electron [AIEEE-2003]

(1) 2. is (3) zero Ex

m
h

h e 2 2 2
st ry 2
CThe number of d-electrons retained in Fem(At.
i number of Fe = 26) ion is :
e
2+
5. [AIEEE-2003]
(1) 6 (2) 3 Ch (3) 4 (4) 5
er ts
E x10pmeters
6. The de Broglie wavelength of a tennis ball of mass 60 g moving with a velocity
i s try[AIEEE 2003]
of
per second is approximately :
m
(3) 10 meters he (4) 10 meters
–25
(1) 10 meters –33

r t
(2) 10 meters
e s –31
C
–16

In Balmer series of E
xp
7.
s t r y following inter-orbit jumps of the electron for Bohr orbits in an atom of
lines of hydrogen spectrum, the third line from the red end corresponds to

m
which one i of the
s [AIEEE-2003]
h e
C (1) 2  5 e r t
(3) 5  2 Exp
hydrogen ?
(2) 3  2 (4) 4  1
8.
i
Which of the following sets of quantum number
strisycorrect for an electron in 4f orbital ?
h e m
ts
[AIEEE-2004]
1C r
(1) n = 3, l = 2, m = – 2, s = + (2) n = 4, l = 4, m = – 4, s = –
1
x p e
2 2
(4) n = 4, l = 3, m = + 4, s =t+ry
E
(3) n = 4, l = 3, m = + 1, s = +
1

s m is 1

t when in a hydrogenheatom electron falls from infinity

2 2

e r
xpbe (Rydberg constant = 1.097×C10 m ) :
9. The wavelength of the radiation emitted,

y E
to stationary state 1, would
r (2) 192 nm
7 –1
[AIEEE-2004]
(1) 9.1 × 10 st
i
–8
nm (3) 406 nm (4) 91 nm

h e m
C
133
 Atomic Structure
10. Which of the following statements in relation to the hydrogen atom is correct ?

s s
(1) 3s, 3p and 3d orbitals all have the same energy [AIEEE-2005]

e r t
(2) 3s and 3p orbitals are of lower energy than 3d orbitals
er t
x p
E in energy than 3p orbital
(3) 3p orbital is lower in energy than 3d orbital
E x p
s r y
tto Bohr's theory angular momentum of electrons r y
tin 5th shell is : [AIEEE-2006]
m i
(4) 3s orbitals is lower
m i
11.
heAccording
C (1) 1.0 h/ (2) 10 h/ h e
C (3) 2.5 h/  (4) 25 h/
12. Uncertainty in the position of an electron (mass = 9.1 × 10 –31 Kg) moving with a velocity 300
ms–1, accurate upto 0.001%, will be :- (h = 6.63 × 10–34 Js) [AIEEE-2006]
(1) 5.76 × 10–2 m (2) 1.92 × 10–2 m (3) 3.84 × 10–2 m (4) 19.2 × 10–2 m

ts
13. The ionziation enthalpy of hydrogen atom is 1.312 x 10 6 J mol–1. The energy required to excite

p e r
(2)x6.56 x 10 J mol (3) 7.56 x 10 J mol (4)
the electron in the atom from n =1 to n =2 is [AIEEE-2008]
(1) 8.51 x 10 J mol E
5
y
–1 5 –1

e r ts9.84 x 10 J mol
5 –1 5 –1

In an atom,san
i trelectron is moving with a speed of E600xp
m
14. m/s with an accuracy of 0.005%.

h e s y be located is (h = 6.6 × 10 kg m s ,
with which the position of the electronrcan
t –34 2 –1

Cmass of electron, e = 9.1 × 10 kg): mi

Certainty

e
–31

C10h m (3) 1.52 × 10 m (4) 5.10 × 10 m erts

m [AIEEE-2009]
–3 –3 –4 –3
(1) 1.92 × 10 m (2) 3.84 ×
15. Calculate the wavelength (in nanometer) associated with a proton moving at 1.0 × 10
E x p ms 3 –1

–27
(Mass of proton = 1.67 × 10 kg and h = 6.63 × 10 Js) : –34

s t r y[AIEEE-2009]
(4) i
(1) 2.5 nm (2) 14.0 nm (3) 0.032 nm
The energy required to break onesmole of Cl–Cl bonds in h
e m 0.40 nm
16.
r t C
ebreaking a single Cl–Cl bond is
Cl is 242 kJ mol . The longest
2
–1

x p
EN = 6.02 × 10 mol )
wavelength of light capable of
(C = 3 × 10 ms yand
r
8 –1 23 –1

t
[AIEEE-2010]
is
A

17. h e m
(1) 494 nm (2) 594 nm (3) 640 nm
energy of He is 19.6 × 10 J atom . The energy ofethe r t s
(4) 700 nm

C of Li is:
–18 –1

xp
+
Ionisation first stationary state (n = 1)
2+

y E
r × 10 J atom
[AIEEE-2010]
–17
(1) 8.82 × 10 J atom –1
i s
(2)t4.41 –16 –1

(3) –4.41 × 10 J atom–17

h
–1
e m (4) –2.2 × 10 J atom –15 –1

s
A gas absorbs a photon of 355C nm and emits at two wavelengths. If one of the emissions r is tat
18.
xp e
680 nm, the other is at :
r y E
[AIEEE-2011]
(1) 743 nm (2) 518 nm (3) 1035 nm (4) s
i t
325 nm
19.
er s
The frequency of light emitted fortthe transition n = 4 to n = 2e
h ofm
He+ is equal to the transition
in H atom correspondingx
E top
which of the following C [AIEEE-2011]

i s t1 y (2) n = 2 to n = 1 (3) n = 3 to n = 2 (4) n = 4 to n = 3

(1) n = 3 to n = r

h e m
C
134
 Atomic Structure
20. The electrons identified by quantum numbers n and l : [AIEEE-2012]

ts energy as s
(a) n = 4 ,  = 1 (b) n = 4,  = 0 (c) n = 3,  = 2 (d) n = 3,  = 1
r r t
Can be placed in order of e
(1) (a) < (c) < (b) E xp
increasing
(a)x
(2) (c) < (d) < (b) < E
pe
t
(3) (d) <s(b)r y < (d)
s <r
t y
If m
i < (c) < (a)
i
(4) (b) < (d)
m
(a) < (c)

Ch
21. e Ch e
the kinetic energy of an electron is increased four times, the wavelength of the de-Broglie
wave associated with it would become : [JEE-Main(online) 2012]
(1) Two times (2) Half (3) One fourth (4) Four times
22. If the radius of first orbit of H atom is a 0, the de-Broglie wavelength of an electron in the third
orbit is : [JEE-Main(online) 2012]
(1) 6  a0 (2) 8  a0
r t s (3) 2  a (4) 4  a
e emission line in the Balmer series of H-Spectrum is :
0 0

The wave number of thepfirst

23.
E x r t s
y
str (2) 9 R
(R = Rydberg constant) :
e
xp (4) 7 R
(1) 3 m R i RE
e y
5
h t
(3)
s r
24. CThe de Broglie wavelength of a car of mass i1000 kg and velocity 36 km/hr is :
4 400 36 6

e m
–34
Ch [JEE-Main(online) 2013] ts
r
(1) 6.626 × l0 m (2) 6.626 × 10 m (3) 6.626 × 10 m (4) 6.626 × 10 m pe
(h = 6.63 × l0 Js)
–31 –34 –38

E x the de-
–30

25.
s t
For which of the following particles will it be most difficult to experimentally
r y verify

m i
Broglie relationship?
s e [JEE-Main(online) 2014]
(3) a proton Ch (4) an a-particle
(1) a dust particle
r t
(2) an electron
If the binding energy of p theeelectron in a hydrogen atom is 13.6 eV, the energy required to
26.
x
Efrom the first excited state of Li is :
t ry
remove the electron ++
[JEE-Main(online) 2014]

m is s
e t
(1) 13.6 eV (2) 30.6 eV (3) 122.4 eV (4) 3.4 eV
27. h
C Based on the equation
p e r[JEE-Main(online) 2014]
E x
try
 1 1 
E = –2.0 × 10 J   
s
–18
2
n n 
2

m i
e
2 1

C
the wavelength of the light that must h be absorbed to excite hydrogen electron from level n = 1s
r t
–34 8 –1
xp e
× 10E m
to level n = 2 will be (h = 6.625 × 10 Js, C = 3 × 10 ms )
(3) 1.325 × 10 m (4) 5.300y
r the velocity of
–7 –7 –10 –10
(1) 2.650 × 10 m (2) 1.325 × 10 m
is tlight,
28. 0

photoelectron ejected from thee r tssurface is

If  and  be the threshold wavelength and wavelength of incident
h em[JEE-Main(online) 2014]
E x p metal
C
2hc     y
 str  (2)
 2h  1 1  2h 2hc
     
m i  
  
0
(1) (3) (4)
m m  
0 0

e
m m
h
0 0

C
135
 Atomic Structure
29. Ionization energy of gaseous Na atoms is 495.5 kjmol –1. The lowest possible frequency of light

s s
that ionizes a sodium atom is

e r t
(h = 6.626 × 10–34 Js, NA = 6.022 × 1023 mol–1)
e r t
[JEE-Main(online) 2014]
(1) 3.15 × 10 s
E x(2)p4.76 × 10 s (3) 1.24 × 10 s E(4)xp7.50 × 10 s
15 –1 14 –1 15 –1 4 –1

Which of t
s r yof hydrogen?
yfollowing is the energy of a possible excitedststate
r
30.
m i the
m i
e
Ch (1) –3.4 eV (2) +6.8 eV
e
Ch(3) +13.6 eV
[JEE-Main(offline) 2015]
(4) –6.8 eV
31. At temperature T, the average kinetic energy of any particle is kT- The de Broglie wavelength
follows the order : [JEE-Main(online) 2015]
(1) Visible photon > Thermal electron > Thermal neutron

ts
(2)Thermal proton > Thermal electron > Visible photon
e r
xpphoton > Thermal electron
(3)Visible photon > Thermal neutron > Thermal electron
(4) Thermal proton > E
y er ts
tthersecond Bohr orbit for hydrogen atom Eis :xp
Visible
32.
is
The radius of
mconst. h = 6.6262 × 10 Js
[JEE Main 2017]

h e –34

st r y
Cmass of electron = 9.1091 × 10 kg mi
(Plank's

heC
–31

charge of electron e = 1.60210C × 10 –19

e r t s
permittivity of vacuum  = 8.854185 ×10 kg m A )
0
–12 –1 –3 2

E x p
(4) 2.12A y
(1) 1.65A (2) 4.76A (3) 0.529A
is tr
33. i f

h e m
For emission line of atomic hydrogen from n = 8 to n = the plot of wave number

r ts
  against  1  will be (The Rydberg



e constant, R is inC
xp
  H wave number unit).
  n 
2

ry E
t
iswith slope - R
[JEE Main (Jan.) 2019]

h e m
(1) Linear- H

Rt
s
(2) Linear with intercept - R
r
H

(3) Non linear e

C Which of the following combination of statements is truexpregarding the interpretation of the
(4) Linear with slope H

34.
r y E
atomic orbitals ?
m i st [JEE Main (Jan.) 2019]
(a) An electron in an orbital of high e
h
C momentum.
angular momentum stays away from the nucleus than an
r ts
electron in the orbital of lower angular e
xis pinversely
(b) For a given value of the principal quantum number, the size of the orbit
r y E
proportional to the azimuthal quantum number.
s t
i is equal to h .
(c) According to wave mechanics, t
e r s
the
h e m
ground state angular momentum
x various azimuthal quantum C
p 2
(d) The plot of  VsE
try
r for numbers, shows peak shifting towards

is
higher r value.
m
C h e
(1) (a), (c) (2) (a), (d) (3) (b), (c) (4) (a), (b)

136
 Atomic Structure
35. Which of the graphs shown below does not represent the relationship between incident light

s s
and the electron ejected from metal surface? [JEE Main (Jan.) 2019]

er t er t
Exp Exp
stry stry
i i
(1) (2)

he m h e m
C C
(3) (4)

e r ts
36.
E xp
The ground state energy of hydrogen atom is –13.6 eV. The energy of second excited state He +
r t s Main (Jan.) 2019]
ion in eV is : y
tr (2) –6.04 e
p (4) –27. 2
[JEE
(1) –54.4 is (3) –3.4 Ex
h e m try of wavelength of about 900 nm. Which
37. CHeat treatment of muscular pain involves iradiation
m s
spectral line of H-atom is suitable h fore
C this purpose ? [JEE Main (Jan.) 2019]
e r ts
x3p
5 –1 –34 8 –1
[R = 1 × 10 cm , h = 6.6 × 10 Js, c = 3 × 10 ms ]
E
H

(1) Paschen, 5  3 (2) Balmer,  2 (3) Lyman,  1 (4) Paschen,
s t r y 

m i
38.
s C h e
The de Broglie wavelength () associated with a photoelectron varies with the frequency (v) of

r
e 1 t
the incident radiation as, [v is threshold frequency] : [JEE Main (Jan.) 2019]
p
0

1
E x 1 1
(1)  
(vs–tvr)
y (2)
1
  (3)  
(v – v )
1
(4)   3

i 2
(v – v ) 4

mis the work function of the metal if the light of wavelength

0
(v – v )
s 4000 Å generates
2

e t
0 0 0

39. h
C photoelectrons of velocity 6 × 10 ms form it ? e r
xp
What
–1
E
try
5

(Mass of electron = 9 × 10 kg –31

m i s
C
8
h e –1

ts
r
Velocity of light = 3 × 10 ms
Planck's constant = 6.626 × 10 Js –34
e
xp2019]
r y E
t
–19 –1

s
Charge of electron = 1.6 × 10 JeV ) [JEE Main (Jan.)
(4)i4.0 eV
(1) 2.1 eV (2) 3.1 eV
e t s em
rthe electron in nth BohrCorbith in a hydrogenic atom is equal to
(3) 0.9 eV
40.
E
If the de Broglie wavelength p
xthen the value of n/z is :
of
1.5 a (a is Bohry
0
is
0
t r radius), [JEE Main (Jan.) 2019]

e m
Ch
(1) 0.40 (2) 0.75 (3) 1.0 (4) 1.50

137
 Atomic Structure
41. The quantum number of four electrons are given below : [JEE Main (April) 2019]

s s
1 1
I.
e r t
n = 4, l = 2, ml = – 2, ms = –
2
II.
r
n = 3, l = 2, m = 1, m = +
l

e t 2
s

1, x
n = 4, l = E
p mx
n = 3, l = 1, E
p 1
y y
1
III.
i s t r m = 0, m = +
l
2
sIV.
is t r = 1, m = –
l
2
s

(1)m I < III < II < IV (2) IV < III < II < I (3) I m
e
Ch If p is the momentum of the fastest electron e
Chejected from a metal surface after the irradiation of
< II < III < I (4) IV < II < III < I
42.
light having wavelength , then for 1.5 p momentum of the photoelectron, the wavelength of
the light should be : (Assume kinetic energy of ejected photoelectron to be very high in
comparison to work function) : [JEE Main (April) 2019]
3
e r ts (3) 1 
4 2
xp
  (4) 
s
(1) (2)
4
r
For any giventseries
E 9 2
t
y of spectral lines of atomic hydrogen,xletper –  be the difference
3
43.
m is E max min

e t r y
Ch s
–1
ratio  / 
in maximum
m i
and minimum frequencies in cm . The Lyman is:
Balmer

h e
C ts
[JEE Main (April) 2019]

e r
xpatom is
(1) 4 : 1 (2) 5 : 4 (3) 9 : 4 (4) 27 : 4
E
try(April) 2019]
44. Which one of the following about an electron occupying the 1s orbital in a hydrogen
incorrect ? (The Bohr radius is represented by a )
m[JEEisMain
e
0

r ts
(1) The electron can be found at a distance 2a from the nucleus
C h
e
0

(2) The total energy of thep

E x energy is double that of its kinetic energy on an average.
electron is maximum when it is at a distance a from the nucleus.
0

s t r
(3) The magnitude y of potential

m i
e
(4) The probability
45. Ch r ts
density of finding the electron is maximum at the nucleus.
e
xp [JEE Main (April) 2019]
2
The graph between || and r(radial distance) is shown below. This represents:
E
i s try
h e m
C e r ts
E xp
s t r y
t s m i
e r C h e
x p
E(2) 3s orbital
(1) 1s orbital
s tr y (3) 2s orbital (4) 2p orbital

m i
C h e
138
 Atomic Structure
46. The ratio of the shortest wavelength of two special series of hydrogen spectrum is found to be

s s
about 9. The spectral series are : [JEE Main (April) 2019]

e r t er t
(1) Paschen and Pfund
E x p (2) Balmer and Brackett
E xp
s tr y
(3) Lyman and Paschen (4) Brackett
s r
and
t yPfund

m i m i
The electrons are more likely to be found: he
47. he
C C [JEE Main (April) 2019]

er ts
E xp r t s
s tr y x p e
i
min the region c E
ythe region a and c
h e
C(3) only in the region a
(1) only
s r
(2)tin
i(4) in the region a and b
e m
Ch e r ts
The radius of the second Bohr orbit, in terms of the Bohr radius, a , in Li is : Ex
p
y
2+

r
48.
t
0

2a 4a 2a
m i s
4a
e
0 0 0 0
(1) (2) (3) (4)
3 3
r t s
9
C h 9

x p e [Jee Main (Jan. 2020)]

ry E
i s t
m
th

s4a
49. The de Broglie wavelength of an electron in the 4 Bohr orbit is: [Jee Main (Jan. 2020)]

Ch(1)e6a e r t
xp 1 1 
0 (2) 8a 0 (3) 2a 0 (4) 0

E
50.
i
For the Balmer series in the spectrum of H atom,
stry  R  n  n  , the correct statements
m
H 2 2

e
1 2

C h [Jee Main (Jan. 2020)]ts

r
e
among (I) to (IV) are :
(I) As wavelength decreases, the lines in the series converge
E x p
s tr y
(II) The integer n is equal to 2
1

tscorresponds to n = 3 hem i
e r
(III) The lines of longest wavelength

xpof hydrogen can be calculatedCfrom wave number of these lines

2

E
(IV) The ionization energy

i s try (2) (I), (II), (III) (3) (II), (III), (IV) (4) (I), (II), (IV)
(1) (I), (III), (IV)

h e m
C
139
 Atomic Structure
51. The figure that is not a direct manifestation of the quantum nature of atoms is :
[Jee-Main (Sep) 2020]

e r ts e r ts
Intensity of
x
E Tp T2 > T 1 Internal
xp
E 500 600
energy of
(1)
radiationry
black
s
body
t
(2)
stry Ar
i i
1 300 400

he m hem Temperature (K)

C Wavelength
C Rb K
Increasing wavelength Kinetic Na
energy of
(3) (4) photoelectrons

s
Absorption spectrum
t
Frequency of incident

e r radiation

E xp r t s
s
The work ifunction
y
tr of sodium metal is 4.41 × 10 J.EIfxphotons
–19
e
p of wavelength 300 nm are
52.
h e mon the metal, the kinetic energy of the ejected
t r y electrons will be
C(h = 6.63 × 10 J s; c = 3 × 10 m/s) _________
incident
–34
m s
i × 10 J. –21

e
8
[Jee-Main (Sep) 2020]

Ch er ts
The region in the electromagnetic spectrum where the Balmer series lines appear isE: xp
ry (Sep) 2020]
53.

i s t
[Jee-Main
(1) Visible (2) Microwave (3) Ultraviolet
h e m
(4) Infrared

The shortest wavelength of e r t s C

54.
Balmer series of He E x p H atom in the Lyman series is  . The longest wavelength in the
1

y
+

r (2) 5
is : [Jee-Main (Sep) 2020]
9
i s t 36 27 
m s
1 1 1 1
(1) (3) (4)

Ch e 5 9 5
e r t 5

The difference between the radii of 3 and 4 orbits ofE x p

y Li is R . The difference between the
rd th 2+
55.
t r is :
1

i
radii of 3 and 4 orbits of He is R . Ratio R
s R
rd th +
: [Jee-Main (Sep) 2020]
m
2 1 2
(1) 3 : 8 (2) 8 : 3
Ch e (3) 2 : 3 (4) 3 : 2
ts
er
E xp is :
56.
ry (Sep) 2020]
The correct statement about probability density (except at infinite distance from nucleus)
s t
t s (2) It can be zero form i [Jee-Main
(1) It can negative for 2p orbital
(3) It can never be zero for 2s e r (4) It can beC
e
hfor 3p orbital
1s orbital

E xp orbital zero

s t ry
m i
C h e
140
 Atomic Structure

EXERCISE # (JEE-ADVANCED)
1.
r s
The quantum numbers +1/2 and –1/2 for the electron spin represent:
t e r t s
ein clockwise and anticlockwise directionxrespectively.
[JEE 2001]

E x p
(A) rotation of the electron
E p
s t r y s t r y
m i
(B) rotation of the electron in anticlockwise and
i
clockwise
m
direction respectively.

Che h e
C and down respectively.
(C) magnetic moment of the electron pointing up

(D) two quantum mechanical spin states which have no classical analogue

2. Rutherford’s experiment , which established the nuclear model of atom, used a beam of :–

e r t s
(A)  - particles, which impinged on a metal foil and get absorbed. [JEE 2002]

E
(B)  - rays, which impinged p
x metal foil and ejected electron. rts
on a

(C) Heliumis trywhich impinged on a metal foil and Egotxscattered.

pe
h e m atoms,
t r yand got scattered.
C m i s
e
(D) Helium nuclei, which impinged on a metal foil

The magnetic moment of cobaltC ofh

the compound Hg[Co(SCN) ] is [Given : Co ] [JEE 2004]ts
3. 4
+2

p e r
(D) 24 y E
x
(A) 3 (B) 8 (C) 15
is tr
The radius of which of the following orbit is same as that of theefirst
h mBohr’s orbit of hydrogen
s
4.

e r t C
p
atom? [JEE 2004]

E x Li (n = 2) (C) Li (n = 3) (D) Be (n = 2)
y
+ 2+ 2+ 3+
(A) He (n = 2) (B)

is t r
5.
e m
(a) The Schrodinger wave equation for hydrogen atom is
r t s [IIT-2004]

Ch x p e
 
E
3/ 2
 1  r
try
1
  2  e
–r/a
 = 0

s
2s
4  2   a  
i
1/2
a 
m
0 0

Where a is Bohr's radius. Let the h e

Cradial node in 2s be at r . Then find r in terms of a . erts
xpvalue of
0 0 0 0

(b) A base ball having mass 100 g moves with velocity 100 m/s. find out the
r y E
wavelength of base ball.
s t
i(Given r = a )
6.
e r s
(a) Calculate velocity of electron intfirst Bohr orbit of hydrogeneatom
horbit.m
p C
0

E x
(b) Find de-Broglie wavelength of the electron in first Bohr [IIT-2005]

(c) Find theis tryangular momentum of 2p-orbital in terms of h/2 units.

h e m orbital

C
141
 Atomic Structure
7. Given in hydrogenic atom rn, Vn, E, Kn stand for radius, potential energy, total energy and
kinetic energy in nth orbit. Find the value of U,v,x,y.
s s
[JEE 2006]

er t er t
p p
Vn
x x
(A) U= (P) 1

r y E Kn

r y E–2
(B)
isrt
1
 E x

ist (Q)

he m r Z n

hem (R) –1
C C
y
(C) n

(Z = Atomic number)
(D) v = (Orbital angular momentum of electron (S) 0
in its lowest energy )
8. Match the entries in Column I with the correctly related quantum number(s) in Column II.

e r ts
Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the

E xp r t s
trIy
ORS. [JEE 2008]

s x p e Column II
(A) em
i
Column
y E (P) Principal quantum number
Ch electron in a hydrogen-like atomicmorbital
Orbital angular momentum of the
ist r
(B) Chewave
A hydrogen-like one-electron (Q) Azimuthal quantum numberts
e r
function obeying Pauli principle
E x p
s y number
trquantum
(C) Shape, size and orientation of hydrogen (R)
m i
Magnetic
like atomic orbitals
s h e
C(S) Electron spin quantum
e r t
xp
(D) Probability density of electron at the nucleus

y E
tr
number in hydrogen-like

m is s
atom

h e
C The hydrogen-like species Li is in a spherically symmetric e r t
xp state S with one radial node.
Paragraph for questions 14 to 16

E
trtoya state S . The state S has one radial node
2+
1

i s
menergy of the hydrogen atom.
Upon absorbing light the ion undergoes transition
e
2 2

C h
and its energy is equal to the ground state
r
[JEE 2010]
ts
9. The state S is :-
xp e
(D) 3s y E
1

(A) 1s (B) 2s (C) 2p

i s tr
10.
r t s e m
Energy of the state S in units of the hydrogen atom ground state energy
1

e h
is :-

p (C) 2.25 C
(A) 0.75
x
E quantum number of the state S is :-
(B) 1.50 (D) 4.50
11.
s r
The orbital angulary
t (B) 1
momentum
i
2

e
(A) 0
m (C) 2 (D) 3
Ch
142
 Atomic Structure
12. The maximum number of electrons that can have principal quantum number, n=3, and spin

tsmetals is listed below. The number of metals s

quantum number, ms = – 1/2, is [JEE 2011]
The work function () of e r e r t
13.
E p some
p which will show
x is : – [JEE 2011]
x light of 300 nm wavelength falls on theEmetal
s t r y
photoelectric effect when
s tr y
m i m i
e e
Metal Li Na K Mg Cu Ag Fe Pt W

Ch Ch
2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75

14. The kinetic energy of an electron in the second Bohr orbit of a hydrogen atom is
[a0 is Bohr radius] [JEE 2012]
h2 h2 h2 h2

ts
(A) (B) (C) (D)
42 ma 02 162 ma 02 322 ma 02 322 ma 02
The atomic masses of Hexand e r
p Ne are 4 and 20 a.m.u. respectively. tThes value of the de Broglie
15.
r E erwavelength of Ne at 727 ºC.
ygas at –73 ºC is "M" times that of the dexBroglie
is t
wavelength of He
E p
M is. m y
h e
CIn an atom, the total number of electronsmhaving t r
is quantum numbers n = 4, |m | = 1 and m = – 1
[JEE 2013]

Che s
16. 
t
s

r
2

x p e
E
is [JEE 2014]
P is the probability of finding the 1s electron of hydrogen atom in arspherical
st y shell of
i of this shell is 4r dr.
17.

h e m
infinitesimal thickness, dr, at a distance r from the nucleus. The volume 2

e r t s
The qualitative sketch of the dependence of P on r is - C [JEE 2016]

E xp
y (B)
P P P P

is tr
h
(A)
e m (C)
r t s
(D)

C xp e
E
try the information given in the three
O r O r O r O r
Answer 18, 19 and 20 by appropriately s
i
columns of the following table. hem
matching

C
is a mathematical functions whose value depends upon p e rts
The wave function  n,l.m1
E x spherical

s t y
polar coordinates (r,q,f) of the electron and characterized by the quantumrnumber n,l and m .

tscolatitude and  is azimuth .m

i 1

r
Here r is distance from nucleus, is
e C h e In the mathematical functions

E xp number and a is Bohr radius.

given in the Table, Z is atomic

try
0

m is
C h e
143
 Atomic Structure
Column 1 Column 2 Column 3

r t s
e (i) 
3

er ts
 Zr 

(I) 1s orbital
Exp   e  0 
(P)
E p
 Z  2  a 
x
y y
n,l .m1
 a0 
i s t r istr
he m hem
C C r/a 0

(II) 2s orbital (ii) One radial node (Q) Probability density at

1
nucleus  3
a0

tsZ 
(iii)  er   re
5
 Zr 
 

p
2

x cos 
 2a 0 

s
(III) 2p orbital (R) Probability density is
E t
z

r
n,l ,m1
 a 

tr y e
0

is E x p
maximum at nucleus

e m
h 3d orbital (iv) xy-plane is a nodalisplane tr y
C(IV) 2

m (S)Energy needed to excite electron

Che
z

ts
from n = 2 state to n = 4 state is
e r
xp
27

E
times the energy needed to

yn = 2 state to
32

i s t r
excite electron from

e m [JEE Adv. 2017]

n = 6 state
h
e r t s C
xp(II) (ii) (Q) (C) (I) (iii) (R) (D) (I) (i) (R)
+
18. For He ion, the only INCORRECT combination is
(A) (I) (i) (S)
r y E (B)

s t
i orbital in Column I, the Only CORRECT combinations for any hydrogen-like
19.
e m
For the given
r t
Chspecies is e
x(R)p (D) (III) (iii) (P)
E
try is
(A) (II) (ii) (P) (B) (I) (ii) (S) (C) (IV) (iv)

i s
(B) (I) (iv) (R)em (C) (II) (i) (Q)
20. For hydrogen atom, the only CORRECT combination
(A) (I) (i) (P)
Ch (D) (I) (i) (S)
e r ts
The ground state energy of hydrogen atom is –13.6 eV. Consider an electronic E xp of He +

y–3.4 eV, 2 and 0,

21. state
whose energy; azimuthal quantum number and magnetic quantum number
s t r
i ? [JEE Adv. 2019]
are
respectively. Which of the followingsstatement(s) is(are) true for them
e r t h e state
(1) It has 2 angular nodes
E x p C
r y
(2) It has 3 radial nodes
s t
i
(3) The nuclear charge experienced by the electron in this state is less than 2e, where e is the
m of the electronic charge
h e magnitude
C(4) It is a 4d state.
144
 Atomic Structure
22. Answer the following by appropriately matching the lists based on the information given
in the paragraph
r t s r t s
e moves around the
e of a one electron atom where the electron
x p
Consider the Bohr’s model
x p
E List-I contains some quantities forrythe nEorbit of the atom and List-II
nucleus, In theyfollowing,
i s t r ist
th

e m e m
Ch Ch
contains showing how they depend on n. [JEE Adv. 2019]
List-I List-II

(I) Radius of the nth orbit (P) n–2

(II) Angular momentum of the electron in the nth orbit (Q)  n–1

e r t s
(III) Kinetic energy of the electron in the nth orbit (R)  n 0

(IV) Potential energy of xthep

y E electron in the n orbit (S)  n
th

e r t s 1

is tr E x p n
(T) 2

h e m t r y (U)  n
C s
mi combination considering List-I and List-II?
1/2

Which of the following options hashthe e

C ts
correct

p e r
(1) (I), (T) (2) (II), (Q) (3) (I), (P) (4) (II), (R)
E x
The figure below is the plot of potential energy versus internuclear distancer(d)
s t yof H molecule
i E (as indicated in
23. 2

the figure) in kJ mol , for d=d sat which the electron-electron h m

e repulsion and the nucleus-
in the electronic ground state. What is the value of the net potential energy 0
–1

e t C
rabsent? As reference, the potential energy of H atom is taken as
0

x p
nucleus repulsion energies are
E
r y
t constant as 6.023 ×10 mol .
zero when its electron
s
and the nucleus are infinitely far apart. [JEE Adv. 2020]

m i
Use Avogadro 23 –1

s
Ch e e r t
E dx
p
y
Potential Energy

is t r H H
 kJ mol 
–1

m
Che ts
E
r
0

xp e
r y E
d 0
i s t
e r t s
Internuclear distance (d)
h e m
E x p C
s t ry
m i
C h e
145
 Atomic Structure

ANSWER KEY

r ts EXERCISE # (JEE-MAIN)
r ts
3. e 1 6. pe2
1. 1 2. 3
xp 4. 3 5. 1
x 7. 3

y E 2y E13.
8. 3
tr
i16.s 1 17. 3
9. 4 10. 1 11. 3 12.
tr
is 2 20. 3 21.
4 14. 1

m m
e 26. 1 27. 2 28.
Che1 23. 3 24. 3
15. 4 18. 1 19. 2
22. 25. Ch
1 1
29. 3 30. 1 31. 1 32. 4 33. 4 34. 2 35. 2
36. 2 37. 4 38. 1 39. 1 40. 2 41. 2 42. 2
43. 3 44. 2 45. 3 46. 3 47. 2 48. 2 49. 2
50. 2 51. 2 52.
e r ts
222.00 53. 1 54. 1 55. 3 56. 4

E xp r t s
s tr y x p e
D em
i EXERCISE # (JEE-ADVANCED)
y E
1.
h 3. C 4. D
t r
C(a) 2.197 × 10 m/s (b) 3.31 Å (c)m2i.sh 7. (A) Q, (B) P, (C) R, (D) S
2. D 5. (a) r = 2a
0 0
–25
(b) 6.626 × 10 Å

Che 2
6

s
6.

e r t
8. (A) Q,R); (B) (P,Q,R,S) ; (C) (P,Q,R) ; (D) (P,Q)
E xp
Cry 15.
9. B 10. C 11. B 12. 9 13. 4 14.
st
21. i 1
5
16. 6 17. B 18. C 19. A 20. D
h e m 22. 2
23. (–5246.49)
e r t s C
E xp
s tr y
m i s
Ch e e r t
E xp
is try
h e m
C e r ts
E xp
st r y
t s m i
e r C h e
E xp
s tr y
m i
C h e
146
 Atomic Structure
HINT AND SOLUTIONS
EXERCISE # (JEE-MAIN)
r ts
e4  3.14  9.218  10
6.6 10
e r ts –34

p p
h –28
x. v = x =
1.
E x 4m
=2.86× 10 m
x
E= 13.6 = 1.51 eV.
–6

r y
2 excitedtstate
s n ist
13.6
ry
i
nd rd
2. will be the 3 energy level. E = eV or E
m m
n 2

e C 10e
9
6.6 h
3.Ch x. v =
–34
h –28 –1
v =  v = 2.1 × 10 ms . 5
4m 4  3.14  25 10
4. The value of  (azimuthal quantum number) for s -electron is equal to zero.
h
Orbital angular momentum =  (   1).
2

s
h
r t
Substituting the value of l for s-electron =
Fe = 1s , 2s , 2p , 3s , 3p p e
0(0  1).
2 
0

x s
2 2 6 2 6 6 2

, 3sE t
5. , 3d , 4s ,
r
26

Fe = 1s , 2s , 2py e
tr p
++ 2 2 6 2 6 6

s x
, 3p , 3d

m i y E
e
2+

r
The number of d -electrons retained in Fe = 6.

6. C =
h   s t
= 11.05 × 10 i = 1.105 ×10 metres.
34

m
h 6.63 10 1000
e
–34 –33

mv 60 10
h
C in the first orbit and its energy increases as n increases.eHere
r ts
xp
7. The electron has minimum energy

To yellow region i.e., 5. In order to obtain less energy electron tends to come 1y orE2 orbit. So
st nd rd
n represents number of orbit, i.e., 1 , 2 , 3 ..........The thired line from the red end corresponds.

tr
st nd

jump may be involved either 5 1 or 5 

m is
8. 
For 4 orbital electrons, n = 4
s C h e
 = 3, m = + 3, + 2, + 1, 0, –1,r–2,
e t
p
–3 s = + 1/2.

1y
E x
 R  str ;
 1  1 1 
ni n 
1 1 –1 –9
9. = 1.097 × 10   m
7
= 91 × 10 m = 91 m.  

h

e m 
2
2
 1  
r t s
2 2

e
1 2

10. C For hydrogen the energy order of orbital is 1s < 2s = 2p < 3s p

x
E= 5 (given)
= 3p = 3d < 4s = 4p = 4d = 4 

st
nh
r y
11. Angular momentum of the electron, mvr =
5h e h m i
2
where n

 Angular momentum =
C2h 2.5  
e r ts
12. According to Heisenberg's uncertainty principle
E xp
h
s t ry
x× p= 
4


t s m i

4 pe
h
 xr=
h

C h e 0.001

–3 –1

x10
x × (m. v) = ; v= × 300 = 3 × 10 ms

x = try
E 4m.v
34
100

s
6.63
i
–2
  = 1.92 × 10 m.
m
31 3
4  3.14  9.110  3 10

C h e
147
 Atomic Structure
13. I.E. = 1.312 × 106 J mol–1

s s
The energy required to excite the electron in the atom from n 1 = 1 to n = 2.

er t  1
er t
E x p
= 1.312 × 106 1   = 9.84 × 105 J mol–1
 4
Exp
ry
v = ist × 600 = 3 × 10 ms stry
14.
m

0.005 –3 –1

mi
Ch e 100
6.63 10 34
Che
x = = 1.92 × 10–2m.
4  3.14  9.11031  3 103
h 6.63 1034
15. =  = 3.97 × 10–10 = 0.397 nm.
mv 1.67  10 1000
–27

16. Cl–Cl(g) 
 2Cl(g) 
e r t s 242  10
H =
J molecule 242 KJ mol =
3
–1

xp 6.6 10  310

6.02 10 23

242  10 E
y e r t s
tr6.02
23 34
 10 3 8

p
hc
E=

m
=
i s =

E x
h e s t r y 10 = 494 10 m = 494 nm
C 242 10 10 i
34
6.6 10  3 10 6.6  3  6.02 8
–6 –6 –9
 = = 23

e m10 3
= 0.494   

Ch
242

er ts
17. +
I.E. of He = 19.6 10 J atom 
–18 –1

E xp
I.E. = – E
s try
i
1

1
+
E for He is = – 19.6 × 10 J atom –18

h e m –1

(E ) 1 He (Z )
e r t
He s2
C
xp
=
E
2
(E ) 1 Li3(Z ) Li2

19.6 10 try

(Em
i s =
4 18

s
Ch e ) 1 LI2 9
e r t
19.6  9  10
= – 4.41 E
18 p
10x J atom
try
2+ –18 –17 –1
E (Li ) = = – 44.1 10  
s
1

i
4

h e m s
18. E=E +E C er t
xp
1 2

E
hc hc hc 1 1 1 1 1 1
  ;   ;  
      355 680 
s t r y
i
1 2 1 2 2

2 = 742.76 nm.
e r t s h e m
E x p C
st r y
m i
C h e
148
 Atomic Structure

 1 1 
19. h = E = 13.6 z2  2  2 

er ts  n1 n 2 

er ts
Exp 





Exp 


s ry
He+ = H × z 
t
2 1

1 
= H
str
 1  1 y
mi   n1  2  n 2  2 
i
  2 2  4 2 
m
Che     
 2   2   e
    
h
2 2 
C
For H-atom
n1 = 1, n2 = 2
20. (a) 4 p (b) 4 s (c) 3 d (d) 3 p
Acc. to (n + ) rule, increasing order of energy (d) < (b) < (c) < (a)

er ts
=
h
E xp r ts
y e
21.
2mKE
istr Exp
h e m 2(9 a ) = 3 try
22. C2r = n
mis
e
0

6  a 0
C h r ts
1  1 1  1 1 1 5
xpe
23.  R 2  2  ; =R  2  2 = R
E
try
  n1 n 2    2 3  36
6.63 1034
mis
e
h
24. = 
mv 1000  36 1000
r t s Ch
x p e
For macro particles E
25.
s t r y (having larger mass) will be most difficult to experimentally verify the de-

m i
Broglie relationship.
s
h e
26. C E = e r t
xp
13.6 Z 13.6  9
2

E
= =30.6 eV
y
2
n 4

is t r
E = –2.0 × 10 J    = 1.5× 10 eJm
 1 1  6.63 10  3 10 –34 8

Ch
–18 –18

ts
27. =
 4 1 
e r
 = 1.325 × 10 m –7

E xp
s tr y
t s m i
28. KE = Ep – W
e r     C h e
1 2 hc hc
– x p
E m   
2hc
 
0

y
mv = ; v=
2 
2hc is
t r
0 0

(4) em    
Ch m
0

149
 Atomic Structure

495.5 103 6.63 10–34  3 108

29. E= =
6.023 1023 

e r ts er ts
30. (E ) = – 13.6×
n H
x p
E= – 3.4 eV
eV
12

Exp
y y
n2
n=2
i s tr E
istr
m= KT = 1 mv m
2

31. he
C KE
3
2 2
2

Che
h
=
mv
h
=
2mK  E

er ts
xp
h
ts
=

2 ry
3
2m  KT E er
is t Exp
 em ry
h t
1
C m
mis
h e
C r ts
2 2
n h
32. r=
4 me k
2 2

xpe
E
r=
22 (6.6262 1034 Js) 2
istry
4  (3.1416)2  9.10911031 kg  (1.60210 1019 C)  9 10
m
2 9

s C h e
r = 2.12 × 10–10 m
er t
r = 2.12 Å
x p
1E
 = R Z  try
 1   1 1
is n n 
  
2 2
33.  =R ×1 × 
m
H H

s
2 2 2 2
n 8 
h e
C  =R × n –R × 8
f i

er t f

1 1
Exp
ry
H 2 H 2

st
f

1
m i
curve of  v is linear s

C h e 2

ts
r
n
with slope = R e
xpthan an
E
H

34.
r y  n.
An electron in an orbital of high angular momentum stays away from the nucleus
s t
s m i
electron in the orbital of lower angular momentum since angular momentum(L)
t
e r quantum numbers,
The plot of  Vs r for various azimuthal
C h e
p
shows peak shifting towards higher

E x
try
r value.

m i s
C h e
150
 Atomic Structure
35.  Graph (2) is wrong

s s
(KE)max = hv - hv

e r t er t
p p
Y = mx + C

E x Ex
y y
Because this graph have a negative intercept.

i s t rz ev 2
istr
36.
he m n atom
E = –13.6
T 2

h em
C For He +
C
22
ET = –13.6 × 2 = – 6.04 ev
3
124 1240
eV =
ts
37. Energy of wave = eV = 1.37 eV
(nm)
r
900

xp e
for paschen seriesy E
er ts
This wave belong to paschen series of atomic spectra

is 1t
r xp
e m× 9 = 1.51 eV
E = 13.6
ry E
h
CSo transition should be  3 ist
e m
38. hv = hv + K.E. ...(1) Ch er ts
xp
0

h2
E
try
K.E. = ...(2)
2m 2
mis
Putting (2) in (1)
s Che
er
h2 t h 2
 hv = hv0 +
Exp 
2m 2
h(v – v ) =
2m
0 2

s try1
i (v – v )
1
   2
 

h e m r ts
1

e
0
(v – v ) 2

C xp
0

ry E
hc
is t
m
39. = kE + W
e
o

C h r ts
1
kE =  9 10  36 10 –31 10

xpe
2

ry E
= 162 × 10–21 J =
162  10 –21
= 1 ev
ist
r ts 1.6  10 19
em
E xp e
Energy of incident light =
12400
ev = 3.1 ev Ch
try= 2.1 ev
4000
 W i=s3.1–1

h em o

C
151
 Atomic Structure

n2
40.  2 rn = nr & rn = ro ×

s s
z

er t er t

xp
n2 
 2  ro   = n (1.5ro)
E Exp

n 1.5ist
r yz 
stry
m mi
Che2

2
= 0.75
Che
41. (I) n = 4 l = 2 ml = –2 ms = –1/2 represents e– present in 4d orbital
(II) n = 3 l = 2 ml = 1 ms = +1/2 represents e– present in 3d orbital
(IV) n = 4 l = 1 ml = 0 ms =+1/2 represents e– present in 4p orbital
represents e– present in 3p orbital
ts
(V) n = 3 l = 1 ml = 1 ms = –1/2

per
According to (n+l) rule,order of energy will be
4dx
3p < 3d < 4p <E ts
t r y per
s
K·E = hv –iw
m Ex
y
42.
e r
0

h
Chv > > > w 
 K.E >>>w 
ist
m
0

h e
C ts

r
0

hc
xpe
 K.E = hv =
E
try

1
mis
 K·E 

s Che
r t
e 
 K·E =
p
2m E xp 2
p2 
1

s t r y 

i  p   p 
em      ts
2 2

r
4
h  
e 2 = 1
2 1 1

C   p   1.5p 
x p 9
E
1 2 1

43.
s
For Lyman series maximum frequency of photon
t r y will be observed when electron makes

makes transition from n = 2 to n = 1 e m i

transition from n =  to n = 1 and a photon of minimum frequency will be observed when

C h r ts
1
=R Z  –  2 1
xp e
E
C 2 2
n n  1 2

st r y
4 mi
1 1  1 1  3R Z R Z 2 2
 = R Z    –R Z    = R Z –
1 ts
2 2
 2 C C

r e
C C C
1  
Lyman
4
e h
4
For Balmer series
E xp C
i stryfrequency n =  to n = 2
Maximum

h e mMaximum frequency n = 3 to n = 2
C
152
 Atomic Structure
  1 1 1 1 R Z2 5R Z2 R Z2
 Balmer = RCZ2  2   –RCZ2  2  2  = C – C  C
2  2 3 
s s
4 36 9
R C Z2
e r t er t
 Lyman
E x p
 4 2 
9
Exp

st r y R CZ 4
stry
i i
Balmer

m m
9
44. he ne
Total energy of electron will be maximum ath
C
45.
C =
There is only one radial node and probability of finding the electrons is maximum near nucleus,
graph belongs to 2s orbital.
46. For Lyman series

ts
1 1 1 
 max
= RHZ2 ×  2  2 
1  
p er
E x r ts
1
R Z
s tr y 2

xpe

i E
H

e m 1  try
max

C h 1 1
is
 3 em
For Pachen series =  R Z  2

  
H

h
2 2

C ts
max

er
xp
1 1
R Z  2

 max
E
H
9
1
istry
m
(max) pachen =
9
s Che
(max) Lyman = 1
e r t
( ) 9
E x p
1ry

max Pachen
( )
i s t
max Lyman

47.
h e m
We are getting maxima at point a & c
r ts
C Electrons are more likely to be found in the region a & c. xpe
r y E
m ist
he
2
n

ts
48. r=a ×
C
0
Z
er
xp
2+
for second orbit of Li

ry E
t
4 4a 0
r = a0 ×
3

3
s mis
r t e
49. r = n
Expe Ch
2 × (16a ) = 4 y
8a =  is
tr
0


h e m
0

C
153
 Atomic Structure
50. For Balmer series n1 = 2 n2 = 3,4,5........
For Balmer series , Energy of 1st line (3  2) is minimum so  will be max

e r ts er ts
Ex p
lines in series converge, Energy is increased so  is decreased
E x p
s r y ry
t of Ar will be equal to KE of Ar and KEisistexplained by KTG.
m i m
e e
51. Internal energy

C h C h
52. E = W + KEmax
KEmax = E – W
hc
– 4.41 × 10–19
ts
=


6.63  10  3x
er
p – 4.41 × 10
y E  10 34

er ts 8
–19

tr
=
p
9


m is 300 10
Ex
he = 2.22 × 10 J –19

stry
C = 222 × 10 J m i
e
–21

Ch er ts
Exp
try
53. Balmer series give visible lines For H-atom

As we know E =
hc
mis
e
54.

r

t s Ch
So  =
hc
x p ei.e.
for  minimum
E
r y E
is
shortest; E t= maximum
h m
foreLyman series n = 1 & for E r ts
C xpe max

Transition must be form n =  to n = 1

ry E
ist
1
R Z 
 1
 
1 
2

h e m
ts
So

C
H

r
2 2
n n 
e
1 1 2

1
Exp
1
= RH Z2 (1 – 0)
stry
t=s R1 mi
1
er

Che
xp
= R × (1)2 1
1
E
i stry E = minimum for Balmer series n = 3 to n = 2 will have E minimum
For longest wavelength

h e
for HemZ = 2
+

C
154
 Atomic Structure

1  1 1 
So  R H Z2  2  2 
2

er ts  n1 n 2 

er ts
E xp
1 1 1
 RH  4  
Exp
ry 2 4 9
try
is1t is
m em
Che 
5
R 
9 2
H

Ch
9
2 = 1 ×
5
42 32 7
–
R1 (r4 – r3 ) 42
ts
2
55.   32 32  3 
R 2 (r4 – r3 ) He 4 3
e r7 3

xp
–

y E 2 2 2

er ts
is tr =  2

E xp
m
56. Probability density

h e
 can2

s t r y
be zero for 3P orbital besides of infinite distance
C m i
Ch e
3p
er ts
 2

Exp
istry
hem
r
er ts C
Exp
stry
mi
Che er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
155
 Atomic Structure

EXERCISE # (JEE-ADVANCED)
1.

e r s e r s
The quantum numbers +1/2 and –1/2 for the electron spin represent two quantum mechanical
t t
E x p
spin states which have no classical analogue.
Exp
s y
 - particlesrare
s r y
t which means it has 3 unpaired
tpresent as Co which has [Ar] 4s 3d configuration,
i i
2. He nuclei.
3.
he m
Cobalt is +2

h e m 0 7

C of the compound is 3(3  2)  15

C electrons. So the spin only magnetic moment
n2 o
4. rn = 0.529 A
Z
For hydrogen, n = 1 and Z = 1 ;  rH = 0.529 Å

e r ts r = 0.529 2 = 0.529 Å 2

E x p
For Be3+, n = 2 and Z = 4 ; Be3
4
t s
r y p e r
 is=tprobability of finding electron with in 2s orbital
x
5. (a)
em
2
2s

r E
y is zero at node)
h
C For node at r = r ,  = 0 mi
 2
s t
= 0 (probability of finding an electron
at node

he
2

C ts
0

er
xp
3
1 1  r 
 =0=
E
2
So,   2 – a  ×
0
er0 / 2a0

try
4 2  a 0   0

 r0 
mis
  2 –  = 0 or 2 =
r
s Che
 a0 
e
a0
r t
 r = 2a
E x p
y
0

hr
 i=st =
6.626 10 –34
6.626 10 –34

m s
–35
or 6.626 × 10–25 Å
e t
(b) = = 6.626 × 10 m
r
3

h
3
  
e
mv 100 100 10 10, 000 10
C xp
ry E
6. (a) For hydrogen atom, Z = 1, n = 1
i s t
Z
h e m
ts
6 –1 6 –1

C
v = 2.18 × 10 × ms = 2.18 × 10 ms
n
p e r
= 3.32 × 10–10Emx= 3.3 Å
–34
6.626 10
y
h
(b) de Broglie wavelength,  =
mv
=
9.110  2.18 10 –31

i st r 6

(c) For 2p, l = 1

e r t s e
hh .. m

E xp =  (  1)
h C
y
Orbital angular momentum = 2

is t r 2 2

h em
C
156
 Atomic Structure

KZe2 
Kn   Vn 1
s = – 2 and En  .
s
2r 
t t
7. so,

Vn  
KZe2
p e r Kn r
p e r
r
E x 
 E x
s t ry
KZe2 
stry
m i
En   
m i
he 2r 
h e
C of the electron in a hydrogen-like atomic
8.C Magnetic moment of orbital angular momentum
orbital depends on azimuthal quantum number and its direction depends on magnetic quantum
number

ts
9. For lower state (S1)
e r
xpstate S has n = 3)
Number of radial node = 1 = n – l – 1
Put n = 2 and l = 0 (asE
y er ts
tr2s (for S state)
higher
p
2

So, it wouldsbe x
m i E
e ry
1

10. CEnergy of state S = – 13.6   eV/atom ist

h 3  2
1
2 
h
2
e m
3  C er ts
xp
2
=  2  (energy of H-atom in ground state)
E
try
2 
= 2.25 (energy of H-atom in ground state).
mis
s Che
t
11. For state S2

p e r
Number of radial node = 1 = n – l – 1 ....... (eq.-1)
Energy of S state =E x of e in lowest state of H-atom
–

s tr
2
y energy

= i– 13.6 eV/atom = – 13.6   eV/atom ; n = 3.

3  2

h e m r t s
e
2

C Put in equation (1) l = 1 so, orbital is 3p (for Sxstate).

n 
p
ry
2
E
1
i s t
12.
h e m2
Electrons with spin quantum number = – will be 1(in s) + 3(in p) + 5(in d) = 9.

C er ts
xp
12400
13. E = = 4.13 ev
E
photon
3000
 
s t r y
Photoelectric effect can take place only if E

t s
photon

m i
Thus,
e r effect. C h e
E x p
Li, Na, K, Mg can show photoectric

s t r y
m i
C h e
157
 Atomic Structure
h
14. mv (4a0) =


er ts h
er ts
so,
x
v=
E p 4m a 0
Exp
s ry
t= mv = m. stry
so, iKE i
2 2
1 1 h h
m 32mm
2

e e
=
h 16m  a
h  a 2 2 2 2 2
2 2
C C
0 0

h
15. = KE  T
2m(KE)

 He m Ne KE Ne 20 1000
= = = 5.
 Ne m He KE He 4  200

e r ts
p = 3,2,1
16. n = 4, ml = 1, –1
can beEx t s
Hence l
H st;r
y p e r
i.e.
m i 2 orbitals
E x
e y
f

h
C H ; 2 orbitals mi
H d ; 2 orbitals
s t r
p

C h e 1 s
e r t
xp
Hence total of 6 orbitals, and we want m = – , that is only one kind of spin. So, 6 electrons.
s

E
2
17. 1s orbital does not have any spherical node.
st r y
m i
18. Number of radial nodes in 2s orbital = n –  – 1= 1
s C h e
e r t
E xp
s tr y
m i s
h
C So,e e r t
r/a
E xp
ry
0

is t
h emfunction so, (D) is incorrect.
ts
19. 1s orbital cannot have angular part of wave
C e r
xp
3
 Zr 
Z 2  
20. For H – atom    e
n,l .m1
a 
 a0 

ry E
0

is t
1 1
13.6   – 
e r ts h e m
E –E 4 9 p
x 27
C
13.6  y –E 
4
2

E –E  1 1  32
s tr 4 36 
6 2

m i
C h e
158
 Atomic Structure

z2
21. Total energy = –13.6 × eV
n2

e r ts er ts
E x p 22
–3.4e = –13.6 × 2 eV
Exp
y y
n

ins =
r
t 13.6  2  16 ; n = 4 istr
m 3.4 m
2 

Che Che
Value of  = 2, So, it’s a 4d orbital.

Number of angular nodes =  = 2

Number of radial nodes = n– –1 = 4–2–1 = 1

e r ts
E xp r ts
Effective nuclear charge at this electron will be equal to 2e since no shielding effect.

tr y pe
(1) Radius iofsthe n orbit  n Ex
22.
h e m th 2

tr y n
C(2) Angular momentum of the electron
m
in i
the s
n orbit th

e
Cinhthe n orbit  n1
(3) Kinetic energy of the electron th

er ts
xp
2

E
try
1
(4) Potential energy of the electron in the nth orbit 
n2
mis
s Che
t
23. For one H atom
r
e 10
 – Exp
–19 2
kq q 9 10  1.69

P.E. = –
r y
1 2

t r 0.529 10 –10

m is9 1.6 1.6 10

Che
=– –19

er ts
xp
0.529
Total potential energy for 2 H-atom (per mole)
ry E
2  9  1.6 1.6 –19
i s t
m
23
=– × 10 × 6 × 10
0.529
C h e ts
= –5246.5 KJ/mole
er
Exp
stry
ts mi
er Che
Exp
istry
hem
C
159
 Electro chemistry

EXERCISE # (JEE-MAIN)
1.
r ts r ts
For a cell reaction involving a two-electron change, the standard e.m.f. of the cell is found to be
e constant of the reaction at 25°C willxpbee: [AIEEE 2003]
x p
0.295V at 25° C. The equilibrium
E (2) 1 × 10 E(4) 29.5 × 10
(1) 10
st r y 10
(3) 1 × 10
st r y –10 –2

i m i
em
2.Ch Standard reduction electrode potentials of
C h e
three metals A, B and C are respectively + 0.5V, –
3.0V and –1.2 V. The reducing powers of these metals are : [AIEEE 2003]
(1) C > B > A (2) A > C > B (3) B > C > A (4) A > B > C

3. For the redox reaction :

e r ts
Zn(s) + Cu (0.1M)  Znp(1M) + Cu(s) taking place in a cell,
2+

E x 2+

r t s
s y
tr E for the cell will be  2.303 F E0.0591 xpe
m
E° is 1.10 i volt.
 RT

y

[AIEEE 2003]
e
Cell Cell

h
C(1) 1.07 volt st r
i(3) 2.14 volt
(2) 0.82 volt
e m (4) 1.80 volt

Ch er ts
4.
E
When, during electrolysis of a solution of AgNO 9650 coulombs of charge pass through
3
xp the
s tr y 2003]
(4) i
electroplating bath, the mass of silver deposited on the cathode will be : [AIEEE
(1) 21.6g (2) 108g (3) 1.08g
h e m 10.8g

e r t s C
Consider the following E0p
5.
x
E E = –0.14 V
values, [AIEEE 2004]
0

s t ry 0

i
E = +0.77V
Fe3  / Fe 2  Sn 2  /Sn

h e mstandard conditions the potential for the reaction, r t s

C Sn(s) + 2Fe (aq) 2Fe (aq) + Sn (aq) is:
Under
xp e
3+ 2+

ry E 2+

(1) 0.91V (2) 1.40V

i s
(3)t1.68V (4) 0.63V

h e m
C one electron change is found to be 0.591 V at 25°C.erThets
equilibrium constant of the reaction is (F = 96,500C mol ; R = 8.314 JK mol ) xp
6. The standard e.m.f. of a cell, involving

E 2004]
–1 –1 –1

s r y
t× 10
[AIEEE
(2) 1.0 × 10 s
t m i
r e
10 5 1 30
(1) 1.0 × 10 (3) 1.0 × 10 (4) 1.0
e h
xp  for NaCl, KBr andCKCl are 126,152 and 150Scm mol
E
try for NaBr is :
0 2 –1
7. The limiting molar conductivities

m is 0

e S cm mol (2) 176 S cm mol (3) 128 S cm mol (4) 302 S cm mol
respectively. The m [AIEEE 2004]

C(1)h278 2 –1 2 –1 2 –1 2 –1

160
 Electro chemistry
8. In a cell that utilises the reaction, [AIEEE 2004]

t s ts
Zn(s) + 2H+(a) Zn2+(aq) + H2(g) addition of H2SO4 to cathode compartment, will :
e r er
(1) increase the E x
E p Exp
y y
and shift equilibrium to the right
r r
cel l

is tthe E and shift equilibrium to the right ist

he m
(2) lower cell

h e m
C (3) lower the E and shift equilibrium toCthe left
cell

(4) increase the Ecell and shift equilibrium to the left

9.
e r ts
The E 0M3 /M 2  values for Cr, Mn, Fe and Co are –0.41, + 1.57, +0.77 and + 1.97V respectively.

E xp the change in oxidation state from +2rttos+3 is easiest?

For which one of these metals

i s try x p e [AIEEE 2004]

(1) Fe m (3) Cry E
C h e (2) Mn
is t r (4) Co

m
heequilibrium constant (K) and E will be respectively
10. For a spontaneous reaction theCG, 0

er ts
xp
Cell

[AIEEEE
ry–ve
2005]
(1) –ve, < 1, –ve (2) –ve, >1, –ve (3) –ve, >1, +ve
is
(4) +ve,t>1,
h e m
e r t s C
11.
x p
Aluminium oxide may be electrolysed
E
at 1000°C to furnish aluminium metal ( 1 Faraday =

s t r y
96500 Coulombs).The cathode reaction is [AIEEE 2005]

m i s
ChAle + 3e  Al
3+ –

e r t
To prepare 5.12 kg of aluminium metal by this method E
xp
i st ry would require,
4
(1) 5.49 × 10 C of electric charge
h e m (2) 5.49 × 10 C of electric charge
1

C e r ts
xp
7 7
(3) 5.49 × 10 C of electric charge (4) 1.83 × 10 C of electric charge

r y E
i s t
The highest electrical conductivitytofsthe following aqueous solution
e m
12.
p e r C h is of [AIEEE 2005]

(1) 0.1 M fluoroaceticE x

y
istracid
acid (2) 0.1 M difluoroacetic acid

(3) 0.1m
Ch e M acetic (4) 0.1 M chloroacetic acid

161
 Electro chemistry

13. Electrolyte  (S cm2 mol–1)

KCl
er ts 149.9
er ts
KNO
Ex
3
p 145.0
Exp
HCl
stry 426.2
stry
m i mi
e e
NaOAC 91.0

Ch NaCl Ch126.5
Calculate HOAc using appropriate molar conductances of the electrolytes listed above at

infinite dilution in H2O at 25°C [AIEEE 2005]

(1) 390.7 (2) 217.5 (3) 517.2 (4) 552.7

e r ts
Given the data at 25°C, xp
14.
y E er ts
i
–
r
tAgI
s xp –

E
Ag + I + e , E° = 0.152V
mAg + e , E° = – 0.800 V
(s) (aq) (s)

Ag e
h
+ –

stry
CWhat is the value of log K for AgI ? mi
(s) (aq)

(Where K = solubility product)C

he sp

r ts
sp

xpe [AIEEE 2006]

  E
try
RT
 2.303  0.59V 
 F 
m is
(1) –8.12
s
(2) +8.612 (3) –37.83
Che (4) –16.13

e r t
E x p
15.
tr y
Resistance of a conductivity
s
cell filled with a solution of an electrolyte of concentration 0.1M is

m
100. The i conductivity –1

sof 0.02M solution of the

of this solution is 1.29 Sm . Resistance of the same cell when filled

h e
C electrolyte will be. e r t
xp
with 0.02M of the same solution is 520. The molar conductivity

y E
r × 10 Sm mol [AIEEE 2006]
i s t1240
m (4) 12.4 × 10 Sm mol
–4 2 –1 –4 2 –1
(1) 124 × 10 Sm mol (2)

C h e –1 –4
ts
–1

r
4 2 2
(3) 1.24 × 10 Sm mol

xp e
r E
y25°C are 91.0 and
16. The molar conductivities,  and  0 0

s t
irequired is :
at infinite dilution in water at
s m
NaOAC HCl

2
e t
426.2 S cm /mol respectively. Torcalculate 
h e
C
0

p
the additional value
x
HOAc

y E
(1) KCl istr
[AIEEE 2006]

m
(2) NaOH (3) NaCl (4) H O
e
2

C h
162
 Electro chemistry
17. The cell Zn | Zn+2(aq)(1M) || Cu+2(aq)(1M) | Cu (E°cell = 1.10 V) was allowed to be completely

s s 
  Zn  
2

er t e r t 
discharged at 298 K. The relative concentration of Zn+2 to Cu+2,   2   is :

Exp x p
E [AIEEE 2007]
 Cu  
 

r y try
(1)m is×t10 m is
e e
4

Ch Ch
9.65 (2) Antilog (24.08) (3) 37.3 (4) 1037.3

18. Given : E 0Cr 3 /Cr = –0.72 V, E 0Fe2  / Fe = –0.42 V. The potential for the cell, [AIEEE 2008]

Cr(s) | Cr3+(aq) (0.1 M) || Fe2+(aq) (0.01 M)|Fe(s) is

(3) – 0.339 V (4) – 0.26 V
ts
(1) 0.26 V (2) 0.339 V

e r
E xp r ts [AIEEE-2009]
19. Given :
s y
tr E = –0.439V. The value Eof xstandard
= i–0.036V,
e
p electrode potential for the
m
0 0

y
E

C h e
Fe3 /Fe

i s tr
Fe2 /Fe

m
change.
will be :–h e
C ts
–
+3
+ e  Fe +2

r
Fe
e
(aq) (aq)

(1) 0.770 V (2) –0.27 V (3) –0.072 V (4) 0.385 V

E xp
s t ry
m i
20.
s
2

C
3
e
The Gibbs energy for the decomposition of Al O at 500 °C is as follows : [AIEEE 2010]
h
Al O  Al + O ,  G r =t
e
2 4 –1
3
2
3
3

E x p +966 kJ mol 2 r

s t r y needed for electrolytic reduction of Al2O3 at 500 °C is at least :-

Vi
The potential difference

e m r t s
Ch
(1) 5.0 (2) 4.5 V (3) 3.0 V (4) 2.5 V

x p e
y
The reduction potential of hydrogen half-cell willrbe
E
21.
t
i(2)s p(H ) = 2 atm and [H ] = 2.0 M
negative if :– [AIEEE 2011]

m
CMhe (4) p(H ) = 1 atm and [H ] = 1.0 M
+ +
(1) p(H ) = 2 atm [H ] = 1.0 M
ts
2 2

(3) p(H ) = 1 atm and [H ] = 2.0 + +

e r
xp
2 2

r E
y of the solution
22.
i s t
Resistance of 0.2 M solution of an electrolyte is 50 . The specific conductance
–1
e ts
r 0.4M solution of theCsame h e m
electrolyte is 260 , its molar
p
is 1.3 S m . If resistance of the

E x
r
conductivity is :–
(1) 6250 Simstmol
y 2 –1 –4 2
[AIEEE 2011]
–1

m× 10 S m mol
(2) 6.25 × 10 S m mol

C h
(3) e
625 –4 2 –1
(4) 62.5 S m mol 2 –1

163
 Electro chemistry
23. The standard reduction potentials for Zn2+ / Zn, Ni2+ / Ni and Fe2+ / Fe are – 0.76, – 0.23 and –
0.44 V respectively. The reaction X + Y+2  X2+ + Y will be spontaneous when[AIEEE 2012]

e r t s e r t s
E x
(1) X = Zn, Y = Ni
p (2) X = Ni, Y = Fe
(3) X = Ni, Y = Zn
E x
(4)
pX = Fe, Y = Zn

st r y0.2 M solution of an electrolyte is 50 . The

s t r y conductance of the solution
24.
m i
Resistance of
m i
e
specific
e Ch of the same electrolyte is 280 . The molar
Ch is 1.4 S m . The resistance of 0.5 M solution
–1

conductivity of 0.5 M solution of the electrolyte in S m 2 mol–1 is : [JEE-MAIN 2014]

(1) 5 × 103 (2) 5 × 102 (3) 5 × 10–4 (4) 5 × 10–3

25.
e r ts
The equivalent conductance of NaCl at concentration C and at infinite dilution are C and ,

respectively. The correctx

E p between  and  is given ast:s[JEE-MAIN 2014]
r
relationship
yB is positive) e
C

i st r x p
(where the constant
m y E
C(1)he =  – (2) C (2)  =  + (2)mCis(3)tr =  + (2) C (4)  =  – (2) (3)
C C C C

C he r ts
26. Given :
xp e
E
try
0 0
E = 0.74 V ; E = 1.51 V
Cr 3  /Cr MnO 4 /Mn 2 

m is
E 0
= 1.33 V ; E 0

s
= 1.36 V
C h e
t
Cr2 O72  /Cr 3 Cl/Cl 

p e r
E x
Based on the data given above, strongest oxidising agent will be :
(1) Cl –

t r y (2) Cr 3+
(3) Mn 2+
(4) MnO –

is
4

27. Ch
e m
Two Faraday of electricity is passed through a solution ofeCuSO r ts . The mass of copper
E xp 4

r y
i(3)st0 g
deposited at the cathode is : (at. mass of Cu = 63.5 amu) [JEE-MAIN 2015]

m
Che
(1) 2g (2) 127 g (4) 63.5 g

e r ts
28. A variable, opposite external potential (E ) is applied to the cell
E xp
Vy
ext
2+ 2+
Zn|Zn (1 M) || Cu (1 M) | Cu, of potential 1.1 V. When E < 1.1
i s t
extr and E > 1.1 V, ext

respectively electrons flow from : ts e m [JEE-MAIN 2015]

e r (2) anode toC
h
E xpcases
(1) anode to cathode in both cathode and cathode to anode

i s ry in both cases
(3) cathode totanode (4) cathode to anode and anode to cathode

h e m
C
164
 Electro chemistry
29. At 298 K, the standard reduction potentials are 1.51 V for MnO –4|Mn2+, 1.36 V for Cl2|Cl–,
1.07 V for Br2|Br–, and 0.54 V for I2|I– .At pH = 3, permanganate is expected to oxidize

e r ts r ts
e[JEE-MAIN 2015]
 RT

E

x
 0.059V  :p E x p
 F
s r
tBr y 
s Itry
(1)Cl iand
m
– –
(2) Cl , Br and I –

m i
(3) Br and – –
(4) I only – – –

he h e
C and carbon dioxide gases. On passing 0.2 Faraday
C Oxidation of succinate ion produces ethylene
30.
electricity through on aqueous solution of potassium succinate, the total volume of gases
(at both cathode and anode) at STP (1 atm and 273 K) is : [JEE-MAIN 2016]
(1) 8.96 L (2) 2.24 L (3) 4.48 L (4) 6.72 L

e r ts
xp
31. What will occur if a block of copper metal is dropped into a beaker containing a solution of 1M

y E e r ts
r will dissolve and zinc metal will be deposited
ZnSO [JEE-MAIN 2016]
tmetal p
4

m i s
(1) The copper
E x
h e s t r y
C(3) The copper metal will dissolve with m
(2) No reaction will occur
i
e
Chwith evolution of hydrogen gas ts
evolution of oxygen gas

er
xp
(4) The copper metal will dissolve

E
32. Given
istry
E0Cl2 /C1–  1.36 V, E0Cl3 /Cr  –0.74 V
hem
e r ts C
7
p
E0Cl2 /C12– /Cr3  1.33V, E0MnO– /Mn2  1.51V
x
Ethe strongest reducing agent is
4

t ry
(1) Cr is
Among the following, [JEE MAIN 2017]

h e m (2) Mn 2+
(3) Cr
r t s
(4) Cl 3+ –

33. C How long ( approximate) should water be electrolysed byx

e
p through 100 amperes current
E passing
ry g of diborane ?
so that the oxygen released can completely burnt27.66
m i s
(Atomic weight of B = 10.8 u)
C h e [JEE MAIN 2018]
ts
e r
xp
(1) 1.6 hours (2) 6.4 hours (3) 0.8 hours (4) 3.2 hours

r
[JEEtMain
E
y 2019 (Apr.)]
s

34. Given that E = 1.23 V;
O2 /H 2O

t s m i
= 2.05 V e ; r E
C h e 

p
 
E = + 1.09 V ; E = + 1.4 V
x is :
S2O82 /SO42

E
Br2 /Br  Au 3 /Au

st ry
The strongest oxidizing
i
agent
(1) O m
e
2 3+

h
2 (2) S O 2 (3) Br (4) Au 2

C
8

165
 Electro chemistry
35. Calculate the standard cell potential (in V) of the cell in which following reaction takes place :
Fe2+ (aq) + Ag+ (aq)  Fe3+ (aq) + Ag (s)

er ts er ts [JEE Main 2019 (Apr.)]

Given that
= xExp Exp
E
s t ry º
V
Ag  /Ag

stry
m i mi
Che E º
=yV
Fe2 /Fe
Che
E ºFe3 /Fe = z V

(1) x – z (2) x + 2y – 3z (3) x – y (4) x + y – z

The standard Gibbs energy for the given cell reaction in kj mol –1 at 298 K is :
ts
36.

p e r
Zn(s) + Cu2+(aq)  Zn2+ (aq) + Cu(s), E°=2 V at 298 K
(Faraday's constant, FE=x r ts MAIN 2019 (Apr.)]
y e
–1

(1) –384 ist

r (2) 384
96000 C mol )
x
[JEE
p (4) 192
e m (3) –192
r y E
h
CA solution of Ni(NO ) is electrolysed st
ibetween platinum electrodes using 0.1 Faraday
h e m
ts
37.
electricity. How many mole ofC
3 2

e r
xp
Ni will be deposited at the cathode? [JEE MAIN 2019 (Apr.)]

E
try
(1) 0.20 (2) 0.15 (3) 0.10 (4) 0.05

m is
h e
ts with decrease in theCconcentration of electrolyte.
38. Consider the statements S1 and S2 :
Conductivity always e r
xpalways increases with decrease in the concentration of electrolyte.
S1: increases

r y E
t
S2: Molar conductivity

m i s s
(1)eBoth S1 and S2 are wrong t
The correct option among the following is: [JEE MAIN 2019 (Apr.)]

Ch (2) Both S1 and S2e r

xpand S2 is wrong
are correct
E
try
(3) S1 is wrong and S2 is correct (4) S1 is correct
i s
m molar conductivity (  ) versus C is correct ? s
C h e t
39. Which one of the following graphs between
e r
xp(Apr.)]
m

r y E
[JEE MAIN 2019

i s t
e r t s h em
E x p C
(1)
s tr y (2) (3) (4)

m i
C h e
166
 Electro chemistry
40. Given: [JEE MAIN 2019 (Apr.)]
Co3+ + e–  CO2+ ; Eº = + 1.81 V

e r t s er ts
Ce + 3e  Ce E
x p
Pb4+ + 2e–  Pb2+ ; Eº = + 1.67 V
Exp
+4

tr y 3+
; Eº = + 1.61 V
stry
Bi + i3es  Bi ; Eº = + 0.20 V i
m power of the species will increasehinethem
3+ –

CheOxidizing C order:
(1) Ce4+ < Pb4+ < Bi3+ < Co3+ (2) Co3+ < Pb4+ < Ce4+ < Bi3+
(3) Bi3+ < Ce4+ < Pb4+ < Co3+ (4) Co3+ < Ce4+ < Bi3+ < Pb4+

ts
41. The decreasing order of electrical conductivity of the following aqueous solutions is:
0.1 M Formic acid (A),
p e r [JEE MAIN 2019 (Apr.)]
0.1 M Acetic acid (B),Ex t s
y
r (C).
tacid p e r
m is E x
yC > B
0.1 M Benzoic

C h
(1) Ae >B>C (2) C > A > B
i (3)tAr>
s (4) C > B > A

The anodic half-cell of lead-acid h e mis recharged using electricity of 0.05 Faraday. The
42.
C battery
e r t s
amount of PbSO electrolyzed in g during the process i : (Molar mass of PbSO = 303 p
x
–1

E
4 4 g mol )

st
[JEE MAIN
ry 2019 (Jan.)]
m i
(1) 22.8 (2) 15.2
s
(3) 7.6
C h e (4) 11.4

e t
r for a cell is 2 V at 300 K, the equilibrium constant (K) for the
43.
x p
If the standard electrode potential
E
reaction
s ry
t(aq) Zn (aq) + Cu(s)at 300 K is approximately.
[JEE MAIN 2019 (Jan.)]

m i s
e t
2+ 2+

r
Zn(s) + Cu
h
C (R = 8 JK mol , F = 96000 C mol ) e
xp
–1 –1 –1

(3) ery
E
(1) e –80
(2) e –160

i s t160
(4) e320

h e m:
44.
C
Consider the following reduction processes [JEE MAIN 2019 (Jan.)]
e r ts
xp
–
Zn + 2e  Zn(s); Eº = –0.76 V
2+

–
Ca + 2e  Ca(s); Eº = –2.87 V
ry E
t
2+

–
Mg + 2e  Mg(s); Eº = –2.36 V
s m is
t
2+

Ni + 2e  Ni(s); Eº = –0.25eVr
C h e
p
–

x
2+

The reducing power ofEthe metals increases in the order :

is ry
<tZn < Ni
h e m
(1) Ca < Mg (2) Zn < Mg < Ni < Ca

C (3) Ni < Zn < Mg < Ca (4) Ca < Zn < Mg < Ni

167
 Electro chemistry
45. In the cell Pt(s)|H2(g, 1bar)|HCl(aq)|AgCl(s)|Ag(s)|Pt(s) the cell potential is 0.92 V when a 10 –6
molal HCl solution is used. The standard electrode potential of (AgCl/Ag,Cl –) electrode is :

e r t s r ts
eMAIN 2019 (Jan.)]

Given, xp
2.303RT
E

 0.06 V at 298K 
E x p
[JEE

s try F 
stry
m i m i
e e
(1) 0.94 V (2) 0.40 V (3) 0.20 V (4) 0.76 V

Ch Ch
46. For the cell Zn(s) | Zn2+(aq) || Mx+ (aq) | M(s), different half cells and their standard electrode
potentials are given below : [JEE Main 2019 (Jan.)]

e r ts
E xp r t s
s r y
–t 0.76 V, which cathode will give a maximumx e
p value of E per electron
If E O

m i
=
y E O

h e Zn 2 / Zn

t r
cell

C transferred?
m i s
e
Ch (3) Fe / Fe r ts
2+ 3+ 3+ 2+ +
(1) Fe / Fe (2) Ag / Au (4) Ag / Ag

xp e
E
47. Given the equilibrium constant :
i stry 2019 (Jan.)]
[JEE MAIN

he m
K of the reaction :
C

e r t s C
Cu(s) + 2Ag (aq)  Cu (aq)
xp
+ 2+
+ 2Ag(s) is

r E
y the E of this reaction at 298 K
is
15
t
10 × 10 , calculate 0

m s
cell

Ch e e r t
xp
RT
[2.303 at 298K is 0.059V]
F
E
ry mV (4) 0.04736 V
i s t0.4736
m
(1) 0.4736 V (2) 0.04736 mV (3)

C h e ts
p e r
E ax
 dE  

 dTry

48. The standard electrode potential E and its temperature coefficient   for cell are 2V

i s t
–4 –1

e r
and –5 × 10 VK at 300 K respectively. ts The cell reactionhiseZn(s)
m+ Cu (aq)  Zn (aq) + 2+ 2+

E xpenthalpy   H  at 300 K inCkJ mol is,

 –1

trmoly and F = 96,000 C mool ]

Cu(s) The standard reaction r

[Use R = 8iJK
m s –1 –1 –1
[JEE MAIN 2019 (Jan.)]
e
C(1)h192.0 (2) –384.0 (3) 206.4 (4) –412.8
168
 Electro chemistry

49.  om for NaCl, HCl and NaA are 126.4, 425.9 and 100.5 S cm2mol–1, respectively. If the

t s ts
conductivity of 0.001 M HA is 5×10–5 S cm–1, degree of dissociation of HA is:
e r r
eMAIN 2019 (Jan.)]
x p
E (2) 0.125 x p
E(4) 0.75
[JEE
(1) 0.50
stry (3) 0.25
stry
m i m i
he h e
C Given that the standard potentials (E°) Cof Cu /Cu and Cu /Cu are 0.34 V and 0.522 V
50. 2+ +

respectively, the E° of Cu2+/Cu+ is : [Jee Main (Jan. 2020)]

(1) –0.182 V (2) –0.158 V (3) 0.182 V (4) +0.158 V

51.
e r
The equation that is incorrect is :ts
(1)    –   xp
  –   s
0
m NaBr

ry E 0
m NaCl
0
m KBr
0
m KCl
e r t [Jee Main (Jan. 2020)]

(2)    is t
–      –   E x p
e m y
0 0 0 0

C(3)h           –   m
m NaBr m NaI m KBr

i st r m NaBr

0 0
e 0 0
m H O
2
m HCl

C h m NaOH m NaCl

r ts
(4)    –   
0
   –  
0 0 0

xp e
m KCl m NaCl m KBr m NaBr
E
is try
h e m at 298 K is:
s
52. Amongst the following, the form of water with the lowest ionic conductance

e r t Cused for intravenous injection

xp
(1) distilled water (2) saline water
(3) sea water
r y E (4) water from a well [Jee Main (Jan. 2020)]

Whatm
is t
e r t s
Ch_________.
53. would be the electrode potential for the given half cell reaction at pH = 5 ?

x p e [Jee Main (Jan. 2020)]

r y E
st
 –
2H O  O + 4 H + 4e ; E = 1.23 V
i
0
2 2

m
red

–1 –1

C
(R = 8.314 J mol K ; Temp = 298 K;
h e oxygen under std. atm. Pressure of 1 bar)
ts
e r
54. For an electrochemical cell
Exp
s tr y
i
2+ 2+
Sn(s)|Sn (aq, 1M)||Pb (aq, 1M)|Pb(s)

when this celle

2
t s
r equilibrium is ____________. e m
h [Jee Main (Jan. 2020)]
p C
[Sn ]
the ratio
[Pb ] 2

E x attains

s ry
t  0.14V, E  0.13V, 2.303RT  0.06 

 em
 Given:E i0 0

h
Sn 2 |Sn Pb2 |Pb
F 
C
169
 Electro chemistry
55. For the given cell ; [Jee Main (Jan. 2020)]

e 2r s e r ts
Cu(s)|Cu2+ (C1M)||Cu2+ (C2M)|Cu(s) change in Gibbs energy (G) is negative, if :
t
(1) C1 = 2C2
x p (2) C2 = Cl
(3) C = C
E mass 108g mol ) is deposited at cathode x
(4)
pC = 2C
E AgNO (aq) solution by a
1 2 2 1

st ry st ry
i i
–1
56. 108g of silver (molar from
m quantity of electricity. The volume (inheL)m
3

C hecertain
C
of oxygen gas produced at 273 K and 1 bae
pressure from water by the same quantity of electricity is ______ . [Jee Main (Jan. 2020)]

57. Let CNaCl and CBaSO4 be the conductances (in S) measured for saturated aqueous solutions of

ts
NaCl and BaSO4, respectively, at a temperature T.

p e r
x
Which of the following is false ? [Jee-Main (Sep) 2020]
(T )  C E
y e r t s
isCtr at a given T xp
(1) C BaSO4 (T ) for T > T
2 BaSO4 1 2 1

(2) C m
e r y E
h
NaCl BaSO4

C(3) C (T )  C (T ) for T > T mi s t

h e 2 1

ts
NaCl 2 NaCl 1

C
(4) Ionic mobilities of ions from both salts increase with T
e r
E xp
Eext
i s try
h e m
e r ts C
58.
E xp Cu rod

y
Zn rod
–ve

is tr Salt +ve
1M

m
1M

s
Bridge

e t
CuSO4

h r
ZnSO4

C E  0.34V e
soln.

xp [Jee-Main (Sep) 2020]

soln.

E
try
Cu 2 |Cu

E 
 –0.76V
m i s
Zn 2 |Zn

Identify the incorrect statementC

h e ts
e r
xp
from the options below for the above cell :
–
(1) If E > 1.1 V, e flows from Cu to Zn
ry E
t
ext

s m is
(2) If E > 1.1 V, Zn dissolves at Zn electrode and Cu deposits at Cu electrode
t e
ext

p e
(3) If E < 1.1 V, Zn dissolves at ranode and Cu depositsCat hcathode
x of e or current occurs
ext

(4) If E = 1.1 V, no E –

try
ext flow

m is
C h e
170
 Electro chemistry
59. 250 mL of a waste solution obtained from the workshop of a goldsmith contains 0.1 M AgNO 3

s s
and 0.1 M AuCl. The solution was electrolyzed at 2V by passing a current of 1 A for 15

e r t e r t
x p
minutes. The metal/metals electrodeposited will be :
EE  169V  x p
E[Jee-Main (Sep) 2020]
 E  0.80V,
r y ry
ist t
0 0

(1)m
Ag  /Ag Au  /Au

m is
Che h e
Silver and gold in proportion to their atomic weights
C
(2) Silver and gold in equal mass proportion
(3) Only silver
(4) Only gold

ts
60. The variation of molar conductivity with concentration of an electrolyte (X) in aqueous

e r
xp
solution is shown in the given figure.

y E er ts
istr Exp
m
Molar

he Conductivity
stry
C m i
Ch e c
e r ts
The electrolyte X is:
E xp
[Jee-Main (Sep) 2020]
(4) HCltry
(1) NaCl (2) KNO (3) CH COOH
3

m is 3

The Gibbs energy change (in J) for the given reaction at [Cu h ] =e[Sn ] = 1 M and 298 K is :
t s C
2+ 2+

r+ Sn(s) ; (E  0.16V, E  0.34 V

61.
Cu(s) + Sn (aq.)  Cu p
2+
x e 2+ 0 0

E
(aq.) Sn 2 |Sn Cu 2 |Cu

s tr yC mol )
i
–1
Take F = 96500 [Jee-Main (Sep) 2020]

62. h e m r tats298 K,
C In K (where k is the equilibrium constant) is ________ × 10xp.
For +
the disproportionation reaction 2Cu (aq)  Cu(s) + Cu (aq)
e 2+

r y E –1

m iFst 0.025)
RT
 0.16V E
e
 0.52V
0 0
Given : (E [Jee-Main (Sep) 2020]
Cu 2 /Cu 

C h Cu  /Cu

r ts
63.
xp e
The photoelectric current from Na (work function, w =2.3 eV) is stopped by the output voltage
E
0

of the cell pt |H (g, 1 bar)|HCl(aq., pH = 1)|AgCl |Ag .

st ry
The pH of aq. HCl required to stop the photoelectric current fromiK(w =2.25eV), all other
(s) 2 (s) (s)

ts
conditions remaining the same,eisr_______ × 10 (to theC h m
einteger). 0

xp
–2
nearest

r y E
t
Given,

m is
e
RT
h
0
2.303 = 0.06 V; E = 0.22 V [Jee-Main (Sep) 2020]
C F AgCl|Ag|Cl –

171
 Electro chemistry
64. An acidic solution of dichromate is electrolyzed for 8 minutes using 2A current. As per the

s s
following equation

e r t r t
e (Sep) 2020]
x p
Cr2O72  14H  6e  2Cr 3  7H2O
x p
[Jee-MAIN
E (in %) is
The amount ofyCrEobtained was 0.104 g. The efficiency of the
y
r t r
t= 96000 C, At. mass of chromium = 52) ________.
3+
process
s
(Take :iF
m60.31 m is
CheGiven C h e
65. An oxidation-reduction reaction in which 3 electrons are transferred has a G° of 17.37 kJ mol–1
at 25°C. The value of EoCell (in V) is __________ × 10–2.
(1 F = 96,500 C mol–1)
e r ts [Jee-Main (Sep) 2020]

E xp r ts
s y e
tr is prepared by the electrolysis of KClEinxbasic
p solution
66.
i
Potassium chlorate
6OHem y
h
– – –
+ Cl  ClO + 3H O + 6e
CIf only 60% of the current is utilized m
3 2
s
–
t r
i reaction, the time (rounded to the nearest hour)
e
Chusing a current of 2 A is …………….
in the
required to produce 10 g of KClO
e r ts
p
3
–1 –1
E x2020]
try
(Given : F = 96,500 C mol ; molar mass of KClO = 122 g mol ) [Jee-Main (Sep)
3

m is
s C h e
e r t
E xp
s tr y
m i s
Ch e e r t
E xp
is try
h e m
C e r ts
E xp
s try
t s m i
e r C h e
E x p
s t ry
m i
C h e
172
 Electro chemistry

EXERCISE # (JEE-ADVANCED)
1.
e r s e r s
Calculate the equilibrium constant for the reaction, 2Fe 3+ + 3I– 2Fe2+ + I3–. The standard
t t
I / I couples. E
xp E x p
reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe 3+ / Fe2+ and
3
–

s r y–

r y
t product of a saturated solution of iAgstCrO in water at 298 K if the emf of
[JEE 1998]

m i m
2.
heFind the solubility
h e
C the cell Ag|Ag (satd.Ag CrO soln.) || AgC+(0.1 M) | Ag is 0.164 V at 298K. [JEE 1998]
+
2 4
2 4

3. A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M Y and 1 M Z at

25°C. If the reduction potential of Z > Y > X, then [JEE 1999]
(A) Y will oxidise X and not Z (B) Y will oxidise Z and X

er ts (D) Y will reduce both X and Z.

xcell,pM | M || X | X, E° (M /M) = 0.44rtVsand E° (X/X ) = 0.33V.
(C) Y will oxidise both X and Z

E
t,roney can deduce that e
+ – + –
4. For the electrochemical
is E x p
m
From this data
y
[JEE 2000]

C(A)heM + X M + X is the spontaneous i str

+ –
reaction

h e m reaction
ts
–

C
(B) M + X  M + X is the spontaneous
+

e r
xp
(C) E = 0.77 V
E
cell

(D) E = –0.77 V
cell

is t ry
e m
16h
5. Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper
cathode. A constant current of t2smA was passed for C
er mintue. It was found that after

E xp (concentration) of the solution was reduced to 50% of its original

electrolysis, the absorbance

s t r ythe concentration of copper sulphate in the solution to begin with. [JEE 2000]
m i
value. Calculate
s
h e
C Pt | Fe , Fe (a =1) || Ce , Ce (a = 1) | Pt( e r t
xp
6. The following electrochemical cell has been set up
3+ 2+ 4+

ry E
3+

= 1.61 V ist
(I) II)

m
0 0
E = 0.77 V and E
Fe3  / Fe 2 

h e Ce4  /Ce3

C the two platinum electrodes. predict the direction ofeflow ts

If an ammetter is connected between
r
of current. Will the current increase or decrease with time?
E xp2000]
[JEE

s tr y [JEE 2001]
7. The reaction,
t s m i
3ClO (aq)  ClO (aq) + 2Clr(aq)
–
e – –

C h e
E x p 3

is an example of
s r y
treaction
m i
(A) Oxidation (B) Reduction reaction

C h
(C) e
Disproportionation reaction (D) Decomposition reaction

173
 Electro chemistry
8. The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KCl is

s s
(A) LiCl > NaCl > KCl (B) KCl > NaCl > LiCl [JEE 2001]

e r t er t
(C) NaCl > KCl > LiCl
x p (D) LiCl > KCl > NaCl
Eof KNO is used to make salt bridge because Ex p
9.
s ry
t of K is greater than that of NO
Saturated solution
st r y
i i
3

he m
(A) velocity +

h e m –
3

C (B) velocity of NO is greater than that ofCK

–
3
+

(C) velocities of both K+ and NO–3 are nearly the same

(D) KNO3 is highly soluble in water [JEE 2001]

ts
10. The standard potential of the following cell is 0.23 V at 15° C & 0.21 V at 35° C

e r
xp
Pt | H2(g) | HCl (aq) | AgCl(s) | Ag(s)

y E e r t s
tHr ,S for the cell reaction by assumingEthat
(i) Write the cell reaction.

is x pthese quantities remain unchanged

m
0 0

y
(ii) Calculate

h e
C(iii) Calculate the solubility of AgCl in m
in the range 15°C to 35°C.
i st r
h e
Ag /Ag couple is 0.80 V at C ts
water at 25°C. Given standard reduction potential of the
+
25°C.
p e r
[JEE 2001]
E x
Standard electrode potential data are useful for understanding the suitabliltyrof
s t yan oxidant in a
arei given below:
11.

h e m
redox titration. Some half cell reactions and their standard potentials
MnO (aq) + 8H (aq) + 5e tMn
– +

e r s – 2+
C
(aq) + 4H O (l); E° = 1.51 V [JEE 2002]
xp+ 6e  2Cr (aq) +7H O (); E° = 1.38 V
4 2

Cr O (aq) + 14 H E
2 –

y
+ 3+
(aq)
t r
2 7 2

m s
Fe (aq) i+ e  Fe (aq); E° = 0.77 V
–
s
e t
3+ 2+

h
C Cl (g) + 2e  2Cl (aq); E° = 1.40 V p e r
x
– –

E
2

s tr y
Identify the only incorrect statement regarding quantitative estimation of aqueous Fe(NO )
(A) MnO can be used in aqueous HCl mi(B) Cr O can be used in aqueous HCl
3 2

e
 2
4

C h (D) Cr O can be used in aqueous H SO ert

2 7
s
xp
 2
(C) MnO can be used in aqueous H SO 2 4 2 4

E
4 2 7

12. In the electrolytic cell, flow of electrons is from:

s t r y
t s m i
r supply e
(A) Cathode to anode in solution
(B) Cathode to anode through e
x p external C h
r y Ethrough internal supply
(D) Anodeito s tcathode through internal supply.
(C) Cathode to anode

h e m
C
174
 Electro chemistry
13. Two students use same stock solution of ZnSO4 and a solution of CuSO4. The e.m.f of one cell

s s
is 0.03 V higher than the other. The conc. of CuSO4 in the cell with higher e.m.f value is 0.5 M.
r t
e in the other cell  F  0.06  . xpe [JEE 2003] r t
E x p
Find out the conc. of CuSO
 2.303 RT
4

E
s tr y 
str y
m i m i
14. he
Zn | Zn (a = 0.1M) || Fe (a = 0.01M)|Fe. h Theeemf of the above cell is 0.2905 V. Equilibrium
C C
2+ 2+

constant for the cell reaction is [JEE 2004]

0.32/0.0591 0.32/0.0295 0.26/0.0295 0.32/0.295
(A) 10 (B) 10 (C) 10 (D) e

ts
15. Find the equilibrium constant at 298 K for the reaction,

e r
xp E = –0.42V, E = –0.40 Vrts
Cu2+(aq) + In2+(aq)  Cu+(aq) + In3+(aq)

r y E e
ist p
0 0 0
Given that E = 0.15V, [JEE 2004]

m
Cu 2  |Cu 

E x In3 |In  In 2  |In 

he tr y
16. CThe half cell reactions for rusting of iron are:is
h em [JEE 2005]
+1
+ O + 2e  H OC –
; E = + 1.23 V, Fe + 2e  Fe ; E = –0.44 V
0
e r t
2+ s – 0

p
2H
x
2 2

E
2
G (in kJ) for the reaction is :
0

i st ry
(A) –76 (B) –322 (C) –122
h e m(D) –176

e r t s C
(a) Calculate G ofEthe xp
y+ Cl (aq) AgCl(s)
0
17. following reaction
t r
f

m i
Ag s +
(aq) –

s
h e e rt
C Given : G (AgCl) = –109 kJ/mole, G (Cl ) = –129 kJ/mole,
0

xp
0 –
G (Ag ) = 77 kJ/mole 0 +

E
f f f

Represent the above reaction in form of a cell

st r y
m i
e
0
Calculate E of the cell. Find log K of AgCl
h ts
10 SP

(B) (b) 6.539 × 10 g of metallic C Zn (amu = 65.39) was added to 100 ml of saturated solution
–2

e r
 Zn  2
E xp
of AgCl. Calculate  log , given that
s t r y
i
2 10
 Ag  

e t
rV ; s Zn + 2e C
e m
hZn E = –0.76V
+ –
Ag + e  Ag
x p
E = 0.80 0

E of Ag will be formed ?
 2+ – 0

t r
Also find how many
s y moles [JEE 2005]

m i
C h e
175
 Electro chemistry
Paragraph for Question No. 18 to 20

s s
Tollen’s reagent is used for the detection of aldehyde when a solution of AgNO 3 is added to
r t e r t
Ag + e  AgE
pe
glucose with NH4OH then gluconic acid is formed
; Ex = 0.8 V Ex p
y y
+ – 0

is r
+tH O C H O (Gluconic acid) + 2H i
r
+s2et ; E = – 0.05 V
red

m m
+ – 0
CH O
e e
6 12 6 2 6 12 7 red

Ch C–
h
Ag(NH ) e  Ag(s) + 2NH ; E = – 0.337
3 2
+
V 3
0

RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K] [JEE 2006]
F RT
18. 2Ag+ + C6H12O6 + H2O  2Ag(s) + C6H12O7 + 2H+
Find ln K of this reaction
e r ts (C) 28.30
(A) 66.13
E x p (B) 58.38
s
(D) 46.29
t
y
tris added to the solution, pH is raised toE11.xp e r
19.
m i
When ammonias Which half-cell reaction is affected

h e s t r y
C(A) E will increase by a factor of 0.65m
by pH and by how much?
i
e
Cofh0.65 from E
0

ts
oxd from E oxd

e r
xp
0
(B) E will decrease by a factor
oxd oxd

E
try
0
(C) E will increase by a factor of 0.65 from E
red red

(D) E will decrease by a factor of 0.65 from E

m is 0

e
red red

ts C h
Ammonia is always is addede inrthis reaction. Which of the following must be incorrect?
20.
E x p
tr
(A) NH combines y with Ag+ to form a complex.
is) is a weaker oxidising reagent than Ag .
3

m s
+ +

e t
(B) Ag(NH
h r
3 2

C (C) In absence of NH silver salt of gluconic acid is

xp
formed. e
(D) NH has affected the standard reduction potential ofE
3

try
glucose/gluconic acid electrode.
s
3

i
m of AgBr is 12 × 10 . If 10 mole of AgNO s
C h e t
r
–14 –7

e
21. We have taken a saturated solution of AgBr.K sp 3

p in
are added to 1 litre of this solution find conductivity (specific conductance) of thisxsolution
E
–7 –1 –1
s t r y [JEE 2006]
terms of 10 S m mol .

t s = 8 × 10 S memol m i;  = 7 × 10 S m
Given : 
 
0
= 6 × 10 S m mol
Ag 
p e r   ;  –3

C
2
h
–1 0
 
Br 
–3 2 –1 0
NO3
–3 2

E x
try
–1
mol

m is
C h e
176
 Electro chemistry
Paragraph for Question Nos. 22 & 23

s s
Redox reactions play a pivoted role in chemistry and biology. The values of standard redox
r t e r t
pe
A simple exampleEisxa Daniel cell in which zinc goes into solution
E x p
potential (E°) of two half-cell reactions decide which way the reaction is expected to proceed.

s
Given ibelow
y y
tr along with their E° (V with
tr are a set of half-cell reactions (acidicismedium)
and copper gets deposited.

he m h e mthis data obtain the correct explanations to

C C
respect to normal hydrogen electrode) values.
Questions 14-16.
Using

I2 + 2e–  2I– E° = 0.54

Cl2 + 2e–  2Cl– E° = 1.36

t s
Mn3+ + e–  Mn2+
r
E° = 1.50
Fe p + ee Fe
x s
3+ – 2+

E t
E° = 0.77

t r y  –
p e r
s
+

i x
O + 4H + 4e 2H O E° = 1.23 [JEE 2007]
E
2 2

22.
h e
Among mthe following, identify the correct statement.
tr y
s
C(A) Chloride ion is oxidised by O mi(B) Fe is oxidised by iodine 2+

Che (D) Mn is oxidised by chlorine

2

r ts
2+
(C) Iodine ion is oxidised by chlorine

x p e
ry E
s t
3+ 3+

i
23. While Fe is stable, Mn is not stable in acid solution because
2+
(A) O oxidises Mn to Mn 3+

h e m
(B) O oxidises both Mn to Mntsand Fe to Fe
2

e
2+
r 3+ 2+
C 3+

xOp
2

E
3+
(C) Fe oxidises H O to
yH O to O
2 2

is
3+
t
(D) Mn oxidises r
m s
2 2

Ch e e r t
Paragraph for Question Nos. 24x top
Chemical reactions involve interaction of t
E 26
ry and molecules. A large number of
m is atoms
atoms/molecules (approximately 6.023
h e 23
× 10 ) are present in a few grams of any chemical
ts
compound varying with theirCatomic/molecular masses. To handle such large numbers e r
E xp areas
conveniently, the mole concept was introduced. This concept has implications in
s t r y The following
diverse

t s m i
such as analytical chemistry, biochemistry, electrochemistry and radiochemistry.

e C h e
rinvolving chemical/ electrochemical
ofx
p
example illustrates a typical case,
a clear understandingE
reaction, which requires

s r y the mole concept. A 4.0 molar aqueous solution of NaCl is prepared

oftthis solution is electrolysed. This leads to the evolution of chlorine gas at one of
m
and 500 mL i
C h
the e
electrodes (atomic mass : Na = 23,Hg = 200; 1 Faraday = 96500 coulombs) [JEE 2007]
177
 Electro chemistry
24. The total number of moles of chlorine gas evolved is

s s
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
r t r t
If the cathode isEax
pe xpe formed from this
Hg electrode, the maximum weight (g) ofEamalgam
25.
s t ry st r y
m i
solution is
m i
e
Ch (A) 200 (B) 225 e
Ch(C) 400 (D) 446

26. The total charge (coulombs) required for complete electrolysis is

(A) 24125 (B) 48250 (C) 96500 (D) 193000

e r ts
xtopliberate 0.01 mol of H gas at the cathode
27. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere

y E e r t sis (1 Faraday = 96500 C

tr p
current. The time required
s x
2

m
–1
i y E
C(A)he9.65 × 10 sec (B) 19.3 × 10 secmi(C)
mol ) [JEE 2008]
4 4 r × 10 sec (D) 38.6 × 10 sec
st28.95 4 4

C he r ts
For the reaction of NO ¯ ion in an aqueous solution, E° is +0.96 V. Values of E° for e
xp
28. some
E
3

try
metal ions are given below
V (aq) + 2e¯  V
2+
E° = – 1.19 V
m is
s C h e
Fe (aq) + 3e¯  Fe
3+

e r t E° = – 0.04 V
Au (aq) + 3e¯x p
E
3+
Au E° = + 1.40 V
Hg t
s r y+ 2e¯  Hg
i of metal that is(are) oxidised by NO ¯ in aqueous solutionsis(are)
2+
(aq) E° = + 0.86 V [JEE 2009]

e m r t
Ch(A) V and Hg e
The pair(s)

xp (D) Fe and V
3

(B) Hg and Fe
E
(C) Fe and Au

i stry
Paragraphefor
h mQuestions 29 to 30
The concentration of potassiumC ions inside a biological cell is at least twenty times higher r
e ts
xpprocesses
than

r E
ysimple model for
the outside. The resulting potential difference across the cell is important in several

i s t
e t s
r a metal M is : Ch e m
such as transmission of nerve impulses and maintaining the ion balance. A

E p
such a concentration cell involving
x|| M (aq ; 1 molar) | M(s)
[JEE 2010]

ry cell the magnitude of the cell potential |E | = 70 mV.

+ +
M(s)| M (aq ; 0.05 molar)

i stelectrolytic
h e m
For the above cell

C
178
 Electro chemistry
29. For the above cell :–
(A) Ecell < 0 ; G > 0 (B) Ecell > 0 ; G < 0 (C) Ecell < 0 ; G0 > 0 (D) Ecell > 0 ; G0 < 0

e r t s e r t s
If the 0.05 molar E x p x p
solution of M is replaced by a 0.0025 molar MEsolution, then the magnitude
r y r y
+ +
30.
i s t is t
e m
of the cell potential would be :–
e m
Ch (A) 35 mV (B) 70 mV
Ch(C) 140 mV (D) 700 mV

31. AgNO3 (a) was added to an aqueous KCl solution gradually and the conductivity of the
solution was measured. the plot of conductance () versus the volume of AgNO3 is

er ts
E xp r ts


stry 
xpe  

m i y E
C h e Volume
istr Volume Volume Volume
(P)
e m (Q) (R) (S)

(A) (P) (B) (Q)

Ch (C) (R) (D) (S)
e r ts
E x p
stry [JEE 2011]
i
32. Consider the following cell reaction :

m
Che
2Fe(s)+O2(g)+4H+(aq)  2Fe2+(a)+ 2H2O() E° = 1.67 V

e r ts
x p
At[Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25°C is –
E(B) 1.77 V
(A) 1.47 V
s t ry (C) 1.87 V (D) 1.57 V

m i s
Ch e Paragraph for Question 33 and 34 er
t
E xp
y
trsalt,
The electrochemical cell shown below is a concentration
s
cell.
2+
m i 2+ –3

Che in concentrations of M2+ ions at the two electrodes.

M | M (saturated solution of a sparingly soluble MX ) | | M (0.001 mol dm ) | M The
2

emf of the cell depends on the difference

er ts
The emf of the cell at 298 K is 0.059V.
E xp2012]
[JEE
The value of G (kJ mol ) for the given cell is (take If = 96500 C mol ) ry
33. –1

is t –1

(A) –5.7 (B) 5.7

e r ts (C) 11.4 hem(D) –11.4
xp C
The solubility productE(K ; mol dm ) of MX at 298 K based on the information available
try cell is (take 2.303 × R × 298/F = 0.059 V)
3 –9
34.
s
sp 2

m i
e
for the given concentration

C h
(A) 1 × 10 –15
(B) 4 × 10 –15
(C) 1 × 10 –12
(D) 1 × 10 –12

179
 Electro chemistry
35. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List-I. The
variation in conductivity of these reactions is given in List-II. Match List-I with List-II and

er ts er ts
select the correct answer using the code given below the lists : [JEE-Adv. 2013]

Exp List-I
Exp List-II

stry
(P) (C2H5)3N + CH3COOH (1)
ry
Conductivity decreases and then increases
st
mi X Y
mi
Che (Q) KI(0.1M) + AgNO3(0.01M) (2)
X Y Che Conductivity decreases and then does not change
much
(R) CH3COOH + KOH (3) Conductivity increases and then does not change
X Y much
(S) NaOH + HI (4) Conductivity does not change much and then
X Y increases

e r ts
R xpS
Codes :
Rs
y2 1E r t
3pe 2
P Q P Q S
3 st4r
(A)
(C) em
i 3 4 1 (B)
(D) ry
4
Ex4 3 1

Ch
2
i s t 1 2

h e m
36. C
The standard reduction potential data at 25ºC is given below
er ts
[JEE-Adv. 2013]

xp
3+ 2+

E
Eº (Fe , Fe ) = +0.77 V ;

try
Eº (Fe2+, Fe) = –0.44 V ;
Eº (Cu2+, Cu) = +0.34 V ;
mis
Eº (Cu+, Cu) = +0.52 V ;
s Che
r t
Eº (O2(g) + 4H+ + 4e–  2H2O] = +1.23 V ;
e
xp
Eº [(O2(g) + 2H2O + 4e–  4OH–)] = +0.40 V ;
E
try
Eº (Cr3 +, Cr) = –0.74 V ;
s
mi
ts
Eº (Cr2+, Cr) = –0.91 V ;

Che er
Match Eº of the redox pair in List-I with the values given in List-II and select the correct

E xp
tryList-II
answer using the code given below the lists :
List-I
i s
m (1) – 0.18 V
(P) 3+
Eº(Fe , Fe)
C h e ts
er
xp
+ +
(Q) Eº(4H O  4H + 4OH ) (2) – 0.4 V
E
2

(R) Eº(Cu2+ + Cu  2Cu+) (3) – 0.04 V

stry
ts mi
(S) Eº(Cr3+, Cr2+)
e r
(4) – 0.83 V

Ch e
Codes :
E xp
Qy R
tr
4 is 1
P S P Q R S
(A)
em 2 3 (B) 2 3 4 1
C(C)h 1 2 3 4 (D) 3 4 1 2
180
 Electro chemistry
37. In a galvanic cell , the salt bridge – [JEE-Adv. 2014]

s s
(A) Does not participate chemically in the cell reaction

e r t er t
E x p
(B) Stops the diffusion of ions from one electrode to another
E x p
s r y
(C) Is necessary for the occurence of the cell reaction
t mixing of the two electrolytic solutions istry
m i
(D) Ensures
m
he
C All the energy released from the reaction
38.
h e
C X  Y,  Gº = –193 kJ mol is used for the
–1
r

oxidizing
M+ and M+  M3+ + 2e¯, Eº = –0.25 V.
Under standard conditions, the number of moles of M+ oxidized when one mole of X is

e r
converted to Y is [F = 96500 C mol–1]ts [JEE-Adv. 2015]

E xpa solution of a weak acid HX (0.01 M)ris ts10 times smaller than the
39. y
tr of a solution of a weak acid HY (0.1
The molar conductivity
s
of
x e
p   , the difference in
m i y E M). If 
e
0 0

r
molar conductivity
h t
X– Y–

C their pK values , pK (HX) – pK (HY),

m
is : i s
e
a a a

Ch acids to be <<1).
(consider degree of ionization of both [JEE-Adv. 2015]
e r ts
E p
x2016]
try
40. For the following electrochemical cell at 298K, [JEE-Adv.
2
+ 4+ 2+
Pt(s) | H (g, 1bar) | H (aq, 1M) || M (a), M (a) | Pt(s)
m is
 M  aq. 
2

s= 10 C h e
 M e t
aqr
x
E = 0.092 V when

xp RT
cell 4

E
Given : E stry= 0.151 V ; 2.303
i
0
= 0.059 V

h e m of x is -
M 4  /M 2 
F
r t s
C The value e
xp (D) 2
E
try
(A) –2 (B) –1 (C) 1
i s
msolution of a weak monobasic acid was determined bys
41.
h e
C of plantinized Pt electrodes. The diatcane betweenerthet
The conductance of a 0.0015 M aqueous

xpsolution
using a conductivity cell consisting
E
tryof limiting molar
2
elecrodes is 120 cm with an area of cross section of 1cm . The conductance of this
was found to be 5 × 10 S. The pH of the solution is 4. Theivalue s
ts m is Z ×10 S cm mol .
–7

conductivity    of this weak e r C h e

xp
0 2 –1 –1
monobasic acid in aqueous solution
E
m

is try
The value of Z is [JEE Adv. 2017]

h e m
C
181
 Electro chemistry
42. For the following cell,

Zn(s) ZnSO4  aq  CuSO4  aq  Cu (s)

r ts r ts
e expression for G
when the concentrationp ofe
Zn is 10 times the concentration of Cu p
E x 2+
x
E Eº (cell ) = 1.1V]
, then 2+

(in J mol ) risy

st
–1

s t r y
i i
[F is faraday constant ; R is gas constant; T is temperature;

e m e m
Ch Ch
[JEE - 2017]
(A) 2.303RT – 2.2 F (B) – 2.2 F
(C) 1.1F (D) 2.303RT + 1.1 F

43. For the electrochemical cell,

e r ts
Mg(s)|Mg2+ (aq, 1 M) || Cu2+ (aq, 1 M)|Cu(s)

E xpis 2.70 V at 300 K. When the concentration

r t s
try changes to 2.67 V at 300 K. The value
2+

e
the standard emf of the cell of Mg is changed to x

i s E x p
m
M, the cell potential of x is ____.
e r y
h R = 11500 KV ) , where F is ithestFaraday constant and R is the gas constant,
C(given, F –1

m
h e
ln(10) = 2.30) C e r
[JEE - 2018]ts
Consider an electrochemical cell: A(s) | A (aq, 2 M) || B (aq, 1 M)| B(s). TheE
xp
44. n+ 2n+

s y
tisrzero,
value of ΔH θ

θ
m i
for the cell reaction is twice that of ΔG at 300 K. If the emf of the cell the ΔSθ (in J

s of B formed at 300 Khis e

–1 –1

r t
K mol ) of the cell reaction per mole
C ____.
e gas constant) = 8.3 J K mol . H, S and G are enthalpy,
E x p
(Given: ln(2) = 0.7, R(universal –1 –1

s t r y
i
entropy and Gibbs energy, respectively.)R [JEE - 2018]

h e m r t s conditions at 1 bar
45.
C and 298 K. Its cell reaction is
Consider
xp
a 70% efficient hydrogen-oxygen fuel cell working under
e standard

y E [JEE-2020]
1 istr
H (g) + m
h e O (g) H O(l).

rts
2 2 2

C
2

The work derived from the cell on the consumption of 1.0 × 10 mol of H (g) is used p to e
xis the
–3

E
2

s t r
compress 1.00 mol of a monoatomic ideal gas in a thermally insulted container. y What

t s m i
e r
change in the temperature (in K) of the ideal gas ?
h e
E xp for the two half-cells areCgiven below.
The standard reduction potentials

i s try+ 4e  2H O (l) , Eº = 1.23 V, 2H (aq.) + 2e  H (g), Eº = 0.00V.

O (g) + 4H (aq.) + – + –

Fm
2 2 2

Usee
h –1

C = 96500 C mol , R = 8.314 J mol K

–1 –1

182
 Electro chemistry

ANSWER KEY
s s
EXERCISE # (JEE-MAIN)

er t r
e 7.t
1. 2
xp 2.
E 10. 3
1 3 3. 4. 4
x p
E 1 14.
5. 1 6. 1 3

y 12. r2y 13.

8. 1
is
9.
tr 3 11. 3
i st 4

e1 m 16. 1 em
C
15.
h 3 17. 4 18.
Ch 19. 1 20. 4 21. 1

22. 2 23. 1 24. 3 25. 1 26. 4 27. 4 28. 2

29. 3 30. 1 31. 2 32. 1 33. 4 34. 2 35. 2

s
36. 1 37. 4 38. 3 39. 3 40. 3 41. 3 42. 3

45. p3 e r t
x s
y E52. 1 53. [–0.93] NTAxAns. rt to 1.53)
43. 3 44. 3 46. 2 47. 1 48. 4 49. 2

51. st2r p e(1.52

50. 4
m i y E
e
h NTA Ans. (2.13 to 2.16) 55. i4st
C[2.15] r
em
54.

toh
56. [5.67 or 5.68] NTA Ans. (5.66C 5.67) 57. (None) NTA Ans. (3)
e r ts
E p (58)
xAns.
try
58. 2 59. 1 60. 3 61. 96500 62. 144.00 63. 142 NTA

–6
m is
e
64. 60 65. 66. 11.00

r t s C h
e
xpEXERCISE # (JEE-ADVANCED)
E
ry 2. K = 2.287 × 10 3. A 4. B
K = 6.26is ×t
m s
7 –12

e t
1. 10
r
C sp

h
5. C 7.95 × 10 M Cp e
x
–5

yE
6. decrease with time 7. 8. B 9. C

H = – 49987 Jmol , S =– 96.5 J mol Ks,tsr=1.47 ×10 M

10. 0 –1

m i0 –1 –1 –5

11. A 12. C 13. Che14. B 15. K = 10

0.05 16.
e
B ts
r
10

p
C

0
E x A
–6
17. (a) E = 0.59 V, log K = –10 10 (b) 52.8, 10 moles
SP 18. A
y
tr 26. D
19.

25.is D
ts m
–1
20. D 21. 55 S m 22. C
e r
23. D 24. B
h e
ABD 29.xpB 31. C D
27. B 28.
E 30. C
y 36. D 37. AB 38. 4 39. 3 40. D
32. D 33. D

35.istAr
em
34. B

41. C6h 42. A 43. 10 44. –11.62 45. 13.32

183
 Electro chemistry

HINT AND SOLTUIONS

s s
EXERCISE # (JEE-MAIN)

er t er t
1. (2)
x p
E power  Exp
SRP  ,
s ry
t Reducing power 
Oxidising
stry
m i mi
Che Che
2. (3)
SRP  , Oxidising power 
Reducing power 

e r ts
3. (1)
Exp r ts
t
E  E is
y
r log  
 
xpe 2

E
0.0591 Zn
m n Cu 


h e
cell cell

stry 2

C mi
Ch e
er ts
xp
0.0591 1
Ecell  1.10   1.07V
E
log

try
2 0.1

mis
s Che
t
4. (4)

number of equivalent ofxofp

r
e = 9650 = 0.1mole
y E electrons

tr of of Ag = 0.1mole
96500

m i
number of s
equivalent
s
h e
C (1) er t
Exp
tVry
5.
E° = E° + E° 2+
= 0.14 + 0.77 = i
3+

m
2+
s
0.91
e
Sn / Sn Fe / Fe

C h r ts
xpe
E
6. (1)

stry
i
0.06
E° = 10 g Keq
n
r ts em
0.591 =
0.0591
Expe
10 g Keq Ch
ry
1
Keq = 10 ist
m
10

Ch e
184
 Electro chemistry
7. (3)
°m NaBr = °m KBr + °m NaCl – °m KCl = 152 + 126 – 150 = 12 Scm2 mol–1

e r ts er ts
Ex p Exp
8. (1)
Zn(s) +is
r y
t (eq) –– Zn (eq) + H (g) stry
m
+ 2+

mi
On adding H SO , equilibrium shift to right he
2H
e
2

C h 2 4
C
0.0591 [Zn 2 ]
E = E° – log  2
n [H ]
[H+] , E 

e r ts
9. (3)
E xp r t s
2

s tr
3
Cr | Cr  0.41V y 2
 3

x p e
i
Mn | Mn 1.57V

Fe e| m Co | Co  y
r E
h t
2 3 2 3
Fe  0.77V 1.97V
CAs Cr will have maximum oxidation potential
m s
i value, therefore its oxidation will be easiest.
Ch e
e r ts
E xp
try
10. (3)

m is
11. (3)
s C h e
e r t
xp
5.12  1000 Q
3
27
r y E
96500

is t 3 7

m
Q=54897×10 C = 5.4897×10 C

h e e r t s
C (2) xp
12. E
y withdrawing effect of two flouring
is ttorelectron
m conductivity.
Difluoroacetic acid will be strongest acid due

C h e ts
r
atoms so as it will show maximum electrical

xp e
13. (1)
ry E
° = ° + ° – °
i s t
ts m
HOAC NaOAC HCl NaCl

e r C h e
p
= 91 + 426.2 – 126.5= 390.7

E x
s r y
t 0.059
i
14. (4)

h e m
C = – 0.8 – 1 log K
0.152  log K = – 16.11
sp sp

185
 Electro chemistry
15. (1)

s s
C = 0.1 M, R = 100 

er t er t
E
K = 1.29 Sm =
x
1
p ×.
 –1

Exp
y y
100 A
r
t R = 520 .
C = 0.02sM,
i 
istr
he m hem
C = 1 × 129
K
520 C
1
 129
M = 520 = 124 × 10–4 Sm2mol-1
1000  0.02

16. (3)
e r ts
CH COONa + HCI CH
E xpCOOH + NaCI From the reaction,s
rt + –
+ try =e
3 3

 0
is =  o
 HCI
+ 0
or 
E x
 po 0 0

o

o

m
NaCI HCI NaCI

y
CH3COONa CH3COOH CH3COOH CH3COONa

heto calculate the value of one should know

CThus is r value of along with and .
tthe 
o

o

m
NaCI HCI

C h e s
17. (4)
er t
0 = + 1.1 –
0.0591 [Zn ] 2

E xp
try
log 2
2
s
[Cu ]

m i
log = 37.3
[Zn ]

[Zn ]
[Cu ] ts
2
= 10
2
37.3

C h e
r
2 2

e
[Cu ]

E xp
18. (1)
s t r y
m i – log [Cr ] 3 2
s
Ch e
E =
cell E 0
cell 2 3
e r t
xp
[Fe ]

= 0.3 –0.04 = 0.26 V ry

E
ist
2
0.059 (0.1)
= 0.3 – log
m
3
6 (0.01)

Che er ts
xp
19. (1)

Fe + 3e  Fe
3+ –
G = –3 × F × E 0

ry E
t
Fe3 /Fe
1

G = –2 × t Fs m i s
Fe +2e Fe
2 –

e r ×E 2

C h e 0
Fe2 /Fe

E x p
y
–
Fe + e Fe
3+
G = G – G
2+

tr – 2 × 0.439 × F = – 1 × E (Fe /Fe ) × F

3 1 2

G = 3 × i s
m/Fe ) = 2 × 0.439 – 3 × 0.036= 0.878 – 0.108= 0.770 V
0.036F 0 3+ +2

e
3

Eh(Fe
C
0 3+ +2

186
 Electro chemistry
20. (4)

s s
2 4
Al2 O3  Al + O2
r t
e× 10 J mol er t
p p
3 3

E x –1
Ex
–1

y
3

y
r
G = +966 kJ mol = 966

is t
G = – nFE
 r istr
m× 10 = – 4 × 96500 × E m
cell

Che966 3

Che
cell

Ecell = 2.5 V

21. (1)
2H+ (aq) + 2e–  H2 (g)

e r ts
Ered = Eºred –
0.0591
E x
PH
p
log 2 2 ; E =0–
0.0591 2
ts
; E =–
0.0591
r
log log2
y
red red

r e
2
n (H ) 2 (1) 2
st
i to be negative for (3) option E x p
m y
Che
E is found
tr
red

m is
h e
C ts
22. (2)

er
xp
 = 1.3 S/m.
E
try
R = 50 

m is
e
M = 0.2
1 
r t s C h
=
R A
×
x p e
E
50ym .
= 1.3 × r
A ist
 –1


h e m r t s
C  = 1 ×  = 1  1.3  50  0.25 Sm xp e
–1
E
try
R A 260

m i s



0.25
 6.25 h e
C Sm mol
 10 4 2 –1

ts
1000  M 1000  0.4
er
E xp
s tr y
23. (1)
t s m i
e r C h e
X+Y X +Y 2+ 2+

E x p
r y
For reactionstotbe spontaneous Eº must be positive.
m i
Che
187
 Electro chemistry
24. (3)
 = 1.4 S/m.

er ts er ts
R = 50 
Exp Exp
M = 0.2
1 st
ry stry
m= i× mi
Che
R A
Che

 = 1.4 × 50 m–1.
A
1  1
= × =  1.4  50  0.25 Sm–1
R A 280

er ts 0.25
xp
   5  104 Sm2 mol–1
1000  M
y E er ts
1000  0.5

25. (1)
is tr Exp
h=e
m try
C c  –B C 

mis
Ch e
26. (4)
er ts
Higher the SRP, better is oxidising agent
Exp
Hence MnO4– is strongest oxidising agent
istry
hem
27. (4)
e r t s C
Cu2+ + 2e–  Cu
x p
E = 63.5 g.
2F
stry1 mole

(2)em
i
28.
Ch er ts
If E > E° Then electron flow from cathode to anode
Exp
try
ext

29. (3)
m i s
5e + 8H + MnO  Mn + 4H h Oe
C ts
– + – 2+
4 2

er
0.06 [H ] f  8

Exp
y
E = 1.51 – log
5 [H ]8 i
istr
(103 )8
r ts em
e Ch
0.06

xp
E = 1.51 – log 7 8
E
5 (10 )
0.06 y
E = 1.51 – str× 32 = 1.126 V
m i
e 5

CSohit will oxidize Br & I – –

188
 Electro chemistry
30. (1)
2e– + 2H2O  H2 + 2OH–
Catnode :

e r ts er ts
x p
CHE– COO
n = 2
Exp f

y y
–

Anodest
i : r  CH = CH + 2COst
2

i r
+ 2e –

m m
2 2 2

Che CH – COO
C h e 2
–

nf = 2 nf = 1

Total equivalent of gases (CH2 = CH2 , CO2 , H2) = 0.2 + 0.2 + 0.2 = 0.6
0.2 0.2
ts
Total moles of gases = + 0.2 + = 0.4

Total Vol. of gases = 0.4x×p

e r 2 2

y E 22.4 = 8.96 L
er ts
is tr E xp
(2) em y
31.
h
CCu + ZnSO –– X istr
e m
h chemical series. ts
4

No reaction Cu lies below Zn inC

electro
er
Exp
32. (1)
istry
SRP  , Oxidising power 
hem
er ts C
E x p Reducing power 

st ry
m i
ts
33. (4)
hBe er
C H +3O →B O +3H O
2 6 2 2 3 2
xp
Moles of O required =3× moles of B H =3
ry E
st
2 2 6

I t
m i
C e
= moles of O ×4 =12  t=3.2hrs
h 2

ts
r
96500

xp e
r y E
34. (2)
st
i therefore S O is
2

er ts h e m 2

C
Since S O has highest value of
p
reduction potential among given species
x
2 8 2 8

r y E
s t
strongest oxidizing
i
agent

h e m
C
189
 Electro chemistry
35. (2)

s s
2  3
 Fe(aq) + Ag(s)
t t
Fe(aq) + Ag (aq)

p er per
– E
Ex Ex
0 0
Eº = E Ag  /Ag Fe3 /Fe2

stry stry
i i
–
Now Eqn.1: Fe + 2e +2
Fe, Eº = y

he m Gº = – 2Fy
hem
C C
Eqn.2: Fe+3 + 3e–  Fe, Eº = z
Gº = – 3Fz
Eqn.2 – Eqn. 1, We get

t= s– 3Fz + 2Fy
Fe+3 + e–  Fe+2 , (Eº)1

p e r
E x Gº
r ts
 
tr y
– 1 × F × (Eº)
s
1
= – 3Fz + 2Fy
xpe
 m i y E

e r
1
= 3z – 2y
0

h t
(Eº) = E
s
Fe3 /Fe2

CNow Eº = E  E m i
Ch e
0 0

ts
Ag  /Ag Fe3 /Fe2

er
xp
= x – (3z – 2y)
E
try
= x – 3z + 2y

mis
36. (1)
s Che
er t
G° = –nFE°
= –2 × 96000 ×E xp
s r y 2
t J = –384 kJ
m i
ts
= –384000

Che er
Exp
try
37. (4)
Reaction at cathode
mis
Ni2+ + 2e– — Ni
Che ts
er
0.1 mole
Exp
0.1
stry
Deposited moles of Ni =
ts
= 0.05
mi
e
2
e r Ch
E xp
38. (3)
is ry with increasing concentration of electrolyte and molar conductivity
tincreases
e mwith increasing concentration of electrolyte.
Conductivity
h
Cdecreases
190
 Electro chemistry
39. (3)
m = mº – A C

er ts
value of A will be same for NaCl and KCl
er ts
Exp
So Slope for both curve will be same.
Exp
try
But mº for KCl > mº for NaCl
s stry
mi
So m KCl > m NaCl
mi
Che (for a given Concentration)
Che
40. (3)
oxidising power  S.R.P value.
  correct order is : Bi+3 < Ce+4 < Pb+4 < CO+3

ts
Eºred oxidising power 
e r
E xp r ts
y e
41. (3)
As,
 m is ofrAcidic Strength or ka is A > C > By Exp
AcidictStrength 
Ka

CAs,he Acidic Strength ()  k () melectrical

istr conductivity ()
order

e
a

C h r ts
42. (3)
xpe
E
try
Anode
PbSO4 + 2e– Pb(s) + SO24
mis
s
Equivalent of PbSO4 electrolysed = 0.05
Che
er t 0.05
xp
Moles of PbSO4 =
E 2

stry 0.05

mi
Mass of PbSO4 = × 303 = 7.6 g

(3)e ts
2
43. h
C er
Exp
try
Ecell  2V
G° = –nF Ecell is
....(2)hem
As, ... (1)
and also, G° = –RTlnKC
C er ts
xp
Equating (1) and (2)

 nF E aq =  RTlnKC
ry E
ist
ts m
2 × 96000 = 8 × 300 lnKC
 KC = e160
er Che
3p
Correct option is x

E
i s try
h em
C
191
 Electro chemistry
44. (3)

SRP  ,
er ts Oxidising power 
er ts
Exp Reducing power 
Exp
ry try
(3)m
ist mis
Che
45.
Che
Cell reaction :
 2H(eq )  2Ag (s)  2Cl(eq)
H 2( g )  2AgCl(s)  

[H  ]2 [Cl  ]2 (106 )2 (106 )2

QC = = = 10–24
PH2
er ts 1

log Q xp s
E t
0.06
E = E° –
n
tr y per
0.92e=m
i s Ex
h E° –
0.06
log 10
stry
–24

C 2
mi
h e
C ts
E° = 0.2V

er
xp
46. (2)
E
    try

Ecell = E ox + E red
anode cathode

mis
E  

s Che
t
= 0.76 +
r
red cathode

x p eSRP will produce maximum E 

E
A electrode having maximum
y
cell

47. (1)
is t r
h m
K e 10 × 10 r ts
C e
15
C

E xp
?
try


s
E
i
Cell

...(1)hem
G° = –nF E
C ts

Cell

er
Also, G° –RTlnKC Exp
...(2)

stry
ts mi
r e
Equate (1) and (2)

 nF E =  RTlnKxp


E
e Ch
y
C

r
Cell

s
2 ×iE
t = 2.303RT log 10

h e m 
Cell
16

C
F

192
 Electro chemistry
48. (4)

S° = nF
dE 

e r ts er ts
p p
dT

E x Ex
G° = –nFE°
s ry
t– T S° stry
i
G = H°
m mi
CheS° = –2 × 96000 × 5 × 10 = –96.5 J
Che –4

G° = –2 × 96000 × 2 = – 384 kJ

G° = H° – T S°
300  ( 96.0)
– 384 = H° –
ts
1000

pe r
E x
H° = –384 – 28.8 = – 412.8 kJ mol–1
r ts
49. (2)
str y xpe
m i y E
e r
   
   –
h
C = 425.9 + 100.5 – 126.4 = 400 mi
mHA mHCl mNaA

st mNaCl

h e
C
K 1000 5 10 1000 –5

er ts
xp
    50
E
m
M 0.001


m

50 1
  0.125 istry

 m 400 8
hem
e r ts C
E x p
y
50. [4]
Sol. (1) Cu + s
i
2+ r
2et  Cu : E° = 0.34V
–

h m+ e  Cu : E° = 0.522V
(2)eCu r ts
e
–

C
+

–
Exp
try
(3) Cu + e  Cu
2+ +

(3) = (1) – (2)

mis
(2  0.34) – (0.522)
C h e ts
E° = = 0.158V
er
1
Exp
stry
ts mi
e
51. (2)
er Ch
Exp
try
52. (1)

mis
C h e
193
 Electro chemistry
53. [–0.93] NTA Ans. (1.52 to 1.53)
Sol. 2H2O  O2 + 4H+ + 4e– E0Red = 1.23 Volt

er ts
but since it is an oxidation reaction
er ts
E x p
Hence, E0rxn = –1.23 Volt
Exp
s r y
tE – 4 log [H ] stry
Ei= i
0.0591 0 + 4

hem hem
C 0.0591
= –1.23 –
4
log (10–5)4 C
0.0591
= –1.23 – × (–20)
4
= –1.23 + 0.2955
= –0.9345
er ts
xp
 Answer should be –0.93 V

y E er ts
r
instead of 1.52 V or 1.53 V

[2.15] m ist Exp

e NTA Ans. (2.13 to 2.16)
Sol. CEh= –0.13 + 0.14 = 0.01 V
54.
stry
0

mi
log K h e
C ts
0.06
r
0
at equilibrium E =
n
xpe
0.06 [Sn 2 ]
E
try
0.01 = log
2 [Pb 2 ]
mis
[Sn 2 ] 0.01 2
s Che
t
log =
[Pb 2 ]
per0.06
[Sn ] 2

E x
y
1/3

r
= 10 = 2.15
t
2

s
[Pb ]

m i
55. h
C (4)e er ts
G = –n F E Exp
ry
Sol. cell
G is negative, if E is positive
ist
m
cell

e
–
Anode : Cu(s) Cu (C ) + 2e : E° +2

Cathode : Cu (s) + 2e Cu(s)

+2
C h –
1

r ts
e
:– E°

Cell reaction : Cu+2(C2)  Cu+2(C1) E°cell = 0 Exp

stry
Ecell = Ecell –
2.303RT
ts mi
e
log Q

p e
nF
r Ch
Elogx
2.303RT C 
nFy
E ==0–  
1

t r
cell

isC < 1  C < C

C  2

>m
E e
Ch
1
0 : if
cell 1 2
C 2

194
 Electro chemistry
56. [5.67 or 5.68] NTA Ans. (5.66 to 5.67)
Sol. 108 gm Ag require 1 equivalent 7 charge

er ts
Equivalent of O2produced = 1
er ts
Exp
Moles of O2 =
1
Exp
stry 4
stry
mi 1
mi
C
57.
he Volume of O2 at STP =  22.71 = 5.67 & 5.68

(None) NTA Ans. (3)

4
Che
Sol. With increase in temperature conductance of ions increases.
58. (2)
Sol. E ocell = 0.34 – (–0.76)

r
= 1.10 volt
e ts
xp
If Eext > 1.10 volt
Cu  Anode
y E er ts
istr
Zn  Cathode
Exp
h em
If Eext = 1.10 volt
try
CZn  Anode
mis
h e
ts
Cu  Cathode
C e r
59. (1)
E xp so
try
+ +
Sol. As voltage is '2V' so both Ag & Au will reduce and their equal gm equivalent will reduce
gmeq Ag = gmeq of Au
m is
Wt

Wt
s C h e
t
Ag Au
E qwt AgE qwt Au

p er
wt
 y 
E
E x
At wt
tEr At wt
Ag qwt Ag Ag
So
wt
(3)em
i s qwt Au qwt Au Au

s
60.
Ch e r t
p
Sol. Given curve of  vs c is for weak electrolyte, so ans.EisxCH COOH.
t ry
m 3

m is
61. (96500)
C h e ts
Sol. E° cell = E° Cu/Cu + E° Sn /Sn 2+ 2+

p e r
= –0.34 – 0.16
E x
= –0.5 V
s tr y
ts m i
e
2+ 2+

r
[Cu ] = [Sn ] = 1 M

x p e C h
E
E° cell = E cell

ry
G = –nF E cell
t × 96500 × (–0.5)
=s–2
i
m = 96500 J
C h e
195
 Electro chemistry
62. (144.00)
 Cu + e–
Sol. Cu+ 

e r ts er ts
Ex p
Cu+ + e– 
 Cu(s)
Exp
s ry
t Cu + Cu stry
m i mi
e
+ 2+

e
2Cu

Ch E E E o
Cell
o
Cu  /Cu
o
Cu 2 /Cu  Ch
= 0.52 – 0.16 = 0.36 V
At equilibrium  Ecell = 0
RT
ts
E oCell  ln K
nF
e r
E  nF o
E xp r ts
RT ry e
Cell

p
ln K =
is t Ex
lnhKe
m0.36  1
try
C is
–1
= = 14.4 = 144 × 10
0.025
e m
63. (142) NTA Ans. (58)
Ch er ts
Sol. K.Emax = h – W = stopping potential.
Exp
H2(g) + 2AgCl(s) — 2Ag(s) + 2Cl–(aq) + 2H+(aq)
istry
[Cl]2 [H  ]2
hem
Q=
p H2
er ts C
log QE
x p
ntry
0.06
E = E° – = K.E
is
max

m ts
Che er
For Na :
2 2
Exp
try
0.06 [0.1] [0.1]
0.22 – log = hv – 2.3
2 1
m i s
 h = 2.64 eV
C h e ts
er
xp
For K :
0.06
ry E
0.22–
2
log (x)2(x)2 = hv – 2.25
ist
r ts = 2.64 – 2.25
em
–0.12 log x = 0.17 p
E x e Ch
t y= 0.12  1.42 = 142 × 10
–log x =rpH
0.17 –2

is
mAns. 142
Ch e
Correct NTA Ans. 58

196
 Electro chemistry
64. (60)
Sol.

e r s
Cr2O72  14H  6e  2Cr 3  7H2O
t er ts
E x p
Change flow = 2 × 8 × 60 coul.
Exp
stry 2  8  60
stry
i i
–2
= F. = 10

hem 96000
hem
C 0.104
Mole of Cr3+ obtained =
52
mole C
0.104
Equivalent of Cr3+ = × 3 eq.
52
= 6 × 10–3 eq.

er ts
xp
6  103

y E
Current efficiency =
102 ts
× 100 = 60
er
s tr is 60.
So correct ianswer
Exp
h e m try
C(–6) mis
Ch e
ts
65.
Sol. G° = –nFE°
er
Exp
try
17.37 × 103 = –3 × 96500 × E°
E° = –0.06
mis
= –6 × 10–2
s Che
e r t
E x p
66. (11.00)
st r y
×m
i
Sol. {2e
Ch t × 60 × 60 / 96500} × 0.60 =
10
×6
er ts
xp
122
E
try
So t = 10.98 hours

mis
Che ts
er
Exp
stry
ts mi
er Che
Exp
istry
hem
C
197
 Electro chemistry
EXERCISE # (JEE-ADVANCED)
KC = 6.26 × 107
1.

er ts er ts
xp
E° = 0.77 – 0.54 = 0.23 =
E
0.06
logK
Exp
r
K = 6.26s×t10
y 2

stry
m i 7

mi
e
2.Ch K = 2.287 × 10
sp
–12
Che
Ag+(cathode) –– Ag+(anode)
0.1 M 2S
2S
Q=
0.1
er ts
E = 0.164 = –
0.06
E xp
 2S 
log  
r ts
s try
2  0.1 
xpe
S = 9.23 × i10 E
m
–3

h e stry
CKsp = 4S = 3
2.287 × 10
mi –12

Ch e
3. (A)
e r ts
E xp
The specie having higher reduction potential oxidizes the specie having lower reduction
potential.
is try
h e m
4. (B)

e r t s C
p reaction is spontaneous.
xtherefore
E°cell = 0.33 + 0.44 = 0.77 Volt
E
ry
since E°cell is positive
s t
× 10i M
7.95 m s
e t
–5
5.
h
C Let initially [Cu ] = C M p er
x
2+

E
 moles of Cu in the solution =
2+ C  250
1000 is
trCymoles
= 0.25

h e m
After electrolysis C e r ts
0.25  C
E x p
y
2+

r
Moles of Cu =
2
is t
2+ 0.25  C
e r ts he m
p C
Eq. of Cu = × 2 = faraday of electricity.
2
0.25 × C = 2 × 10y× E
x
r
–3

st
16 × 60/69500
2m 10 i  16  60
C e
3

h
–5

C
= 7.95 × 10 M
0.25  96500
198
 Electro chemistry
6. decrease with time

s s
Cell reaction :

e r t e r t
E x p Fe2+ + Ce4+ –– Ce3+ + Fe3+
E x p
Q=1
r y
tE° = 1.61 – 0.77 = 0.84 V
Es= stry
i i
m which will decrease with time.
m Direction of flow of current is cathodehtoeanode
Che
C
7. (C)
Disproportionate reaction

e r ts
8. (B)
E xp r ts
conductance try pe
s
1

m i Ex
e y
Hydrated radius of ion

C h istr
e m
9. (C)
Ch e r ts
E xp
10. 0 –1 0
H = – 49987 Jmol , S =– 96.5 J mol K , s =1.47 ×10 M –1 –1

s t r y –5

m i
e
+ –
(i) H (g) + 2AgCl(s) –– 2Ag(s) + 2H (aq) + 2Cl (aq)
h
2

(ii) G° = H° – TS° = –nF°

e r t s C
At 15°C : H° –x288
E p × S° = –2 × 96500 × 0.23
s t ry: H° – 308 × S° = –2 × 96500 × 0.21
m i
At 35°C
s
Ch e On solving
er t
H° = –49587 J/mole
E xp
S° = –96.5 J/mole-K
i s try
h e m
C e r ts
11. (A)
E xpestimated
– 2+ 3+

s t r
MnO ion can oxidise both Fe to Fe as well as Cl to Cl . So Fe(NO ) cannoty –
be
i
4 2 3 2

t
quantitatively with MnO ion in HCl.
e s 4
–

e m
r | Cl (aq) | | MnO (aq)C|hMn (aq). is euqal to (1.51 – 1.4)
Eº for the cell Pt, Cl (g) p
x
– – 2+
(1 atm)
E
Cell 2 4

= 0.11 V.
is try
hem
12. C(C)
199
 Electro chemistry
13. (0.05)

E + 0.03 = Eº –
r ts
0.06
log
[Zn 2 ]
.
er ts
pe] p
2 0.5
0.06 E[Znx Ex
y y
2
E = Eº –
i st r
2
log
C
. M = 0.05 M.
istr
he m hem
C
14. (B) C
Zn + Fe2+ –– Fe + Zn2+
0.1
Q= = 10
0.01
0.0591
er ts
xp
E = E° – logQ
2
y E er ts
is–tr xp
0.0591

e m
0.2905 = E° log(10)
ry E
t
2
C h is
E° = 0.32
h e m
E° =
0.0591
logK = 0.32 C er ts
xp
2
E
try
K = 100.32/0.0295

mis
s Che
15. KC = 1010
In  In + 2e , E° p eVr t
x
+ 3+ –

E
= 0.42

s r y
t In , E° = – 0.4 V
2+

m i
In + e  +

h e
______________________________
C er ts
In  In + e
2+ 3+ –

Exp
try
______________________________
is
em
Eº = 0.44 V
Eº = 0.15 + 0.44 = 0.59 V Ch ts
er
xp
cell

0 = 0.59 –
0.059
log K.
ry E
1
ist
K = 1010 .
r ts em
Expe Ch
16. (B)
istry
e
Fe 
h mFe + 2e , 2+ –
0.44 V.
C
200
 Electro chemistry
1
2H+ + O2 + 2e– H2O, 1.23 V.
2

r ts r ts
pe+ H O, Eº = 0.44 + 1.23 = 1.67 volt.Expe
___________________________________________________________________

Fe + 2H + O E
1 +
x
Fe 2+

s t 2y
r
2

s
2

t ry
Gº = i– 2 × 1.67 × 96500 = – 322.3 kJ.
m m i
e
Ch (a) E = 0.59 V, log K = –10 (b) 52.8,
0
e
Ch10 moles –6
17. 10 SP

(a) Ag+(aq) + Cl–(aq) –– AgCl(s)

Gorxn = –109 – (–129) – 79

ts
= –57 kJ/mole
e r
–57 × 100y
xp
G° = –nFE°
= –1E× 96500 × E° r ts
tr pe
=s0.591 V
E° i Ex
hem try
C G° = –RT n Ksp = –57 × 100mi
1 s
C he r ts
log Ksp = –10
xpe
E
istry
(b) 2Ag+(aq) + Zn(s) –– Zn2+(aq) + 2Ag(s)
hem
e r ts
E° = 0.8 + 0.76 = 1.56 V C
x p
2y E
0.06
E° = log Kq = 1.56

i s tr
hemKq = 10 52

r ts
C xp e
18. (A)
2Ag + C H O + H  2Ag(s) + C H O t +r
E
y, Eº = 0.8 – 0.05 = 0.75 volt.
is
+ +
2H
m
6 12 6 2 6 12 7

0.0592
C h e ts
0 = 0.75 – log K.
er
xp
2
ln K = 2.303 × log K = 2.303 × 25.34 = 58.38.
r y E
is t
19. (A)
e r ts h e m
+
[H ] = 10 M. –11

x p
Elog(10 ) = – 0.05 + 0.65 C
= – 0.05t–ry
0.0591
is 2
–11 2
E
m
oxide

Cor,he H = 0.65 volt.

201
 Electro chemistry
20. (D)
Standards electrode potential does not depend upon on concentration.

r ts er ts
xpe p
(55 S m–1)
x
21.
AgBr (s)  Ag E
r y + Br + –

ry E
s t
+ 10i ) × s = K = 12 × 10 . ist
e(s m –7 –14

hem
Ch s = 3 × 10 M.
sp
–7
C
[Ag+] = 4 × 10–7 M ; [Br–] = 3 × 10–7 M ; [NO3–] = 10–7 M.
Ktotal = Ag+ + Br– + NO3–
Ktotal = 4 × 10–4 × 6 × 10–3 + 3 × 10–4 × 8 × 10–3 + 1 × 10–4 × 7 × 10–3.
Ktotal = 24 + 24 + 7.
e r ts
K = 55 Scm .
E xp
–1

r ts
y
total

s tr xpe
22. (C)
m i y E
h e s tr
CEº = 1.36 + (– 0.54) = 0.82 V (+ ve). Spontaneous.
Cl –
+ 2I  I + 2Cl . –

i
m
2 2

h e
C er ts
23. (D)
Exp
Mn3+ + e–  Mn2+, 1.50 volt.
istry
2H2O  O2 + 4H+ + 4e–, 1.23 volt.
hem
e r ts
_____________________________________ C
4Mn + 2H O  4Mn
3+
x p
EH O. + O + 4H , 2+ +
Ecell = 1.5 – 1.23 = 0.27 volt. (+ ve).
r y
2 2

So Mn willtoxidise
is
3+

m ts
2

C (B)e
24. h
xp e r
Mol of NaCl = 4 × 0.5 = 2 mol.
1y
E
s =r × 2 = 1 mol.
t
i
1
m
No. of mole of Cl evolved = × mol of NaCl
e
2
2 2
25. (D)
Ch er ts
Taking the 1 : 1 molar combination of Na–Hg amalgam.
Exp
stry
i
weight = 2 × 23 + 2 × 200 = 446 g.

e r t s hem
26. (D)
2Na + 2e  2Na.E–
x p C
ry = 2.
+

is trequired
m
No. of Faraday

h e
C total charge = 2 × 96500 = 193000 coulomb.


202
 Electro chemistry
27. (B)
  t (sec)
r ts
Faraday law equivalents of H2 produced =
e t 96500
er ts
0.01  2 =E
x p
 3
Exp
s tr y 10 10
= 96500  2 = t
stry
i 96500
m t =19.3  10 sec mi
Che 4

C h e
28. (ABD)
The species having less reduction potential with respect to NO 3– (Eº = 0.96 V) will be oxidised
by NO3–. These species are V, Fe, Hg.

29. (B)
e r ts
E xp r ts
y e
30. (C)

is r M) || M (aq, 1 M) | M(s)
t0.05 xp
E
+ +
M (s) | M (aq,

h e m try
s
–
M (s)  M (aq) + e
CCathode : M (aq) + e  M (s) mi
+
Anode :
+

h e –

C er ts
xp
_____________________

E
try
M+ (aq) |c  M+ (aq) |a

mis
0.0591
s
M (aq) |a
Che
t
Ecell = E°cell –
r
log
M (aq) |c
e
1

= 0 –E x p
y
0.0591

istr 1
log

h e m = + ve = 70 mV and hence G = – nFE = – ve.

r ts
C e
cell

0.0591
log 20 = 140 mV. Ex
p
= 70 mV +
1
s t ry
m i
31. (D)
C h e ts
er
Exp
stry
ts mi
er Che
Exp
istry
hem
C
203
 Electro chemistry
32. (D)

E = Eº –
0.059

e r t s[Fe 2 ]2
log  4
er ts
p p
4 [H ] PO2
x
E (10 ) = 1.67 – 0.03 log10 ry Ex
= 1.67 – try
3 2

i s
0.06
log
ist 7

m 0.03 m
3 4
4 (10 )  0.1 2
he h e
C = 1.67 – × 7 = 1.67 – 0.105 = 1.565C= 1.57 V.
2

33. (D)

ts
G = – nFEcell = – 2 × 96500 × 0.059 × 10–3 kJ/mole
e r
xp
= – 11.4 kJ/mole.

y E er ts
i s tr Exp
34. (B)
h em try
CM|M 2+
(aq) || M (aq) | M2+

mis
h e
C ts
0.001 M
er
xp
–
Anode : M  M (aq) + 2e 2+

E
Cathode: M2+ (aq) + 2e–  M
istry
____________________________
hem
e r ts
M2+ (aq)c  M2+ (aq)a C
x p
E M (aq) 
r y
E = 0 –ist log 
0.059 2

m 
ts
a

e
cell 3

Ch
2  10 
per
Ex
try
0.059  M (aq)  2
0.059 =  log  
s
a
2  10 
mi 3

he ts
 M (aq)  C r
– 2 = log  
2
a

xpe
 103 
ry E
ist
ts
10–2 × 10–3 = M2+ (aq)a = solubility = s
r em
3
E 4 ×p
K = 4s = 4 × (10 ) = x
e
10 –5 3 –15 Ch
try
sp

m is
Ch e
204
 Electro chemistry
35. (A)

s s
X Y

r t
e As CH COOH is a weak acid, its conductivity r t
(P) (C 2 H 5 )3 N + CH3COOH  CH3COO– (aq) + (C2H5)3NH+ (aq)
e is already less. On
Exp x p
Ereaction takes place and new
y y
3

istr addition of weak base,

is t r
acid-base
m ions are created. Som
Che C h e 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.

e r ts
(R) CH3COOH + KOH  CH3COOK (aq) + H2O

E xpOH (aq) is getting replaced by CH rCOO

–
t s –

try e
, which has poorer
p
3

m is E
conductivity. So conductivity x dereases and then after the end
e t r y
Ch i s
point, due to common
place. So,m
ion effect, no further creation of ions take

h e conductivity remain nearly same.

(S) NaOH + HI  NaI (aq) C+ H O e r ts
xandp
2
+

y
+
E
after end point, due to OH , it increases.istr
As H is getting replaced by Na conductivity dereases
–

So answer of 39 is : (P) – (3) ; (Q) – (4) ; (R) – (2) ; (S) – (1).h e mis (D).
e r t s C Answer

E xp
try
36. (D)
Eºis
h e
(P)
m Fe3+, Fe

r t s
C xp e
E
 1 × 0.77 + 2 × (– 0.44) = 3 × x
i s try
V ~ – 0.04 V. he
m
C ts
0.11
 x=–
e r
xp
3

(Q) 4H O  4H + 4OH + –

ry E
s t
2

2H O  O + 4H + 4es
t m i
r4OH e
+ –
– 1.23 V
2

x p e
2

+ 0.4C
h
E
– –
+ O + 2H O + 4e  V
y
2 2

is t r
_____________________________________

h e m 4H O  4H + 4OH +
– 0.83 V –

C
2

205
 Electro chemistry
(R) Eº(Cu2+ + Cu  2Cu+)

e r ts er ts
× 1p= 0.34 × 2
x × 1 + 0.52 x
E Exp
s r y
tCu + e  Cu
x = 0.16 V.
stry
 i
m + Cu  Cu + e
2+ –

– 0.52 V em
0.16 V i +

Che _______________________________Ch
+ –

Cu2+ + Cu  2Cu+ – 0.36 V

However, in the given option, – 0.18 V is printed.
(S) Eº(Cr3+, Cr2+)

e r t s
x × 1 + 2 × (– 0.91)p
x – 1.82r=y
E x = 3 × (– 0.74)
r ts
s t – 2.22
xpe
 m
i y E
he x = – 0.4 V
C Hence, most appropriate is (D). mi s tr
–h
e
(P) – (3) ; (Q) – (4) ; (R)C (1) ; (S) – 2.
e r ts
E xp
rythat the ions in
37. (AB)

i s
Salt bridge is introduced to keep the solutions of two electrodes separate, tsuch
h e m of diffusion.
ts reaction. However,Cit is not necessary for occurence of
electrode do not mix freely with each other. But it cannot stop the process
r
It does not participate in theechemical
cell reaction, as we E xpthat designs like lead accumulator, there was no salt bridge, but still
s
reactionsitakes
y
trplace.
know

38. h (4)e
m r ts
C xp e
E
try
–
M  M + 2e
+ 3+

G = –nFE For 1 mole of M

0 0
m is
+

G = –2 × 96500 × (–0.25) J C h e ts
r
0

xp e
= + 48250 J/mole = 48.25 KJ/mole
r y E
Energy released by conversion of 1 mole of
is t
X  Y G = –193 KJ
e r ts h e m
x p
E = 48.25 = 4 C
y
193
r
+

t
Hence mole of M convert

m is
C h e
206
 Electro chemistry
39. (3)
    
X

er ts Y

er ts
  
Exp   
x
  
E p   

y y
H X H Y


i tr
s 
 (1) 
istr
m = , So  (HX) =  hemand  (HY) =  
HX HY

CheAlso
m
C m

m 1 m

m 2
m 

(Where 1 and 2are degrees of dissociation of HX and HY respectively.)

Now, Given that
m (HY) = 10 m (HX).

e r ts
xp(2)

 m 2 = 10 × m 1

y E er ts
 
is tr
 = 10  2 1

E xp
K =em, therefore K =y
C h
a
C2
1– 
but  << 1,
is tr C . a
2

e m
C×h = . ts
2
K a (HX) 0.01α12 0.01  1  1
 = =  10 
er
xp
K a (HY) 0.1α 22 0.1   1000

E
try
 log (Ka (HX)) – log (Ka (HY)) = –3.
 pKa (HX) – pKa (HY) = 3.
mis
s Che
e r t
40. (D)
E x p
st r y 4+
–– 2H (aq) + M (aq) + 2+

i
H (g) + M (aq)
2

e m
[H ] [M ] 1  [M ]
 2 2 2

r ts
Ch P [M ] = 1  [M ] = 10 e x

xp
Q = 4 4
H2

y E
log10  x = 2istr
0.059 x

m
E = 0.092 = 0.151 –
2
Che ts
er
xp
41. (6)

=G×

= 5 × 10–7 ×
120
= 6 × 10–5 Scm–1
ry E
A 1
ist
r ts em
e Ch
104

Exp
[H+] = c = 10–4 M   =
0.0015

istry
hem
C
207
 Electro chemistry

K  1000 6  105  1000

 m   = 40 Scm2mol–1

s s
0.0015 0.0015
r t er t
pe
 Ex  Exp
   y  
s tr
m  m

stry
i  
i
m

he m
m

hem
C   
40 
= 6 × 10
m
10 4
2
C
0.0015
 Z = 6

e r ts
xp(aq) + Cu (s)
42. (A)

y
2+
E
Zn (s) + Cu (aq) ––Zn 2+

e r t s
is tr] x p
e m [Zn 2

ry E
h t
Q = = 10
s
c

C G° = –2 × F × 1.1 i
2
[Cu ]

e m
Ch er ts
xp
G = G° + RT n Q = –2.2 F + RT n 10= 2.303 RT – 2.2 F
E
istry
43. (10)
hem
r t s
Mg (s) + Cu2+ (aq) –– Cu (s) + Mg2+ (aq)
e RT  1 C
E x p
Initially :
tr y
E = 2.7 = E° –

n    E° = 2.7
 1
is [Mg ] = x
2 F

h e m 2+

r ts
e
When :
C xp
E = 2.67 = 2.7 –
300 x
 1r y
 n   E
ist
2  11500
n x = 2.3  x = 10 m
Che er ts
Exp
44. –11.62
stry
ts
2A (s) + B2n+ (aq) –– 2A n+ (aq) + B(s)
mi
er Che
xp
Given H° = 2G°

r y E
G° = H° –S°
is t

emG° = 2G° – TS°

Ch G° = TS°
208
 Electro chemistry

 G = G° + RT n Q = 0

r t s  22 
G° = –8.3 × 300 × n   = 300 × S°
e er ts
xp  1 
E× n 4 = –8.3 × 2 × 0.7 = –11.62 J/K ry Exp
S° =y
i st r – 8.3
ist
hem h e m
C (13.32)
45. C
1
For the cell : H2(g) +  H2O ( )
O2(g) 
2
EoCell = 1.23 – 0 = 1.23 V

r ts
 G oCell = – n F EoCell
e
E xpJ/mole
= –2 × 96500 × 1.23
r t s
s tr y x p e
m i
= –237390 J/mole
y E
he = –237.39 k J/mole
C  efficiency of the cell is 70% mi s t r
h e
C 70
e r ts
xp
 Work obtained per mole reaction = 237.39 × k J/mole
100
E
tr×y10 k J
70
s
–3 –3
 when 10 mole H (g) is used then work obtained = 237.39 ×
2

m i 100

s C h e
r t
The work obtained is used to compress monoatomic gas
e
present in insulated container
 q=0
E x p

t r
Uy = nC T = W
is
V

he m W 237.39  0.7 10 kJ 3

r ts
C  T =
nC

3
xp e
E
3
1  8.314 10 kJ
V

try
2
T = 13.327 K
m is
C h e ts
e r
E xp
s t r y
t s m i
e r C h e
E x p
st r y
m i
C he
209
 Ionic Equilibrium

EXERCISE # (JEE-MAIN)
1.
e r t s r ts
The solubility in water of a sparingly soluble salt AB2 is 1.0 × 10–5 mol L–1. Its solubility
e[AIEEE-2003]
product will be
x p
E (2) 1 × 10 x p
E(4) 4 × 10
(1) 1 × 10 ry
s t
– 15

str
–10
y –15 –10

i i
(3) 4 × 10

he m h e m
C its solubility product is: [AIEEE-2002]
2.C The solubility of Mg(OH) is x mole/lit. then
2
3
(1) x (2) 5x3 (3) 4x3 (4) 2x2

3. The molar solubility in mol L–1 of a sparingly soluble salt MX4 is 's'. The corresponding

e r ts
p
solubility product is KSP. 's' is given in terms of KSP by relation : [AIEEE-2004]
(1) s = (K / 128) E (2)xs = (128K ) tss = (K /256)
y e r
1/4 1/4 1/5 1/5

tr
(3) s = (256K ) (4)
p
SP SP SP SP

m is E x
h e st r y
C i
–
4. The conjugate base of H PO is [AIEEE-2004]
m (3)
2 4

h e
C ts
(1) H PO (2) P O (4)
r
3 4 2 5

xp e
r y E
5.
t
Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be : [AIEEE-2005]
is
(1) 3.88 × 10 6
(2) 3.98 × 10 (3) 3.98 × 108

h em(4) 3.68 × 10 –6 –6

e r t s C
The solubility productxofpa salt having general formula MX , in water is : 4 × 10 . The
Eions in the aqueous solution of the salt is :
–12

y
6.
r
2

is
concentration t of M 2+
[AIEEE-2005]

h m× 10 M (2) 2.0 × 10 M (3) 4.0 × 10 M r(4)ts1.6 × 10 M

(1)e1.0
e
–4 –6 –10 –4

C x p
r y E
7. What is the conjugate base of OH ?
m ist –
[AIEEE-2005]
(2) Ohe
C ts
2– –

r
(1) O (3) H O (4) O
e
2 2

Exp
s tr yand 5.0 × 10 –5 –10

i [AIEEE-2007]
8. The first and second issociation constants of an acid H A are 1.0 × 10 2

respectively. the overall dissociationsconstant of the acid will be m

er t e
h (4) 5.0 × 10
p
(2)x5.0 (3) 5.0 × 10C
E
5 –5 15 –15
(1) 0.2 × 10 × 10

s t r y
m i
C h e
210
 Ionic Equilibrium
9. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffer solution of HA in which

s s
50% of the acid is ionised is [AIEEE-2007]

e r t e r t
(1) 7.0
E x p (2) 4.5 (3) 2.5
E x p (4)
9.5
st r y s t r y
Inm
i
a saturated solution of the sparingly soluble e m i
Ch
10. e Ch
strong electrolyte AglO (molecular mass = 283) 3

the equilibrium which sets in is : [AIEEE-2007]

If the solubility product constant Ksp of AgIO3 at a given temperature is 1.0 × 10–8, what is the

r ts
mass of AgIO3 contained in 100 ml of its saturated solution ?
e
(1) 28.3 × 10 g –2

E x p
(2) 2.83 × 10 g –3
(3) 1.0 × 10 g
ts
(4) 1.0 × 10 g–7 –4

y e r
r acid, HA, is 4.80. The pK of a weakxpbase, BOH, is 4.78. The pH of an
The pK ofis at
11.
e m a weak
r y E: b

C(1)h9.58
aqueous solution of the corresponding salt.
i s
BA,twill be [AIEEE-2008]

h e m (3) 7.01
C ts
(2) 4.79 (4) 9.22

e r
12. –4

E xp
Solid Ba(NO ) is gradully dissolved in a 1.0 × 10 M Na CO solution. At what concentration
ry
3 2 2 3
2+
of Ba will a precipitate begin to form?(K for Ba CO = 5.1 × 10 )
SP
is t[AIEEE-2009]
3
–9

(3) 4.1 × 10 M em
h
–8 –7 –5 –5

s
(1) 8.1 × 10 M (2) 8.1 × 10 M (4) 5.1 × 10 M

e r t C
13.
E x
Solubility product of silverp bromide is 5.0 × 10 . The quantity –13
of potassium bromide (molar
mass taken as r
s y
tof AgBr is :
–1

i
120 g mol ) to be added to 1 litre of 0.05 M solution of silver nitrate to start the

e m r t s
Ch(1) 5.0 × 10 g (2) 1.2 × 10 g (3) 1.2 × 10 xgpe (4) 6.2 × 10 g
precipitation [AIEEE–2010]
–8 –10 –9 –5

r y E
14. In aqueous solution the ionization constants ifor
m stcarbonic acid are [AIEEE–2010]
K = 4.2 × 10 and K = 4.8 × 10 he
1
–7
2
C –11

e r ts
Select the correct statement for a saturated 0.034 M solution of the carbonic acid :- xp
r y E
+
(1) The concentration of H is double that of CO
i
2–
s t
ts M m
3

e r 2–
h e
p is greater than that of HCOC
(2) The concentration of CO is 0.034 3

(3) The concentration of x

E 2– –

try of H and HCO are approximately equal

CO 3 3

m is
(4) The concentrations +
3
–

C h e
211
 Ionic Equilibrium
15. At 25° C, the solubility product of Mg(OH)2 is 1.0 × 10–11. At which pH, will Mg2+ ions start
precipitating in the form of Mg(OH)2 from a solution of 0.001 M Mg2+ ions ? [AIEEE–2010]

e r ts er ts
(1) 8
E x p (3) 10
E x
(4)
p
(2) 911

s r y
t involving H PO are given below: istry
m i m
–

e e
16. Three reactions
h h
2 4

C (i) H PO 3+ H O  H4O + H PO C PO + H O  HPO + H O

2 (ii) H 3
+
2 4
–
2 4
–
2 4
2–
3
+

(iii) H2PO4– + OH–  H3PO4 + O2–

In which of the above does H2PO4– act as an acid ? [AIEEE-2010]
(1) (ii) only (2) (i) and (ii) (3) (iii) only (4) (i) only

e r ts
The K for Cr(OH) isE xp r t
–30
s
try e
17. 1.6 × 10 . The molar solubility of this compound in water is:
p
sp 3

m i s E x [AIEEE–2011]

h e st r y
C m i
Ch e
e r ts
E xp
try
18. An acid HA ionises as
HA H +A + –
is
The pH of 1.0 M solution is 5. Its dissociation constant would bee: m
t s C h [AIEEE–2011]
(2) 5 er
p
–10 –8 –5
(1) 1 × 10
x (3) 5 × 10 (4) 1 × 10
E is 1.7 × 10 , the combination amongst the following which gives a
s t ry
i
–10
19. If K of CaF at 25ºC
m of CaF is :
sp 2

h e
precipitate
e r ts
[JEE-MAIN(online)–2012]
C (1) 1 × 10 M Ca and 1 × 10 M F (2) 1 × 10 MxCap and 1 × 10 M F
2

E
–2 2+ –5 – –4 2+ –4 –

s r y
t M Ca and 1 × 10 M F
i
–3 2+ –5 – –2 2+ –3 –
(3) 1 × 10 M Ca and 1 × 10 M F (4) 1 × 10

The pH of a 0.1 molar solutionC h e m ofs

of the acid HQ is 3. The value of the ionization constant, Ka t
20.
e r
this acid is :
E xp
[AIEEE–2012]
×r
(4) 1 t 10y
(1) 1 × 10 –7
(2) 3 × 10
s
(3) 1 × 10
m
–7
i s –3 –5

r
Solid Ba(NO ) is graduallyedissolved
t e
hM Na CO solution. At which
21.
x p in a 1.0 × 10 C –4

concentration of Ba ,E
3 2 2 3

s r y
t= 5.1 × 10 )
2+
precipitate of BaCO begins to form ? 3

m i –9

e
(K for BaCO

C(1)h5.1 × 10 M (2) 8.1 × 10 M (3) 4.1 × 10 M (4) 7.1 × 10 M

sp
–5
3 [JEE-MAIN(Online)–2013]
–7 –5 –8

212
 Ionic Equilibrium
22. NaOH is a strong base. What will be pH of 5.0 × 10–2M NaOH solution ? (log2 = 0.3)

ts s
[JEE-MAIN(Online)–2013]
(2) e r e r t
(1) 13.70
E x p 13.00 (3) 14.00
E x p
(4) 12.70

try s r y
tthe correct order of solubilities of
Whichis i
23.
he m soluble salts Hg Cl , Cr (SO ) , BaSO e m
one of the following arrangements represents
h
C sparingly 2
C and CrCl respectively ?
2 2 4 3 4 3

[JEE-MAIN(Online)–2013]
1 1 1 1 1 1
 K 3  K 8 1
 K 4 1
 K 3  K  4  K 3
(1)  sp  ,  sp  , (K sp ) 2 ,  sp  (2) (K sp ) ,  sp  ,  sp  ,  sp 
2

 4   108   27   4   27   108 

e r ts
 K   K p  K 
1 1 1 1 1 1

 , Ex ,  s
K  K  K 
t  4 
1 3 4 3 3 4 1 3

 108ry  27   4  r
sp sp sp sp sp sp

 108   27 e
(3) (K ) ,  2
 (4)   ,  , (K ) , 2

t p
sp sp

m is Ex
h e s tr y 5 g of acetic acid and 7.5 g of sodium
24.
Cacetate and making the volume equal tom
What
i
would be the pH of a solution obtained by mixing

h e
ts
500 mL? [JEE-MAIN(Online)–2013]
(Ka = 1.75 × 10 , pKa = 4.76) C
–5
e r
E xp
try
(1) 4.76 < pH < 5.0

m i s
e
(2) pH < 4.70

r t
(3) pH of solution will be equal to pHs of acetic acid C h
xp e
(4) pH = 4.70
r y E
is t
h e m r ts of HCl with a pH of 1
25. How
e
many litres of water must be added to 1 litre of an aqueous solution
C to create an aqueous solution with pH of 2 ? xp
ryL
(3)t2.0
E [AIEEE–2013]
(1) 0.1 L (2) 0.9 L
m i s (4) 9.0 L

C h e tofs
e r
xp
+
26. In some solutions, the concentration of H O remains constant even when small amounts
strong acid or strong base are added to them. These solutions are known as: y E
3

i s t r
r ts
e(2) True solutions (3) Ideal e m[JEE-MAIN(Online)–2014]
hsolutions (4) Buffer solutions
(1) Colloidal solutions
E x p C
s t r y
m i
C h e
213
 Ionic Equilibrium
27. Zirconium phosphate [Zr3(PO4)4] dissociates into three zirconium cations of charge +4 and four

s s
phosphate anions of charge –3. If molar solubility of zirconium phosphate is denoted by S and

er t e r t
Exp E x p
its solubility product by Ksp then which of the following relationship between S and Ksp is
correct ?
s r y
t/144} s r
t } y [JEE-MAIN(Online)–2014]
(1)S = i{K
m
1/7

m i
(2) S = {K 1/7
/(6912)
e (4)eS = {K /6912}
sp sp

Ch (3)S = (K /6912)
sp
1/7
Ch sp
7

28. pKa of a weak acid (HA) and pKb of a weak base (BOH) are 3.2 and 3.4, respectively. The pH
of their salt (AB) solution is [JEE-MAIN–2017]
(1) 7.2
e r t s
(2) 6.9 (3) 7.0 (4) 1.0

E xpan acid with methyl orange as indicatorr,twhich

s of the following is a
29.
tr ? y
An alkali is titrated against
s x p e
m i
correct combination
E [JEE-MAIN–2018]

h e End Pointtry
C(1) Strong
Base Acid
m i s
Strong
C hePink to colourless r ts
(2) Weak Strong Colourless to pink
xp e
ry E
t
(3) Strong Strong Pinkish red to yellow

m is
(4) Weak Strong
s
Yellow to Pinkish red
h e
Cof Ba . When 50 mL of a 1 M
e r t
30.
E x p
An aqueuous solution contains an unknown concentration 2+

solution of Na y
t r
is product of BaSO is 1 ×10 . What is the origional concentration
SO is added, BaSO just begins to precipitate. The final vloume is 500mL.
2 4 4

e m
The solubility –10

t s
r [JEE-MAIN–2018]
of Ba ? 2+

Ch e
4

E x p
–10 –9
y
(3) 2r×10
t
–9 –9

is
(1) 1.0 × 10 M (2) 5 × 10 M M (4) 1.1 ×10 M

m
31. An aqueous solution contains 0.10ChMeH S and 0.20 M HCl. If the equilibrium constants eforrthets
formation of HS from H S is 1.0 × 10 and that S from HS ions is 1.2 × 10xp
2
–
2
–7 2–

r y E –
then the –13

2–
concentration of S ions in aqueous solution is
i s t [JEE-MAIN–2018]
(2) 5 × 10rts e m
(1) 5 × 10 –19

x p e
–8
(3) 3 × 10
C h –20
(4) 6 × 10 –21

r y Esalts is the most basic in aqueous solution? [JEE-MAIN–2018]

32.
i s t
Which of the following

h e m COO) (2) Al(CN)

C
(1) Pb(CH 3 2 (3) CH COOK
3 (4) FeCl
3 3

214
 Ionic Equilibrium
33. The minimum volume of water required to dissolve 0.1 g lead (II) chloride to get a saturated

s s
solution (Ksp of PbCl2 = 3.2×10–8; atomic mass of Pb = 207 u ) is : [JEE Main-2018 Online]

er t e r t
(1) 0.36 L
E x p (2) 0.18 L
(3) 17.98 L
E x p
(4)1.798 L

s r y s ry
t volumes of NaOH and HCl of
tfour solutions are prepared by mixing different
34.
m i
Following
m i
C hedifferent concentrations, pH of which one ofh e
C will be equal to 1 ?
them
[JEE Main-2018 Online]
M M M M
(1) 75mL HCl + 25mL NaOH (2) 100mL HCl + 100mL NaOH
5 5 10 10

(3) 55
M M
HCl + 40mL NaOH
e r t s M
(4) 60mL HCl + 40mL NaOH
M
10 10
E x p 10
t s
10

y e r
tMrH SO solution is added to 30 mL ofE0.2xMpNH OH solution. The pH of the
is
mmixture is : [pk of NH OH = 4.7]. try
e
35. 20 mL of 0.1 2 4 4

C h i s
m (3) 9.0
resultant b 4 [JEE Main-2019 (Jan)]

h e
(1) 9.4 (2) 5.0
C (4) 5.2
e r ts
E x p
A mixture of 100m mol of Ca(OH) and 2g of sodium sulphate was dissolvedyin water and the
36. 2

i s r
tthe
volume was made up to 100 mL. The mass of calcium sulphate formed
e m and concentration of

t s are : (Molar massC ofh

r
–

e
OH in resulting solution, respectively, Ca(OH) , Na SO and CaSO are
,p
2 2 4 4

74, 143 and 136 g mol x

EL
–1 –6
respectively; K of Ca(OH) is 5.5 × 10 )[JEE Main-2019 (Jan)]
y
sp 2

i s t
(1) 13.6 g, 0.14rmol –1
(2) 1.9 g, 0.14 mol L –1

h mg, 0.28 mol L

(3)e1.9 –1
(4) 13.6 g, 0.28 mol L ts
r –1

C x p e
E
i
–12
s trofyAg CO in 0.1M AgNO is :
m
37. If K of Ag CO is 8 × 10 , the molar solubility
sp 2 3 2 3 3

C h e ts
r
[JEE Main-2019 (Jan)]
–10 –13 –12
xp e –11

E
(1) 8×10 M (2) 8 ×10 M (3) 8×10 M (4) 8×10 M

s t r y
If solubility product of Zr (PO ) issdenoted by K and its molar
t m i
38.
e r between A and K isCcorrect
3 4 4
e
h ? [JEE Main-2019 (Apr)]
solubility is denoted by S,
sp

E x
then which of the following prelation
y
sp

r
ist (2) S =  K  (3) S =  K  (4) S =  K 
1 1 1 1

(1) S =m
 K 7 6 9 7

Che  6912 
sp sp sp sp

 144   929   216 
215
 Ionic Equilibrium
39. In an acid-base titration, 0.1 M HCl solution was added to the NaOH solution of unknown

s s
strength. Which of the following correctly shows the change of pH of the titration mixture in

er t er t
Exp
this experiment?
Exp [JEE Main-2019 (Apr)]

stry stry
mi mi
Che Che

(1) D (2) A (3) C (4) B

e r ts
p 400 mL of 0.1 M H SO and 400tsmL of 0.1 M NaOH will
40. Consider the following statements [JEE Main-2019 (Apr)]

E xcontaining r
s tr y1.3.
(a) The pH of a mixture
x p
2
e 4

m i
be approximately
y E
e product of water is temperature dependent.
C(b)hIonic i str
h e m
C ts
–5
(c) A monobasic acid with K = 10 has a pH = 5. The degree of dissociation of this acid is
r
a

50%.
x p e
ry E
(d) The Le Chatelier’s principle is not applicable to common-ion effect.
is t
The correct statements are :
h e m
(1) (a), (b) and (c)
e r
(2) (a) and t s
(b) (3) (b) and (c)C (4) (a), (b) and (d)
The pH of a 0.02 M E
p
NHxCl solution will be [given K (NH OH) = 10 and log 2 = 0.301]
–5
41.

s tr y 4 b 4

m i s2.65
[JEE Main-2019 (Apr)]

Ch(1)e5.35 e r t
xp
(2) 4.65 (3) 4.35 (4)

r y E
i s t
42.
e m
What is the molar solubility of Al(OH) in 0.2 M NaOH solution? Given that, solubility
h [JEE Main-2019 (Apr)] ts
3

product of Al(OH) = 2.4×10 C

3
–24
:
pe r
–23 –22 –21
E x
–19

y
(1) 12 × 10 (2) 3 × 10 (3) 12 × 10 (4) 3 × 10

i s tr
e r s
ist1.84 × 10 M in water. h e m
C [JEE Main-2019 (Apr)]
–5
43. The molar solubility of Cd(OH)
in a buffer solution ofE
p
pHx= 12 is:
2 The expected solubility of Cd(OH) 2

is trMy (2) 2.49 × 10 M (3) 1.84 × 10 M (4) × 10 M

m
–11 –10 –9 –9

e
(1) 6.23 × 10

C h
216
 Ionic Equilibrium
44. The strength of an aqueous NaOH solution is most accurately determined by titrating :

s s
(Note : consider that an appropriate indicator is used) [Jee Main (Jan. 2020)]
r t e r t
xpe flask and concentrated H SO in a Econical xpflask
(1) Aq. NaOH in a pipette and aqueous oxalic acid in a burette
(2) Aq. NaOH in E
tryflask
tryin a burette and concentrated H SO in iasconical
a volumetric 2 4

m s
(3) Aq.iNaOH
min a conical flask
e e
2 4

Ch C h
(4) Aq. NaOH in a burette and aqueous oxalic acid

45. The stoichiometry and solubility product of a salt with the solubility curve given below is,
respectively : [Jee Mains (Jan. 2020)]

s
t2
3

M
er [Y]/mM

Exp 1 r ts
s try x pe
m i 1 2 3y E
C h e i str
[X]/mM

h e m (2) X Y, 2 × 10 M
ts
–6 –9

C
3 3
(1) XY, 2 × 10 M
r
2

(3) XY , 1 × 10 M –9 3
(4) XY , 4 × 10 M
xp
–9
e 3

E
2 2

–5

st r y
i
46. The K for the following dissociation is 1.6 × 10
sp

PbCl    Pb  2Cl

2 

h e m
s
correct for a mixture ofC
2(s) (aq) (aq)

e
Which of the following choices is
r t 300 mL 0.134 M Pb(NO ) and 100
xp
3 2

E
mL 0.4 M NaCl ? [Jee Main (Jan. 2020)]
(1) Q = K
s t r y provided (2) Q < K
i
sp sp

m s of hydroxide ions
(3) Not enough data (4) Q > K
e t
sp

47. h
C in a saturated solution of Cr(OH) will be : e r –31

xp [Jee Main (Jan. 2020)]

The solubility product of Cr(OH) at 298 K is 6.0 × l0 . The concentration
3

E
ry × 10 ) (4) (4.86 × 10 )
t(2.22
3

(1) (18 × l0 ) –31 1/2

(2) (18 × l0 )
m i s
(3) –31 1/4 –31 1/4 –29 1/4

Two solutions, A and B, eachC h e

of 100 L was made by dissolving 4 g of NaOH and 9.8 g t ofs
48.
e r
H SO in water, respectively. The pH of the resultant solution obtained from mixing
E xp40 L of
y (Jan. 2020)]
2 4

solution A and 10 L of solution B is ___________ :

i s t
[Jee r
Main

3 g of acetic acid is added to 250rmL

e t s h e m
49.

mL of this solution E
1 xp C
of 0.1 M HCl and the solution made up to 500 mL. To 20

s t ry mL of 5 M NaOH is added. The pH of the solution is _________.

i
2

h e many changes in volume.

[Given ; pK of acetic acid = 4.75, molar mass of acetic acid = 60 g/mol, log3 = 0.4771]
a

C Neglect [Jee Main (Jan. 2020)]

217
 Ionic Equilibrium
50. For the following Assertion and Reason the correct option is

s s
Assertion (A) : When Cu (II) and sulphide ions are mixed, they react together extremely

e r t e r t
pquickly to give a solid.
Reason (R) : ExThe equilibrium constant of Cu (aq) + S E
p
[Jee-Main (Sep) 2020]
x CuS(s) is high
y because the solubility product is low. y
2+ 2–

r r
(aq)

i s t i s t
e m e m
Ch (1) (A) is false and (R) is true. Ch
(2) Both (A) and (R) are true but (R) is not explanation for (A).
(3) Both (A) and (R) are false.
(4) Both (A) and (R) are true and (R) is the explanation for (A)

51.
r ts
While titrating dilute HCl solution with aqueous NaOH, which of the following will not be
e
required ?
E xp r ts
[Jee-Main (Sep) 2020]

s tr y
(1) Clamp and phenolphthalein
e
(2) Burette and porcelain tile
x p
i
(3) Pipette and distilled water
mbuffer is obtained on mixing : try E
(4) Bunsen burner and measuring cylinder
52.
h e
C(1) 100 mL of 0.1 M HCl and 200 mL ofm0.1iMs NaCl
An acidic

e
ChmL of 0.1 M CH COONa
[Jee-Main (Sep) 2020]
(2) 100 mL of 0.1 M HCl and 200
e r ts
xp
3

(3) 100 mL of 0.1 M CH COOH and 100 mL of 0.1 M NaOH

E
try
3

(4) 100 mL of 0.1 M CH COOH and 200 mL of 0.1 M NaOH

3

m is
100 mL of 0.1 M HCl is taken in a beaker and to it 100 mL ofh0.1
s C e
t
53. M NaOH is added in steps of

p e r measured. Which of the following graphs correctly depicts the

x
2 mL and the pH is continuously
E
change in pH?
s tr y [Jee-Main (Sep) 2020]

m7 i s
h e
C pH e r t
pH 7 Exp
(2)try
(1)
m i s
C h e ts
vol. of NaOH vol. of NaOH
e r
xp
. .

r y E
7
i s t
pH
e r t s h em
p C
pH 7
(3)
E x (4)

s ry
tNaOH
m. i
vol. of vol. of NaOH

C h e .

218
 Ionic Equilibrium
54. Arrange the following solutions in the decreasing order of pOH : [Jee-Main (Sep) 2020]

s s
(A) 0.01 M HCl (B) 0.01 M NaOH
r t r t
p e xpe
(C) 0.01 M CH COONa (D) 0.01 M NaCl
x
3

E (2) (A) > (C) > (D) >E(B)

r
(3) (B)i>s(D)
y
(1) (B) > (C) > (D) > (A)
t > (C) > (A) s
(4) (A) >i(D)
y > (B)
t>r(C)
he m h e m
C
55.
C
A soft drink was bottled with a partial pressure of CO2 of 3 bar over the liquid at room
temperature. The partial pressure of CO2 over the solution approaches a value of 30 bar when
44 g of CO2 is dissolved in 1 kg of water at room temperature. The approximate pH of the soft
drink is _______ × 10–1.
(First dissociation constant of Her s
t= 4.0 × 10 ; log2 = 0.3 ; density of the soft drink = 1 g mL )
[Jee-Main (Sep) 2020]

xp
–7 –1
CO
E t s
2 3

Given 64.00
tr y p e r
m is E x
e
Ifhthe
y
solubility product of AB is 3.20 × 10stMr, then the solubility of AB in pure water is
56.
C 2
m i –11 3
2

________ × 10 mol L . [Assuminge

Ch ts
–4 –1
that neither kind of ion reacts with water]

er
xp
[Jee-Main (Sep) 2020]
E
is try
h e m
er ts C
E xp
s t ry
m i s
Ch e e r t
E xp
i stry
h e m
C er ts
E xp
s t r y
t s m i
er C h e
E x p
s t r y
m i
C h e
219
 Ionic Equilibrium

EXERCISE # JEE-ADVANCED
1.
ts t s
What will be the resultant pH when 200 ml of an aqueous solution of HCl (pH = 2.0) is mixed

e r r
e [JEE 1998]
x p
with 300 ml of an aqueous solution of NaOH (pH = 12.0) ?
EPb(OH) in water is 6.7 × 10 M. Calculate xp
E solubility of Pb(OH) in a
st r y st r y
i i
–6
2. The solubility of the
m solution of pH = 8. m
2 2

C hebuffer
C h e [JEE 1999]

3. A buffer solution can be prepared from a mixture of [JEE 1999]

(A) sodium acetate and acetic acid in water
(B) sodium acetate and hydrochloric acid in water

r t s
(C) ammonia and ammonium chloride in water
e
E x p
(D) ammonia and sodium hydroxide in water.
t s
y
tMrsolution of the following salts increasesEinxthe e r
p order
s
The pH of i0.1
m y< NH4Cl < NaCl < NaCN
4. [JEE 1999]

h
(A) eNaCl < NH Cl < NaCN < HCl
4
s r
(B)tHCl
C(C) NaCN < NH Cl < NaCl < HCl mi(D) HCl < NaCl < NaCN < NH4Cl
Che ts
4

The average concentration of SO in the atmosphere over a city on a certain day x is p e r

5.
when the average temperature is 298 K. Given that the solubility of SO inry
2
E 10 ppm,

i s2
t water at 298 K is
1.3653 moles litre and the pK of H SO is 1.92, estimate the pH m
–1

s
a 2 3

C h e of rain on that day.

e r t
p
[JEE 2000]

E x
tr y
is to completely neutralise 10 mL of this solution is s
6. An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mL. The volume of 0.1 N

e m r t
Ch(A) 40 mL
NaOH required [JEE 2001]

x p e (D) 4 mL
E
(B) 20 mL (C) 10 mL

r y
7.
m ist of its solubility product (Ls) with its solubility
For sparingly soluble salt ApBq, the relationship
(S) is:
C he [JEE 2001]
rts
(D) Ls = S , (p.q) pe
x
p+q p q p+q p p pq p q pq p+q

E
(A) Ls = S , p . q (B) Ls = S , p . q (C) Ls = S , p . q

500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mLis oft0.2
y
r M HCl at 25°C.
ts of acetic acid in theheresulting
m solution and pH of the
8.

e r C
xp
(a) Calculate the degree of dissociation
solution. E
ry is added to the above solution, determine final pH. Assume there is no
(b) If 6 g iofst
m
NaOH

h e
C in volume on mixing. K of acetic acid is 1.75 × 10 M.
change a
–5
[JEE 2002]

220
 Ionic Equilibrium
9. Will the pH of water be same at 4°C and 25°C ? Explain. [JEE 2003]

r ts e r ts
xpZnSe and HgS are 10 , 10 , 10 andE10xprespectively,
10. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16M sulphide
ion. If K , MnS,E
y y
–15 –23 –20 –54

tr first ? tr
FeS,
sp which one

m is
will precipitate
m is [JEE 2003]

Che(A) FeS (B) MnS

C h e
(C) HgS (D) ZnS

11. HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on reacting with caustic soda. The
degree of hydrolysis of NaX is [JEE 2004]
(A) 0.01%
e r t s (B) 0.0001%
(C) 0.1% (D) 0.5%

E xp
with 0.1 M NaOH, calculate the pH at endr t s
12.
y
t=r5 × 10 and h << 1.
0.1 M of HA is titrated
s x p e point.

m i –6

y E
Che
Given Ka(HA) [JEE 2004]

i str
CH NH (0.1 mole, K = 5 × 10 ) ise
h m to 0.08 moles of HCl and the solution is diluted to
ts
–4
13. 3 2
C added b

e r
xp
one litre, resulting hydrogen ion concentration is [JEE 2005]
(D) 2 ×E
try
–11 –11 –5 –2
(A) 1.6 × 10 (B) 8 × 10 (C) 5 × 10 10

m i s
s C h e
14.
(A) CO , H CO , HCO pe
r t
The species present in solution when CO is dissolved in water : 2 [JEE 2006]

x
2– 2–

(C) CO , HCOy E
2 2 3 3 (B) H CO , CO 2 3 3

3
2–

is t r 3
–
(D) CO , H CO 2 2 3

h e m r t s
15. C Solubility product constants (K ) of salts of types MX, MX
x p e
E
SP and M X at temperature 'T' are 2 3
–8 –14

tr y –15 –3

is
4.0×10 , 3.2 ×10 and 2.7 ×10 , respectively. Solubilities (mol dm ) of the salts at
temperature 'T' are in the order :
e m [JEE 2008]
(A) MX > MX > M X Ch (B) M X > MX > MX e r ts
xp
2 3 3 2

(C) MX > M X > MX

2 3 (D) MX > M X > MX
r y E 3 2

is t
2.5 mL of M weak monoacidictbase
2
e r s h e m 2 –12

C
16. (K = 1 × 10 at 25°C) is titrated with M HCl in
p
b

x
5 5

ry E +

t at 25°C)
water at 25°C. The concentration of H at equivalence point is [JEE 2008]

m i s –14

e
(K = 1 × 10
w

C h
(A) 3.7 × 10 M –13
(B) 3.2 × 10 M –7
(C) 3.2 × 10 M (D) 2.7 × 10 M –2 –2

221
 Ionic Equilibrium
17. The dissociation constant of a substituted benzoic acid at 25°C is 1.0 × 10 –4. The pH of a 0.01

s s
M solution of its sodium salt is [JEE 2009]

e r t e r t
18.
x p
Aqueous solutions of HNO , KOH, CH COOH
3 and CH COONa
3 of
x p
identical concentrations
Eis(are) – [JEE -2010]
E of solutions which form a buffer uponrmixing
3 are
provided. They
s r
tand CH COOH
pair(s)
s y
tCH COONa
i (B) KOHiand
he mHNO and CH COONa
(A) HNO 3 3

h e mCOOH and CH COONa 3

C (C) 3 3 C (D) CH 3 3

19. In 1 L saturated solution of AgCl [Ksp(AgCl) = 1.6 × 10–10], 0.1 mol of CuCl
[Ksp(CuCl) = 1.0 × 10–6] is added. The resultant concentration of Ag+ in the solution is
1.6 × 10–x. The value of ‘x’ is. [JEE -2011]

e r ts
The Ksp of Ag2CrO4 is 1.1 × 10–12 at 298 K. The solubility (in mol/L) of Ag 2 CrO4 in a 0.1 M
p
20.
AgNO solution is Ex t s
(A) 1.1 × 10str
3
y (B) 1.1 × 10 (C) 1.1 × 10 xp
r
e (D) 1.1 × 10
[JEE 2013]

m i –11 –10

y E
–12 –9

e
h initial rate of hydrolysis of methyl acetateis(1M)
CThe r
t by a weak acid (HA, 1M) is 1/100 of that th

m
21.

h e
C ts
of a strong acid (HX, 1M), at 25ºC. The K of HA is [JEE 2013]
r
a

(A) 1 × 10 –4
(B) 1 × 10 –5
(C) 1 × 10 –6
(D) 1 × 10
x p e –3

ry E
Paragraph For Questions 22 and 23
is t
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH
constant pressure, a temperature s increase of 5.7 ºC was h e m in an insulated beaker at

contents. (Expt-1). Because e r t C measured for the beaker and its

E x p the enthalpy of neutralisation of a strong acid with a strong base is

–1

s t y
r (Expt-2), 100 mL of 2.0 M acetic acid (K = 2.0 × 10 ) was mixed with
a constant (–57.0 kJmol ), this experiment could be used to measure the calorimeter constant.

i
–5
In a second experiment
100 m s
a

C e
h5.6 ºC was measured.
mL of 1.0M NaOH (under identical conditions to (Expt-1)) where
e r t a temperature rise of

E x p
y
–1 –1 –1

tacidr obtained from the Expt-2 is [JEE 2015]

(Consider heat capacity of all solutions as 4.2 Jg K and density of all solutions as 1.0 g mL )
22.
m
Enthalpy of dissociation (in kJ mol ) of acetici s
–1

C h e ts
r
(A) 1.0 (B) 10.0 (C) 24.5 (D) 51.4
e
xp2015]
23. The pH of the solution after Expt-2
ry E [JEE
(A) 2.8 (B) 4.7 (C) 5.0
i s t
(D) 7.0

e r ts h e m
p product of AB (K )C= 2×10 and the value of ionization
24. The solubility of a salt of weak acid (AB) at pH 3 is Y ×10 mol L –3
. The value of Y is ____. –1

(Given that the valueE ofx

tr(Ky) = 1× 10
solubility –10
sp

m s
constant ofiHB –8 [JEE 2018]
e
a

C h
222
 Ionic Equilibrium
25. Dilution processes of different aqueous solutions, with water, are given in LIST-I. The effects
of dilution of the solutions on [H+] are given in LIST-II.

e r t s e r t s
(Note: Degree of dissociation (a) of weak acid and weak base is << 1; degree of hydrolysis of

E x p x
salt <<1; [H+] represents the concentration of H+ ions)
E p
s ry LIST-I
tmL of 0.1 M NaOH + 20 mL of r y LIST-II
1.ist The value of [H ] does not change
[JEE 2018]
P. i
m 0.1 M acetic acid) diluted to 60 mL hem on dilution
(10 +

Che C
Q. (20 mL of 0.1 M NaOH + 20 mL of 2. The value of [H+] changes to half
0.1 M acetic acid) diluted to 80 mL of its initial value on dilution
R. (20 mL of 0.1 M HCl + 20 mL of 3. The value of [H+] changes to two

e t s
0.1 M ammonia solution) diluted to 80 mL times of its initial value on dilution
rof Ni(OH) in 4. The value of [H ] changes to 1
E x p t s
r
S. 10 mL saturated solution +

y e
2

tr with excess solid Ni(OH) is Extimes p of its initial value on dilution

2

m is
e y
equilibrium
h tr
2

C diluted to 20 mL (solid Ni(OH)

m
is i s
still
e
2

present after dilution). Ch 5. +

The value of [H ] changes to 2
e r ts
E xpdilution
times of its initial value on

i
Match each process given in LIST-I with one or more effect(s) in LIST-II. The
s trycorrect option is
(A) P4; Q2; R3; S1
h
(B) P4; Q3; R2;
e mS3
(C) P1; Q4; R5; S3 rts C R4; S1
xp e (D) P1; Q5;

A solution of 0.1 M E
26.
s tr y with the volume of HA added is shown in the figure below. What is the pK
weak base (B) is titrated with 0.1 M of a strong acid (HA). The variation of

of them
i
pH of the solution
base ? The neutralization reaction is given by B + HA  BH +sA .
b

Ch e e r t + –
[JEE-2020]

Ex p
y
12
10
ist r
pH he
8
m
C 6
e r ts
4
E xp
2

s t r y
t s m i
e
0 2 4 6 8 10 12

p e r Volume of HA (mL) Ch
An acidified solution E of x 2+

ryof H required to prevent the precipitation of ZnS ?

27. 0.05 M Zn is saturated with 0.1 M H S. What is the minimum molar
2
concentration t
is
+
(M) [JEE-2020]
Use Km
e
–22
(ZnS) = 1.25 × 10 and
h dissociation constant of H S, K = K K = 1 × 10
sp

COverall 2 NET 1 2
–21

223
 Ionic Equilibrium

ANSWER KEY
EXERCISE # JEE-MAINS

er ts r t
e 7.s
1. 3 2.
xp3
E 10. 2
4 3. 4. 4 5.
x p3
E 3 14.
6. 1 1

9 . ry 12. r4y 13.

8. 4
is t 4 11. 3
i st 4

e3 m 16. 1 em
C
15.
h 1 17. 3 18.
h
C 19. 4 20. 4 21. 1

22. 4 23. 1 24. 1 25. 4 26. 4 27. 3 28. 2

29. 4 30. 4 31. 3 32. 3 33. 2 34. 1 35. 3

36. 3 37. 1 38. 1

rt s39. 2 40. 1 41. 1 42. 2

45. pe
43. 2 44. 4
E x [BONUS] NTA Ans. (4)
rt s
46. 4 47. 2

[10.60] NTA t
s r y x p e
48.
i Ans. (10.6) 49.
m 2 53. 4 54. 4 try55. 37 56. 2.00 E
[5.23] NTA Ans. (5.22 to 5.24) 50. 2

4he 52.
51.
C m is
Che e r ts
E xp
is try
EXERCISE # JEE-ADVANCED
h e m
1. pH = 11.3010 2.
r ts–3
s = 1.203 × 10 M 3.
ea 0.0175% , b 4.757
ABC C 4. B 5. pH = 4.86

E x p
y
6. A 7 A 8. 9. No it will be > 7

is tr
10 C
m
he 18. CD 19. 7 20. A 21. Aper22.t A 23. B
11. A 12. pH = 9 13. B 14. A
s
15. D 16. D

17. C 8
E x
24. 4.47 25. D 26. 3.00 27.
i s try
0.20

h e m
C e r ts
E xp
s t r y
t s m i
e r Ch e
E x p
s t r y
m i
C h e
224
 Ionic Equilibrium
HINT AND SOLTUIONS
EXERCISE # JEE-MAIN

er ts er ts
1. Ksp
Exp = 4s3= 4 × (1.0 × 0–5)3= 4 × 10–15
Exp
t
Ksp i=s4s
ry stry
2.
m = 4x
3

mi
C he 3
Che
3. MX4  M4+ + 4X–
s 4s
Ksp
er ts
= s × (4s)4

xp
= 256 s5
E r ts
 Ksp ry e
s =  st xp
1/5

m i y E
Ch e  256 

istr
e m
4. 2 4
–
H PO  H + HPO
Ch +
4
2–

er ts
Acid C.B.
Exp
istry
5. pH = 5.4
hem
[H+] = 10–5.4
er ts = 100.6 × 10–6= 4 × 10–6 C
Exp
MX  Mtr+y2x
iss 2s
2+ –
6.
m ts
2

Che xper
Ksp = 4s3 = 4 × 10–12
E
s = 10–3 M
istry
hem
ts
[M2+] = 10–3 M
C er
7. –
OH  H + O + 2–
Exp
stry
Acid
ts
C.B.
mi
e r Che
8.
Exp
H2A  H+ + HA– Ka1
HA  H + Ay Ka
tr
– + 2–

i s
2

e m
––––––––––––––––
h
CH A
2  2H + A K +
= Ka × Ka 2–
overall 1 2
225
 Ionic Equilibrium

[A  ]
9. pH = pKa + log
s s
[HA]

er t er t
E xp
pH = pKa= 4.5(if acid is half ionize)
Exp
pOH = 9.5
s t ry stry
m i mi
10. he
C Ksp = s = 1.0 × 10 2 –8
Che
s = 0–4 M
= 10–6 × 283 g/L
= 283 × 10–5 g/100 mL

e r ts
= 2.83 × 10–3 g/100 mL

E x p 1 ts
r
1 1

try
– pKb) = (14 + 4.8 – 4.78)
e
11. pH = (pKw + pKa = × 14.02 = 7.01
2
i s
2
Ex p 2

pptm
For e y
12.
h = Qip
CKsp
to start n

is tr
h e m
2+
[Ba ] × 10 = 5.1 × 10 –4
C –9

er ts
2+
[Ba ] = 5.1 × 10 M –5
E xp
n
is try
m
13. For ppt to start

s C h e
Ksp = Qip
e r t
0.05 × [Br] = 5 × 10
E x p –13

t r
[Br ] = 10y
s = 1 × 10
M – –11

moles of iBr
m s
– –11

Ch e e r t
xp
–11 –9
mass of KBr = 1 × 10 × 120 = 1.2 × 10 g
E
14. K >> K
1 2
i stry
H CO  H + HCO
h e+
m –

C ts
2 3 3

er
xp
c–x x x–y
 x
r y E
i s t
s m
–
HCO  H + CO + 2–

r t e
3 3

x–y x+y y
x p e C h
 x  x
ry E
i s t] = 1.2 × 0 M
m
– –6
[H ]  [HCO
+

h
[CO
e
C ] = Ka = 4.8 × 10 M
3
2–
3

2
–11

226
 Ionic Equilibrium
15. Ksp = Qip
10–3 × [OH–]2 = 1.1 × 10–11
r ts er ts
[OH–]min = 10–4
pOH = 4  pH =E 10x
pe Exp
s t r y stry
m i mi
16. he
C In reaction (ii) H PO given H ion.
Ch
2
e 4
2– +

17. Ksp = 27s3

27s3 = 1.6 × 10–30

ts
1/3
 1.6 1030 
s=  
e r
 27 
Exp r ts
s t ry xpe
i
m H + A y E
e r
+ –

h t
18. HA  pH = 5
C1 – x x x mis –5

e
+
[H ] = 10
10  10 5
Ch 5
–10
er ts
xp
Ka = = 10
E
1

istry
19. If Ksp < Qip
hem
r
Ksp = 1.7 × 10–10
e t s C
For option (4)
Ex p
Qip =t1r×y10 × (1 × 10 )
is
–2 –3 2
= 10–8
m ts
Che xper
20. HQ  H+ + Q– pH = 3
E
0.1 – x x x + –3
[H ] = 10
istry
h e m
ts
10 3  10 3
Ka = = 10–5
C er
xp
0.1

ry E
For pptn to start ist
ts m
21.

er Che
xp]
Ksp = Qip
–9
E
ry× 10
5.1 × 10 = [Ba ] × [CO 2+ 2–

t5.1
3

[Ba ] × 10is=
2+ –4 –9

h e m
C
2+ –5
[Ba ] = 5.1 × 10 M

227
 Ionic Equilibrium
22. [OH–] = 5 × 10–2

s s
pOH = 2 – log5

er t er t
Ex p
 pH = 12 + log5 = 12.7
Exp
s ry
t Hg + 2Cl stry
23. Hg Cl i
m
2+ –

mi
e e
2 2 2

C h s 2s
Ch
1/3
 Ksp 
Ksp = 4s 3
 s=  
 4 
Cr2(SO4)3  2Cr3+ + 3SO42–

e r ts
2s 3s

p
s =x
E ts
1/5

Ksp = 108s 
try
5 Ksp 

per
For em
is  108 
E x
h BaSO Ksp = s 
s t ry
s = (Ksp)2 1/2

C i  Ksp 
4

Ksp = 27s h e m 1/4

C ts
4

r
For CrCl 3 s=  
 27 
xpe
E
istry
m
5
e
24. Moles of CH3COOH = = 0.083

r ts
60
Ch
Moles of CH3COONa =
xpe 7.5
= 0.091

r y E 62

+t
pH = 4.76is
0.091

e m log
r ts
ChpH > 4.76
0.083

xpe
E
Range of pH  pKa ± 1
istry
hem
[H+]i = 0.1 C er ts
xp
25. pHi = 1
pHƒ = 2 [H+]ƒ = 0.01
ry E
ist
ts m
MiVi = MƒVƒ

er  Vƒ = 10 L
Che
p
0.1 × 1 = 0.01 × Vƒ
=x
water should be addedE
try
9L

m is
26. h e
C notes.
Refer

228
 Ionic Equilibrium

27. Zr3(PO4)4  3Zr+4 + 4PO43–

er ts 3s 4s

er ts
xp
Ksp = (3s)3 × (4s)4 = 6912 s7
Exp
 Kps  y E y
tr r
1/7

s= 
is ist
he m  6912
hem
C C
1
28. pH = (pKw + pKa – pKb)
2
1
= (14 + 3.2 – 3.4)

ts
2

e r
xp
1
s
= ×13.8 = 6.9
2
y E e r t
i s tr E x p
h e mof methy orange = 3.1 – 4.4 t r y
s
29. pH range
Cin titration of W.A. Vs SA at end point pH
m i be less than 7.
Ch e should

er ts
30. pptn to start
Exp
Ksp = Qip
istry
[Ba2+]ƒ [SO42–]ƒ = Ksp BaSO4
hem
50  1 Mi  450
er ts C
500

500
E p
= 1×10–10
x
s t ry
i
–9
M = 1.1 × 10 M
m ts
i

Ch e er
 H+ + HS– –7
Exp
try
31. H2S  Ka = 1.0 × 10
1

Ka = 1.2 × 10is
 H+ + S2–
HS– 
m
–13

C
2

h e ts
–––––––––––––––––––
er
 2H+ + S2– Ka = 1.2 × 10–20 Exp
y
H2S 

[H  ]2  [S2  ] istr
1.2 × 10–20 =
r ts em
pe Ch
[H 2S]

1.2 × 10 = ry
E
(0.2)  [S x 2 2

t 0.1
–20 ]

is
[S e] =m
h
C 3 × 10 M
2– –20

229
 Ionic Equilibrium
32. CH3COOK is salt of WA + S.B.

s s
So pH > 7
r t er t
Ksp PbCl = 3.2 ×E
pe
10x = 4s Exp
y y
–8 3

r r
33.
st= 2 × 10 M = 0.414 g/L t
2

m i s –3

m is
C heVol. of water require to dissolve 1g of C
PbCl h
=
e0.1
= 0.241 L 2
0.414
+
34. (i) M Mol of H = 15
M Mol of OH– = 5

s
10
[H+]ƒ =
e r t pH = 1
100
= 0.1 

Ex p ts
2NH OH + HtSO y
r  (NH ) SO + H O per
35.
is Ex
6em
4 2 4 4 2 4 2

h –
str y
C2 i
2 0
–m
0 2
h 4e
C 
er ts
xp
[NH ] 4
pOH = pKb + log = 4.7 + log = 4.7 + log2
2
E
try
[NH4OH]
pH = 9.3 – log2 = 9
mis
s Che
e r t
36. Ca(OH)2
x p +
E0.014 m mole
CaSO Na2SO4
+ 2NaOH 4

0.1 m mole
s t r y 0 0

m i s
e t
0.086 m mole 0 0.014 m mol 0.014 m mole

Ch e r
xp
Mass of CaSO = 0.014 × 136 = 1.90 g
E
4

try
0.014 –
[OH ] =
0.2
= 0.28 M

m is
C h e ts
er
37. Ag CO  2Ag + CO + 2–

Exp
y
2 3 3

s 1 2s + 0.1 s 1
i
1
st r
 0.1
er ts he m
8 × 10 = (0.1) × s xp
–12
E
2 C
Mry
1

s = 8 × 10 t
is
–10

m
1

Che
230
 Ionic Equilibrium

38. Zr3(PO4)4  3Zr4+ + 4PO43–

s

er ts 3s 4s

er ts
xp
Ksp = 6912 s7
Exp
 Ksp  y E y
tr r
1/7

s= 
is ist
he m  6912
hem
C C
39. Initial pH > 7 ,at equivalence point pH = 7

400  0.1 2  400  0.1

40. (a) [H+] = = 0.05 M

ts
800

p e r
]x
pH = 1.3

y E –
er ts
r
+

T ,istKw 
p
(b) Kw = [H ] [OH

m Ex
h e stry
C(c) HA  H + A
mi + –

c h
C e s
c(1 – ) c
er t
c 
xp
2 2

E
1 –5 –5
  
try
Ka = 10 = 10 ×
1  1  2

m is
s C h e
(d)
e r t
Le-Chatelier principle is applicable to common ion effect.

pH = (pKw – pKbE
xp = 1 (14 – 5 – log2 × 10 ) = 5.35
y
1
r
–2
– logc)
t
41.
2
i s
m Al + 3OH
2
s
42. h
C e e r t
xp
3+ –
Al(OH) 3

E
try
s 3s + 0.2
 0.2
m i s
h
C 10 Me ts
r
–24 –22
3

e
(0.2) × s = 2.4 × 10 s = 3 ×

E xp
y
3 –5 3

r
43. Ksp = 4s = 4 × (1.84 × 10 )

is t
 Cd + 2OH
s m
–

t e
2+
Cd(OH) 
r h
2

28p+e C
s
x
E  0.01
0.01

s r y
t× (1.84 × 10 )
m i
e
2 –5 3

h
s × (0.01) = 4
Cs = 2.49 × 10 M –10

231
 Ionic Equilibrium
44. (4)

r ts er ts
45.
pe
[BONUS] NTA Ans. (4)
[Y],mM Ex Exp
s t ry stry
i
Sol. em 2 mi
C h (1,2)
Che
(2,1)
1

[X],mM
1 2

e r ts
Since both (1, 2) and (2, 1) are present on the curve which is possible only when we consider
salt to be XY.
E xp r t s
str y –3
x p –3
e
i  –6 2

E
So, K = [X][Y]
sp = 10 × 2 × 10 = 2 10 M
but e
h m has 2 × 10 M which is wrong dimensionally
–6

try
3

is be BONUS
option so either the answer
Cshould be : XY, 2 × 10 M or questionm
Che
–6 2
should

er ts
46. (4)
E xp
0.134
×300 = 0.1005M ist
ry
m
2+
Sol. Concentration of Pb in resulting solution =

s
400
C h e
e r t 0.4
xp
–
Concentration of Cl in resulting solution = ×100 = 0.1M

r E
y (0.1) = 0.1005 × 10 > K
400

i s t
Q = (0.1005) 2 –2
sp

(2) m s
47.
h e e r t
Sol.C Ksp = s(3s) 3

E xp
4
27s = 6 × 10 –31

i s try
h e m
ts
1
 6
s =  10 
 –31
C
4

er
 27 
E xp
s = (0.222 × 10 ) –31 1/4

stry
ts –31 1/4
m i
–31 1/4
3s = (81 × 0.222 × 10 )
r
= (18 × 10 )
e C h e
E x p
[10.60] NTA Ans.y(10.6)
48.
is t r
h e m 4
 .001M
C
Sol. Molarity of NaOH solution =
40 100
232
 Ionic Equilibrium

9.8
Molarity of H2SO4 solution =  .001M
98 100

e r t s
2NaOH + H2SO4  Na2SO4 + 2H2O
er ts
E x p
0.04 mole 0.01 mole
Exp
s t r y
0.02 mole 0
stry
m i m i
he h e
0.02
C Molarity of NaOH in resulting soltion =
C50 0.004M

pH = 14 + log (0.004) = 10.60

49. [5.23] NTA Ans. (5.22 to 5.24)

Sol.
e r ts
mmoles of HCl in 250 ml solution = 0.1 × 250 = 25

mmoles of CH COOHE
p
inx250 ml solution = ts
r
3

str y 3
60
× 1000 = 50
x pe
i
mof HCl in 20 ml solution = 500 × 20 =t1ry E
Ch e
mmoles
25
is
m
he = 50 × 20 = 2
mmoles of CH COOH in 20 mlC solution
er ts
xp
3
500
E
try
1
After adding
2
ml, of 5M NaOH
mis
s Che
r
HCl  NaOH  NaCl  H2O
e t
1

E x p 1

r y
0 0 1

ist NaOH  CH COONa  H O

h m
CH COOH
e
3

r ts
3 2

e
1.5

C
2

0.5 0

Exp 1.5

try
[CH COONa]
is
3
pH = pK + log a
[CH COOH]

1.5 he
m 3

C er ts
xp
= 4.75 + log

E
0.5
= 4.75 + log 3
stry
ts mi
er = 4.75 – 0.4771 = 5.23
Che
E x p
50. (2)
istry
h em+ S  CuS(s)
Sol. Cu (aq) 2+ 2–

C
233
 Ionic Equilibrium

1
Keq =
K sp

e r t s e r ts
E x p Ex p
If Ksp is low then Keq will be high but Keq decide only extent of reaction not the rate of reaction.

(4) ist
r y stry
51.
m mi
Sol. he
C h e
C and no busen burner and measuring cylinder
Titration of HCl with NaOH is acid-base titration
is required for this.

52. (2)

ts
Sol. Acidic buffer solution contains weak acid and its salt with strong base.
e r
xp s
Option (1) : Solution is containing strong acid and its salt with strong base.

y E e r t
tr p
0.1100mm 0.1200mm

i s
Option (2) : HCl  CH COONa
(aq) 3   CH
m Resulting solution containes weaktracid
COOH
E x
(aq)  NaCl
3 (aq) (aq)

e y and its salt with strong base.

0 10mm 10mm

C h is
e m
h  CH COONa  H O
Option (3) : CH COOH C
ts
0.1100mm 0.1100mm

3 NaOH (aq) (aq) 3 (aq)

p e
2
r (l )

Resulting solution contains only salt of weak acid and strong base. Ex
0 0 10mm

i s try
h e m
s C
53. (4)

Sol. At neutralization point pHp =e r t

E x 7 because acid and base both are strong.

s t r y
m i s
h
C e pH 7
e r t
E xp
vol. of NaOH
i st ry
h e m
ts
.
C er
xp
54. (4)

r y E
t
Sol. pH of 0.01 M HCl = 2

s m i s
pH of 0.01 M NaOH = 12
e r t h e
pH of 0.01 M CH COONa
E x p
> 7 C
y
3

pH of 0.01 M t
i s r
NaCl =7
m
heof pOH : A > D > C > B
Corder
234
 Ionic Equilibrium
55. (37)

s s
Sol. Using Henry’s law

er t er t
kH ×
1
Exp
= 30
Exp
y y
1000

ist r18
istr
he m 3
n
hem
C C
CO 2
k × H
1000
18
n CO2 = 0.1

Molarity of CO2 = 0.1 M

er ts
 CO2 dissolved remains in the form of H2CO3
xp
 HE  HCO r ts
H CO  y
tr 0 0


pe –

0.1M is x
2 3(aq) (aq) 3(aq)

e m ry E
Ch 0.1 – x x x
ist
e m
Ch ts
2

r
x –7
K = 4 × 10 =
a
(0.1 – x)
xpe
[ x << 1]y E
 x2 = 0.1 × 4 × 10–7
is tr
x = 2 × 10–4
hem
er ts
 pH = –log (2 × 10–4) C
Exp
= 3.7
stry
m i
56. h
C e er ts
xp
(2.00)
E
try
Sol.  A(aq.)
AB2(s)  2 
 2B(aq.) :K
is
SP

m
S 2S

KSP = S1 × (2s)2 = 4s3

Che ts
er
xp
3.2 × 10–11 = 4 × S3
S = 2 × 10–4 M/L
ry E
ist
r ts em
Expe Ch
istry
hem
C
235
 Ionic Equilibrium

EXERCISE # JEE-ADVANCED
1.
r
e - s
HCl + NaOH  NaCl + H2O
t er ts
xp
2m mol 3mmol
1mmol E 2m mol -
10
Exp
0
st r y stry
m i = 2×10 mi
e e
1 – –3

Ch
[OH ]=
500
Ch
pH = 11 + log2 = 11.3

2. pH = 8  pOH = 6
[OH–] = 10–6 M
e r ts
Pb(OH)2  Pb2+ + 2OH–
E xp r ts
s
2
K = 4s = 4×(6.7) y
trPb + OH
×10 = 1.2×10 3

xpe –18 –15

i
sp

e m
Pb(OH)  2+

ry E –

h t
2

C s 2s+10
mis –6

h e
C ts
–6 –15

r
s(2s + 10 ) = 1.2×10
–2 –15
xpe
E
s×10 = 1.2×10
s = 1.2×10–3 M
istry
HCl  pH < 7 NaCl  pH = 7
hem
4.

e r s
t NH Cl  pH < 7 C
xp
NaCN  pH > 7 4

NaCN < NaCl > NHE

s tr y Cl > HCl 4

m i s
Ch e 10
e r t –6

p
5. Amount of SO in atmosphere = = 10×10
x
2 6

E
10

t r y
is
Molar conc. of SO in water = Amount of SO × Solubility
2 of SO 2 2

m
Che
–6
= 10×10 ×1.3653
= 1.3653×10 M –5

er ts
 H+ + HSO3
Exp
y
H2SO3

1.3653×10–5 – x istr
ts m
x x

e r Che
xp
x2
= 10–1.92
E
Ka =

try pH = 4.865
5
1.3653  10  x

m is
x = 1.364×10 –5

C h e
236
 Ionic Equilibrium
6. Equation of H2C2O4.2H2O = Equation of NaOH
10 63

ts
 2 = 0.1×V(L)
er er ts
p p
250 126

Ex Ex
25try y
1
V(L) =
i=s40 istr
m em
Che h
V(mL)
7. ApBq(s)  pAq+(aq) + qBp–(aq) C
s ps qs
p q
Ksp = (ps) (qs)
= ppqq(s)p+q

er ts
[CH COOH] = 0.1 MEx
p ts
8.
[HCl] = 0.1sMtr
3
y f

per
m i Ex
y
f

(a) h e
C 0.1–x
CH COOH  CH COO + H
istr – +

m
3 3

h e
ts
x x+0.1
x(x  0.1) C er
xp
–5

E
1.75×10 =
0.1  x
x = 1.75×10–5
istry
0.1× = 1.75×10–5
hem
er ts C
 = 1.75×10–4
[H ] = 0.1 pH = 1E
x p
+

s tr y
m i
Ch e er ts
(b) Moles of NaOH =
6
= 0.15 mol
Exp
t+ rHyO
40
CH COOH + NaOH  CH COONa is
m -
e
3 3 2

n 0.1 0.05 h
C 0.05 -
0
r ts
e
i

nf 0.05 0
Exp
stry
 0.1 moles NaOH will be consumed by 0.1 mol of HCl

ts mi
e r C h e
pH = pK = 4.75
Ex
a
p
r y
t pH 
Hs,
T, K , i
m
+
9.
e
w

C h
237
 Ionic Equilibrium
10. Which has minimum value of Ksp i.e. HgS

e r t s er ts
11.
x p
X– + H2O  4X + OH–
E0.1 h 0.1 h Exp
0.1(1–h)
ry try
Km
isKt  10 = 10 14

mis
Che K (HX) 10
= h
a
w
5
–9

Che
Ch 2 0.1h 2
Kh =  = 10–9
1 h 1 h
0.1 h2 = 10–9

ts
h2 = 10–8
e r
xp
h = 10–4

y E er ts
tr p
% h = 0.01 %

m i s Ex
h e str y
C i
HA + NaOH  NaOH + H O hem
12. At end point HA will completes reacts with NaOH

C 2

er ts
xp
–
[A ] = 0.05 M
E
try
1
pH =
2
(pKw + pKa + logC)
mis
s Che
=
1
er t
(14 + 6 – log5 + log0.05)
2
E x p
= (20 – log5r–y
t
1

m i s log20)

ts
2

he r
C pH = 9
xpe
13. CH3NH2 + HCl  CH NH Cl
ry E  

st
3 3

mi
0.1 mol 0.08 mol 0
he
C mol ts
0.02 mo 0 0.05
er
[CH3 NH 2 ]
Exp
[OH–] = Kb×
[CH3 NH3 ]
stry
ts mi
= 5×10–4 × e
0.02
r 5
= ×10–4
Che
Exp0.08 4
y
s t=r ×10 = 8×10 M
i
+ K w –10 –11

m
[H ] =
e

[OH ] 5

Ch
238
 Ionic Equilibrium

14. CO2 + H2O  HCO3 + H+

HCO3  CO32 + H
er t
+
s er ts
Exp Exp
For MX ry
st stry
= si = 4×10 i
15.
Km
em
Ches = 2×10 M
2 –8
sp
–4
Ch
For MX2
Ksp = 4s2 = 32×10–14
s2 = 8×10–15
s = 2×10–5 M
er ts
For M X
Exp r ts
y e
3

istr
K = 27s = 2.7×10
sp
4

Exp –15

h e mM –14

try
s
s = 10
CMX > M X > MX mi
Ch
3
e 2

er ts
16. BOH + HCl  BCl + H2O
Exp
It equivalence point
istry
hem
s
Moles of BOH = moles of HCl

er t C
p
2 2
2.5× =
Ex
×V(mL)

y
5 15
r
V(mL) = 7.5tmL
is
Ve=m ts
Ch
10 mL
er
xp
f

E
try
1
[BCl] = = 0.1 M
10
mis
B + H2O  BOH  H


Che ts
0.1(1 h) 0.1 h 0.1 h

er
K w 1014
Exp
Kh =  12 = 10–2
stry
i
K b 10

r ts em
e Ch
0.1  h 2

xp
10–2 =
1 h
E
h = 0.27
i stry
 [H m
C h e +
] = 0.1×h = 0.027 M

239
 Ionic Equilibrium
1 1 1
17. pH = (pKw + pKa + logC) = (14 + 4 + log0.01) = ×16 = 8
2 2 2

e r t s er ts
18.
xp
(A) HNO3 + CH3COOH (S.A. + W.A.)
E Exp
r y
t+ CH COONa (S.B. + Salt)
It can’t be a buffer
s stry
m i mi
Che
(B) KOH
It can’t be a buffer
3

Che
(C) CH3COONa + HNO3  CH3COOH + NaNO3
It can form buffer if volume of CH3COONa and HNO3is different.
(D) CH3COOH + CH3COONa
It is a buffer
e r ts
E xp r ts
19. For CuCl
K = s = 10str
y xpe
sp
m i 2 –6

y E
h e –3

CAgCl(s)  As (aq) + Cl (aq) mi

s = 10
str
h e
+ –

C –3
er ts
xp
s s+10
s(s + 10–3) = 1.6×10–10 E
s×10–3 = 1.6×10–10 istry
hem
s = 1.6×10–7
e r ts C
20. For Ag CrO x
K p
E(aq) + CrO
= 1.1×10– 12

y
2 4 sp

i
Ag CrO 
str2Ag + 2

m 2s+0.1 s
2 4

ts
4

Ch e er
 0.1 Exp
(0.1)2 ×s = 1.1×10–12
istry
hem
8 = 1.1×10–10 M
C er ts
r  [H+]1
Exp
y
21.

Ka  C
istr
ts m
1
1

100
er Che
Exp –2

ry
K  C = 10

K = 10 ist
a

m
–4

e
a

Ch
240
 Ionic Equilibrium
22. Form exp.-1

s s
5.7×1000 = C×5.7

e r t er t
Form exp-2
Exp Exp
q = C×5.6
s t ry stry
m 5.6i
q = 5.65 kJ
mi
he
C H =  = –56 kJ. / mol Che
0.1
Hion = –56 + 57= 1 kJ/ mol

23.
0 rt
e s 0
CH3COOH + NaOH  CH3COONa + H2O

xp0.1 mol 0
0.2 mol 0.1 mol

y E er ts
tr p
0.1 mol 0
s
pH – pK =i4.7
m Ex
h e
a

stry
Cs = K  H  1
  

m i
24.
Ch e
ts
sp
K  a

er
 103 
Exp
try
10
= 20 10  8  1
 10 
mis
2 105 = 4.47×10–3 M
s Che
=
e r t
x p
E  CH COONa + H O
(P) CH COOH y
25.
i s r
t 1m mol
3 + NaOH 3 2

h e m2m mol 0 -
r ts
C 1m mol 0 xpe
E
1m mol -

s t ry
If forms a buffer and pH does not change with dilution.
i
(Q) CH COOH + NaOH  CH COONa
e m
C0h
+HO
ts
3 3 2

er
xp
2m mol 2m mol -
0 0 2m mol -
ry E
CH3COO– + H2O  CH3COOH + OH–
ist
r ts em
CH =+

Expe Kw  Ka
Ch
1 str
y C

[H ] 
+
mCi
C h e
241
 Ionic Equilibrium

(R) NH3 + HCl  NH4Cl

2m mol

e r ts 2m mol

er ts 0
0
NH + H O E
x p 0
Exp 2m mol

r

y ry
+

t t
NH OH + H
s s
2 4

i i
4

he[Hm
K
C  [H ]  C
hem
C C
+ w +
]=
K b

(S) Ni(OH)2(s)  Ni2+(aq) + 2OH–(aq)

On dilution [OH–] remains same in saturated solution of Ni(OH)2

26. (3.00)
e r ts
Sol. At 3 ml pH of solution isx11p s
y
r +A E er t
B + HA  t
i s BH + –

Exp
mlm
at 3e ry
h s
CSo pOH  pKb  3 (As basic buffer is formed)
best buffer action is shown
i t
h e m
C er ts
So P  3 Kb
Exp
istry
27. (0.20)
hem
Sol. For ZnS
er ts
Ksp (ZnS) = [Zn2+] × [S2–] = 1.25 × 10–22 C
Exp = 0.05 × [S2–] = 1.25 × 10–22

tr y [S2–] = 25 × 10–22
For H S is
h e m 2  2H+ + S2–
H2S 
r ts
C –22
x p e
E
0.1 M 25×10

=try
 2  2
2–
[H ]  25 10 –22

s
[H ] [S ]
i
–21
K = = 1 × 10  110 –21

m
a

e
[H S] 0.1
h ts
2

1
C er
xp
+ 2
[H ] =

E
25
1
stry
ts
[H+] =
5
mi
er Che
xp
[H+] = 0.2 M
E
istry
hem
C
242
 Liquid Solution

EXERCISE # (JEE-MAIN)
1.
r ts r ts
Which one of the following aqueous solutions will exhibit highest boiling point ?
e e
E x p Exp [AIEEE-2004]

y y
(1) 0.01M Na2SO4 (2) 0.01M KNO3 (3) 0.015M urea (4) 0.015M glucose

i s r is r
t from Raoult's law ?
tthe following liquid pairs shows a positive deviation
2.
he m
Which of
h e m
C (1) Water-hydrochloric acid
C (2) Benzene-methanol
[AIEEE-2004]

(3) Water-nitric acid (4) Acetone-chloroform

3. Which one of the following statement is False ? [AIEEE-2004]

ts
(1) Raoult's law states that the vapour pressure of a component over a solution is proportional

er
xp
to its mole fraction

E ts
(2) The osmotic pressure () of a solution is given by the equation  = MRT where M is the
y er
istr
molarity of the solution
Exp
hem try
(3) The correct order of osmotic pressure for 0.01M aqueous solution of each compound is

C is
BaCl2 > KCl > CH3COOH > Sucrose
m
Ch e
(4) Two sucrose solutions of same molality prepared in different solvent will have the same
freezing point depression
e r ts
E xp the
try[AIEEE-2005]
4. If a is the degree of dissociation of Na SO , the vant of Hoff's factor (i) used for calculating
2 4
molecular mass is
m i s
(1) 1 –  (2) 1 + 
s
(3) 1 – 2
C h e (4) 1+2

e r t
5.
75 torr and that of E
Benzene and toluene form
x p nearly ideal solutions. At 20°C, the vapour pressure of benzene is

s ry
t 78 g of benzene and 46 g of toluene in torr is -
toluene is 22 torr. The partial vapour pressure of benzene at 20°C for a

m i
solution containing
s37.5
[AIEEE-2005]

Ch(1)e25 (2) 50 (3) 53.5

e r t
(4)

Two solutions of a substance (non electrolyte) arey E xinpthe following manner. 480 ml of
tr solution. What is the molarity of the final
6. mixed

m
1.5 M first solution + 520 mL of 1.2 M second i s
mixture ?
C h e [AIEEE-2005]
ts
(1) 1.50 M (2) 1.20 M (3) 2.70 M (4) 1.344 M
p e r
E x
s t r y [AIEEE-2006]
i
7. Equimolar solutions in the same solvent have

t s
(1) Same freezing point but different boiling point
e r freezing point Ch e m
(3) Different boiling andx
E p
(2) Same boiling point but different

t y same freezing points

different freezing point
(4) Same boilingrand
m is
C h e
243
 Liquid Solution
8. 18 g of glucose (C6H12O6) is added to 178.2g of water. The vapour pressure of water for this
aqueous solution at 100° C is [AIEEE-2006]
(1) 7.60 Torr
e r ts
(2) 76.00 Torr (3) 752.40 Torr
e r t s
(4) 759.00 Torr

x p x p
E of 290 mm at 300 K. The
Ealcohol and propyl alcohol has a vapourrpressure
9.
r y
A mixture of ethyl
s t of propyl alcohol is 200 mm. If the imole s y
t fraction of ethyl alcohol is 0.6, its
i
vapour pressure
m pressure (in mm) at the same temperature m
hevapour
C (1) 350 (2) 300 h e will be
C (3) 700 (4) 360
[AIEEE-2007]

10. A 5.25% solution of a substance is isotonic with a 1.5% solution of urea

(molar mass=60g mol–1) in the same solvent. If the densities of both the solutions are assumed
to be equal to 1.0 gcm–3, molar mass of the substance will be [AIEEE-2007]

ts
–1 –1 –1
(4) 210.0 g mol–1
r
(1) 90.0 g mol (2) 115.0 g mol (3) 105.0 g mol

At 80°C, the vapoureE

e
xp of pure liquid 'A' is 520 mm Hgrandtsthat of pure liquid 'B' is
1000 mm Hg.tIfray eand 1 atm pressure, the amount
11. pressure

i s E x p
mixture solution of 'A' and 'B' boils at 80°C

e m r y
t48 mol %
C(1)h52 mol %
of 'A' in the mixture is (1 atm = 760 mm Hg) [AIEEE-2008]
(2) 34 mol %
m i s
(3) (4) 50 mol %

The vapour pressure of water atC h e

20°C is 17.5 mm Hg. If 18 g of glucose (C H O ) is added tots
12. 6 12 6

p er
mmE
x
178.2 g of water at 20°C, the vapour pressure of the resulting solution will be [AIEEE-2008]
(4) 17.325 y
tr
(1) 17.675 mm Hg (2) 15.750 mm Hg (3) 16.500 mm Hg Hg
is
mpressure of the solution
13.
ofsY is 550 mm Hg. At the
Two liquids X and Y form an ideal solution. At 300K, vapour
h e
Csame temperature, if 1 mol of Y is
containing 1 mol of X and 3 mol
e r t
E x p vapour pressure of the solution increases by 10 mm Hg. Vapour
further added to this solution,

t ry
is600 (2) 500 and 600 (3) 200 and 300 (4)s300 and 400
pressure (in mmHg) of X and Y in their pure states will be, respectively : [AIEEE-2009]

h e m
(1) 400 and
r t
C x e
pand ethanol. Which one of the
14. A binary liquid solution is prepared by mixing n-heptane
r y E
t
is from Raoult's law
folloowing statements is correct regarding the behaviour of the solution ? [AIEEE-2009]

h m
(1) The solution is non-ideal, showing –ve deviation
e ethanol shows –ve deviation from Raoult's law ts
C
(2) n-heptane shows +ve deviation while
er
(3) The solution formed is an ideal solution.
E x p
y
(4) The solutionis non-ideal, showing +ve deviation from Raoult's law

i s tr
15.
r s point of water h(Tem
tfreezing
If sodium sulphate is considered to be completely dissociated into cations and anions in
aqueous solution, the changeein
E x p C f ), when 0.01 mol of sodium

y
–1

(1) 0.0186 K tr
sulphate is dissolved in 1 kg of water, is (K = 1.86 K kg mol ) :
f [AIEEE-2010]

m i s (2) 0.0372 K (3) 0.0558 K (4) 0.0744 K

C h e
244
 Liquid Solution
16. On mixing, heptane and octane form an ideal solution. At 373 K, the vapour pressures of the
two liquid components (heptane and octane) are 105 kPa and 45 kPa respectively.

e r t s r t s
Vapour pressure of the solution obtained by mixing 25.0 of heptane and 35 g of octane will be
(molar mass of heptane = 100 g mol–1 and of octane = 114 g mol–1) :
e
(1) 144.5 kPa
E x p
(2) 72.0 kPa (3) 36.1 kPa
E x p
(4) 96.2 kPa
[AIEEE-2010]

s ry r y
t of dissociation () of a weak electrolyte, iAsBt is related to van't Hoff factor (i) by
17.
them
i
The degree
m
e e
x y

C h expression :
(1)  =
x  y 1
(2)  = C h
x  y 1
(3)  =
i 1
[AIEEE-2011]
(4)  =
i 1
i 1 i 1  x  y  1  x  y  1

18. Ethylene glycol is used as an antifreeze in a cold climate. Mass of ethylene glycol which should
be added to 4 kg of water to prevent it from freezing at – 6°C will be : [AIEEE-2011]
–1 –1

ts
(Kf for water = 1.86 K kgmol , and molar mass of ethylene glycol = 62 gmol )
(1) 400.00 g
e r
(2) 304.60 g (3) 804.32 g (4) 204.30 g

A 5% solution of caneE xp(molar mass 342) is isotonic with 1%roftsa solution of an unknown
rymass of unknown solute in g/mol is : xpe
19. sugar

is t
solute. The molar
E
[AIEEE-2011]

h e m
(1) 136.2 (2) 171.2 (3)
t r y
68.4 (4) 34.2

20. CThe molality of a urea solution in which m s

i of urea, [(NH ) CO] is added to 0.3000 dm
e
3

h
0.0100g

ts
2 2
of water at STP is :
C –4
[AIEEE-2011]
e r –2
(1) 0.555 m (2) 5.55 × 10 m (3) 33.3 m (4) 3.33 × 10 m
E x p
21. The freezing point of a 1.00 m aqueous solution of HF is found to be –1.91°C.
s t ry ofTheHFfreezing
–1

m i
point constant of water, K , is 1.86 K kg mol . The percentage dissociation at this
e
f
concentration is
(2) 30% ts
r C h [JEE (MAIN)-2012 ONLINE]

eideal solution. At 30ºC, the total vapour pressure of a solution

(1) 2.7% (3) 10% (4) 5.2%

E x p
22.
r y
Liquids A and B form
s
an
t 1 more mol of A is added to the first solution. The vapour pressures of pure A
i
containing 1 mol of A and 2 moles of B is 250 mm Hg. The total vapour pressure becomes 300
mat the same temperature are s
h e
mm Hg when

C (1) 450, 150 mm Hg (2) 250, 300 mm Hg (3) 125, 150 mm e r t

xpHg (4) 150, 450 mm Hg
and B [JEE (MAIN)–2012 ONLINE]

E
i s trgyof water freezes at –0.23ºC. The apparent
degree of dissociation of the salt is : m
23. A solution containing 0.85 g of ZnCl in 125.0
e
2

h
Catomic mass(3); Zn73.5%
[JEE (MAIN)-2012 ONLINE]
r ts
e
(k for water = 1.86 K kg mol–1,
ƒ = 65.3 and Cl = 35.5)
(1) 1.36% (2) 2.47% (4) 7.35%
E p many
xhow
y of the solution
–1

r
24. K for water is 1.86 K kg mol . If your automobile radiator holds 1.0 kg of water,
grams of ethylene glycol (C H O ) must you add to get the freezingtpoint
f
2 6

s
2

m is
lowered to –2.8°C ?
(2) 72 g r
e t h e [AIEEE-2012]
(1) 27 g
E p (3) 93 g
C (4) 39 g
x dissolved in 108g of water produces the relative lowering of vapour
25.
s trThey molecular mass of the solute is :
12g of a nonvolatile
pressure ofi0.1.
solute

m
[JEE (MAIN)-2013 ONLINE]

C h e
(1) 60 (2) 80 (3) 40 (4) 20

245
 Liquid Solution

26. A molecule M associates in a given solvent according to the equation M   (M)n. For a
certain concentration of M, the van’t Hoff factor was found to be 0.9 and the fraction of

e r t s
associated molecules was 0.2. The value of n is :
r ts
[JEE (MAIN)-2013 ONLINE]
e
(1) 2
x p (2) 4 (3) 5
x p
(4) 3
E is 37.0 torr at the same
Eof pure benzene is 119 torr and that ofrytoluene
s r y t is in equilibrium with a solution
t Mole fraction of toluene in vapour phaseiswhich
i
27. Vapour pressure

heofm
temperature.
h e m 0.50, will be :
C C
benzene and toluene having a mole fraction of toluene
[JEE (MAIN)-2013 ONLINE]
(1) 0.137 (2) 0.205 (3) 0.237 (4) 0.435

28. How many grams of methyl alcohol should be added to 10 litre tank of water to prevent its
freezing at 268 K ?
(Kf for water is 1.86 K kg mol–1)
ts
[JEE (MAIN)-2013 ONLINE]
(1) 899.04 g
e
(2) 886.02 g
r (3) 868.06 g (4) 880.07 g

E xp r ts) (aq), 0.250 M KBr(aq)

29.
and 0.125 M NarPO y
Consider separate solution of 0.500 M C H OH(aq), 0.100 M Mg (PO
(aq) at 25°C. Which statement is true p
st electrolytes ?
2 5

x e 3 4 2

salts to be i
about these solutions, assuming all
E
3 4

h0.125m
e M Na PO (aq) has the highest osmotic
strong
y
trpressure.
[JEE-MAIN-2014]

C(1) 3 4

m i s
(3) They all have the same osmotich
2 5
e
(2) 0.500 M C H OH (aq) has the highest osmotic pressure.

(4) 0.100 M Mg (PO ) (aq) hasC

pressure.
e r ts
xp
3 the highest osmotic pressure.
4 2

E
try ONLINE]
30. For an ideal Solution of two components A and B, which of the following is true ?
(1) H < 0 (zero)
m is
[JEE(MAIN)-2014
e
mixing
(2) A – A, B – B and A – B interactions are identical

r t
(3) A – B interaction is stronger thans C h
A – A and B – B interactions
(4) H > 0 (zero)
xp e
E
mixing

s t r y pressure for a 0.10 M solution of Fe(NH ) (SO ) at 25°C is 10.8 atm.

31.
m i and experimental (observed) values of Van't Hoff factors(i) will be respectively :
The observed osmotic 4 2 4 2

e
Ch(R=
The expected
e r t(MAIN)-2014 ONLINE]
xp (4) 5 and 4.42
– –1
0.082 L atm k mol ) [JEE
(1)3 and 5.42 (2) 5 and 3.42
ry E
(3) 4 and 4.00

i s t
32.
e m
The molarity of a solution obtained by mixing
h
750 mL of 0.5(M)HCl with 250 mL of 2(M)HCl
[JEE (MAIN)-2013]s
will be :-
C e r t
(1) 0.875 M (2) 1.00 M (3) 1.75 M (4) 0.975 M
E xp
s tr y substance was
33.
dissolved in 100 g of acetone att20°C, s its vapour pressure e m i
The vapour pressure of acetone at 20°C is 185 torr. When 1.2 g of non-volatile

p e r C h was 183 torr. The molar mass

–1
E
(g mol ) of the substance x is : [JEE (MAIN)-2015]
(1)128
i s try (2) 488 (3) 32 (4) 64

h e m
C
246
 Liquid Solution
34. A solution at 20°C is composed of 1.5 mol of benzene and 3.5 mol of toluene. If the vapour
pressure of pure benzene and pure toluene at this temperature are 74.7 torr and 22.3 torr,

e r ts e r t s
respectively, then the total vapour pressure of the solution and the benzene mole fraction in

x p
equilibrium with it will be, respectively :
E E x p[JEE (MAIN)-2015 ONLINE]

st r y
(1) 38.0 torr and 0.589
r y
(2) 30.5 torr and 0.389
st
m i
(3) 35.8 torr and 0.280
i
(4) 35.0 torr and 0.480
mbenzene using freezing point depression is
C
35. heDetermination of the molar mass of C
acetic h e
acid in
affected by : [JEE (MAIN)-2015 ONLINE]
(1) association (2) dissociation (3) complex formation (4) partial ionization

36. 18 g glucose (C6H12O6) is added to 178.2 g water. The vapour pressure of water (in torr) for

ts
this aqueous solution is : [JEE (MAIN)-2016]

e r
xpat 300 K and 500 torr partial pressurertiss0.01 g L . The solubility
(1) 759.0 (2) 7.6 (3) 76.0 (4) 752.4

E
trtorry partial pressure is : e[JEE (MAIN--2016-ONLINE]
–1
37. The solubility of N
(in g L ) atis
–1
in2water
E xp
h e m 750
t r y
C
(1) 0.02 (2) 0.005
m i s
(3) 0.015 (4) 0.0075

e
Chsolution ts
38. An aqueous solution of a salt MX at certain temperature has a van't Hoff factor of 2.
r
2
The degree of dissociation for this of the salt is :
xp
[JEE (MAIN--2016-ONLINE]
e
(1)0.50 (2) 0.80 (3) 0.67 (4) 0.33
E
The freezing point of benzene decreases by 0.45°C when 0.2 g of aceticis trisyadded to 20 g of
39.
h e m association of acetic
acid

t s C
benzene. If acetic acid associates to form a dimer in benzene, percentage
e r
p
acid in benzene will be: [JEE (MAIN)- 2017]
(K for benzene = 5.12 x
E
–1
K kg mol )
y (2) 80.4%
f
(1) 64.6%
is t r (3) 74.6% (4) 94.6%
40.
h e m
For 1 molal aqueous solution of the following compounds, which
r t s [JEE (MAIN)-2018]
one will show the highest

C (1) [Co(H O) Cl ]. 3H O
freezing point ?
xp e
(4) [Co(H E
2 3 3 2 (2) [Co(H O) ]Cl
2 6 3

try
(3) [Co(H O) Cl]Cl .H O O) Cl ]Cl. H O
s
2 5 2 2 2 4 2 2 2

i
m Henry's law not correct ?
41.
C
Which one of the following statements
h e regarding
ts
e r
xp
[JEE MAIN-2019(Jan.)]
E
(1) The value of K increases with function of the nature of the gas
s t r y
iof the gas in the liquids.
H

(2) Higher the value of K at a givenspressure, higher is the solubility m

er
H
t e
h to the mole fraction of the
(3) The partial pressure x
E ofp C
the gas in vapour phase is proportional

s tr y
(4) e
i
gas in the solution.
m gases have different K (Henry's law constant) values at the same temperature.
C h Different H

247
 Liquid Solution
42. Liquids A and B form an ideal solution in the entire composition range. At 350 K, the vapor
pressures of pure A and pure B are 7 × 103 Pa and 12 × 103 Pa, respectively. The composition

r t s r ts
of the vapor in equilibrium with a solution containing 40 mole percent of A at this temperature
e e
is :
E x p E x p [JEE MAIN-2019(Jan.)]

y y
(1) xA = 0.76 ; xB = 0.24 (2) xA = 0.28 ; xB = 0.72

i st r
(3) xA = 0.37 ; xB = 0.36
istr
(4) xA = 0.4 ; xB = 0.6

43. he
m
Elevation in the boiling point for 1 molal h e mof glucose is 2 K. The depression in the
C C solution
freezing point for 2 molal solution of glucose in the same solvent is 2 K. The relation between
Kb and Kf is: [JEE MAIN-2019(Jan.)]
(1) Kb = 1.5 Kf (2) Kb = Kf (3) Kb = 0.5 Kf (4) Kb = 2 Kf

44. The freezing point of a diluted milk sample is found to be –0.2°C, while it should have been

r ts
–0.5°C for pure milk. How much water has been added to pure milk to make the diluted sample ?
e
E xp r t s
[JEE MAIN-2019(Jan.)]

tr y e
(1) 2 cups of water to 3 cups of pure milk (2) 1 cup of water to 3 cups of pure milk
s x p
i E
(3) 3 cups of water to 2 cups of pure milk (4) 1 cup of water to 2 cups of pure milk
m yin benzene. 'w' g of the acid dissolved in 30
h e
45. CMolecules of benzoic acid (C H COOH) dimerise st r
ipoint equal to 2K. If the percentage association of
6
e
5
m
h is 80, then w is :
C [JEE MAIN-2019(Jan.)]ts
g of benzene shows a depression in freezing
the acid to form dimer in the solution
p e r
x
–1 –1

E
(Given that K = 5 K kg mol , Molar mass of benzoic acid = 122 g mol )
f

tr(i)yis :-
(1) 1.5 g (2) 1.0 g (3) 2.4 g (4) 1.8 g
46. K HgI is 40% ionised in aqueous solution. The value of its van't Hoff factor
2 4
i s
m[JEE MAIN-2019(Jan.)]
(2) 2.0 ts h e
C (4) 1.8
(1) 1.6
e r (3) 2.2

E xp
Freezing pointry
47.
s t
i Y. If molecular weight of X is A, then molecular weight ofsY is :
of a 4% aqueous solution of X is equal to freezing point of 12% aqueous

e m
solution of
r t[JEE MAIN-2019(Jan.)]
Ch(1) 2A (3) 3A Ex
e
p (4) 4A
try
(2) A
i s
min 250 g water is cooled to - 10º C. If K for water iss
48.
h e
A solution containing 62 g ethylene glycol
1.86 K kg mol , the amount ofC
f

t
–1
water (in g) separated as ice is :
e
[JEE MAIN-2019(Jan.)]
r
(1) 64 (2) 32 (3) 16 (4) 48
E xp
s t r y at 298 K.
49. The vapour pressures of pure liquids A and B are 400 and 600 mmHg,
ts m ito the volume of the final
respectively
On mixing the two liquids, the sum
mixture. The mole fractionp
r
ofeliquid B is 0.5 in the mixture.
e
hThe vapour pressure of the final
of their initial volumes is equal
C
x
E of components A and B in vapour phase, respectively are :
t ry
solution, the mole fractions
s
i
mmmHg, 0.4, 0.6
[JEE MAIN-2019(April)]

h e
(1) 450
C(3) 500 mmHg, 0.5, 0.5
(2) 500 mmHg, 0.4, 0.6
(4) 450 mmHg, 0.5, 0.5
248
 Liquid Solution
50. For the solution of the gases w, x, y and z in water at 298 K, the Henrys law constants (KH) are
0.5, 2, 35 and 40 k bar, respectively. The correct plot for the given data is :

er ts er ts [JEE MAIN-2019(April)]

Exp Exp
stry stry
i i
e(1)m h(2)em
Ch C

e r ts
E xp r t s
(3)
str y (4)

x p e
m i y E
h e st r
51. CLiquid 'M' and liquid 'N' form an idealm i The vapour pressures of pure liquids 'M' and
C e
h at the same temperature. Then correct statement is :rts
'N' are 450 and 700 mmHg, respectively,
solution.

(x = Mole fraction of 'M' in solution;

x p e
E
M
x = Mole fraction of 'N' in solution;
N

s tr y
y = Mole fraction of 'M' in vapour phase;
M
m i
y = Mole fraction of 'N' in vapour phase)
s h e [JEE MAIN-2019(April)]
(2) (x – y )C
N
x

y
e r t
p
(1) M M
< (x – y )
x
M M N N

E
x N yN

 try
x iys
x y x y
(3) M M
(4) M
 M

h e m N N x
N y N

r t s
52. C The osmotic pressure of a dilute solution of an ionic compound
e
xp XY in water is four times that
r E
y complete dissociation of the given ionic
i
of a solution of 0.01 M BaCl in water. Assuming
2
s t
e m –1
compounds in water, the concentration of XY (in mol L ) in solution is:
h [JEE MAIN-2019(April)] s
C e r t
xp
–4 –2 –2 –4
(1) 16 × 10 (2) 6 × 10 (3) 4 × 10 (4) 4 × 10

r
Molal depression constant for a solvent is 4.0 kg mol . The depression intthe
E
yfreezing point of
53.
the solvent for 0.03 mol kg solutionsof K SO is :
–1

m s
i MAIN-2019(April)]
–1

e t
rthe electrolyte) Ch
2 4
e [JEE
p
(2)x0.36 K
(Assume complete dissociation
E
of
(1) 0.12 K
str y (3) 0.24 K (4) 0.18 K

m i
C h e
249
 Liquid Solution
54. At room temperature, a dilute solution of urea is prepared by dissolving 0.60 g of urea in 360 g
of water. If the vapour pressure of pure water at this temperature is 35 mmHg, lowering of

e r ts
vapour pressure will be: (molar mass of urea = 60 g mol–1)
e r ts
[JEE MAIN-2019(April)]
(1) 0.017 mmHg
E x p
(2) 0.027 mmHg (3) 0.031 mmHg
E x p
(4) 0.028 mmHg

s tr y ry
int100 g of two different solvents A and
non-electrolyte solute is dissolved s
55.
i
1g of a non-volatile
Bmwhose ebullioscopic constants are in the ratiom
i
C he T (A) C h e of 1: 5. The ratio of the elevation in their
b
boiling points, , is : [JEE MAIN-2019(April)]
Tb (B)
(1) 10 : 1 (2) 5 : 1 (3) 1 : 5 (4) 1 : 0.2

56. A solution is prepared by dissolving 0.6 g of urea (molar mass = 60 g mol –1) and 1.8 g of

r ts
glucose (Molar mass = 180 g mol–1) in 100 mL of water at 27ºC. The osmotic pressure of the
e
E xp
solution is: (R = 0.08206 L atm K–1 mol–1)
t s
[JEE MAIN-2019(April)]
r
(1) 4.92 atm
s tr y (2) 2.46 atm (3) 8.2 atm
x p e
(4) 1.64 atm
i
mthe vapour pressure of CS is 512 mm E
yHg and that of acetone is 344 mm Hg. A
57.
h e
Csolution of CS in acetone has a totalm
At 35°C,
s t r
i pressure of 600 mm Hg. The false statement
2

h e vapour
amongst the following is:
C [Jee Main (Jan. 2020)]
e r ts
xp
(1) CS and acetone are less attracted to each other than to themselves
2
(2) a mixture of 100 mL CS and 100 mL acetone has a volume < 200 mL
2

ry E
(3) Raoult's law is not obeyed by this system
(4) heat must be absorbed in order to produce the solution at 35°C m is t
s C h e
e t
r a solvent and the other containing a mixture of that solvent
58.
p
x are together sealed in a container. Over time :
Two open beakers one containing
E
s t r yof the solution decreases and the volume of the solvent increases
with a non volatile solute

i of the solution increases and the volume of the solventsdecreases

(1) The volume
m
e
Ch(3)
(2) The volume
The volume of the solution does not change and the volume e ofr
t
xp [Jee Main (Jan. 2020)]
the solvent decreases
(4) The volume of the solution and the solvent does notE
ry
change

i s t
59.
h e
A graph of vapour pressure and temperaturem for these different liquids X, Y, and Z is shown
s
below : C e r t
Z
E xp
Vapour pressure

800 X Y

tr y
(mm Hg)

500
s m i s
e t
r200
400
h e
E x p C
s tr y 0 293 313 333 353

i
m inference are made :
Temp

h e
The following
C(A) X has higher intermolecular interactions compared to Y.
[Jee Main (Jan. 2020)]

250
 Liquid Solution
(B) X has lower intermolecular interactions compared to Y
(C) Z has lower intermolecular interactions compared to Y

r t s r t s
e (A)eand (C)
The correct inference(s) is/are :
(4)p
(1) (B)
E x p (2) (C) (3) (A)
E x
s r y ry
t amount of NaCl should be added [to 600giofstwater ( = 1.00g/mL) to decrease the
60.
i
m point of water to –0.2°C ? ______.
How much
m freezing point depression constant for
hefreezing
C water = 2K kg mol ) –1
C h e (The
[Jee Main (Jan. 2020)]

61. A cylinder containing an ideal gas (0.1 mol of 1.0 dm 3) is in thermal equilibrium with a large
volume of 0.5 molal aqueous solution of ethylene glycol at its freezing point. If the stoppers S 1
and S2 (as shown in the figure) are suddenly withdrawn, the volume of the gas in litres after

r ts
equilibrium is achieved will be______.
e
xp
(Given, Kf (water) = 2.0 K kg mol–1, R = 0.08 dm3 atm K–1 mol–1)
s
[Jee Main (Jan. 2020)]

y E er t
istr Exp
hem try
C mis
Ch e
er ts
E xp
st r y When a few
i
62. An open beaker of water in equilibrium with water vapour is in a sealed container.

e m
grams of glucose are added to the beaker of water, the rate at which water molecules :
h
e r ts C [Jee-Main (Sep) 2020]

x p
(1) leaves the solution increases
(3) leaves the vapourE
(2) leaves the solution decreases

str y decreases (4) leaves the vapour increases

The m size iof a raw mango shrinks to a much smaller size when kept in a concentrated salt
63.
h e Which one of the following processes can explain thise ts (Sep) 2020]
? r[Jee-Main
C (1) Diffusion
solution.
xp (4) Dialysis
(2) Osmosis
ry
(3) ReverseE osmosis

i stand  in water at 298 K is given below :

64.
h e m
Henry’s constant (in kbar) for four gases , ,
   
C er ts
50 2 2 10
p
–5

x2020]
K 0.5
E
H
3 –3
(Density of water = 10 kg m at 298 K)
t r
[Jee-Main
s y (Sep)

s i
at a given pressure hem
This table implies that :
t
(1)  has the highest solubility inrwater
e solution at  is 250 bar C
E x p
ofry
(2) The pressure of a 55.5 molal
(3) Solubility t
(4) Them is of a 55.5 molal solution of  is 1 bar
at 308 K is lower than at 298 K

Che
pressure

251
 Liquid Solution
65. A set of solutions is prepared using 180 g of water as a solvent and 10 g of different non-volatile
solutes A, B and C. The relative lowering of vapour pressure in the presence of these solutes are

r t s r t s
in the order [Given, molar mass of A = 100 g mol–1; B = 200 g mol–1 ; C = 10,000 g mol–1]
e e
E x p E x p [Jee-Main (Sep) 2020]

tr y
(1) A > B > C
s
(2) A > C > B
t r y
(3) C > B > A
s
(4) B > C > A

m i i
mg of a protein A is isotonic with one litre of
66. he
C 3
C h
If 250 cm of an aqueous solution containing e
0.73
another aqueous solution containing 1.65 g of a protein B, at 298 K, the ratio of the molecular
masses of A and B is _______ × 10–2 (to the nearest integer). [Jee-Main (Sep) 2020]
Given 177.00

67.
ts
At 300 K, the vapour pressure of a solution containing 1 mole of n-hexane and 3 moles of n-
e r
xp
heptane is 550 mm of Hg. At the same temperature, if one more mole of n-heptane is added to

y E r t s
this solution, the vapour pressure of the solution increases by 10 mm of Hg. What is the vapour
e
is tr x p
pressure in mm Hg of n-heptane in its pure state __________?
E
[Jee-Main (Sep) 2020]

h e m
osmotic pressure of a solution of NaCl s r yatm and that of a glucose solution is 0.20
is t0.10
68.
Catm. The osmotic pressure of a solutionm
The
i
with 2 L of the glucose solutionCis h
e formed by mixing 1 L of the sodium chloride solution
s
–3
x×10 atm. x is ____. (nearest integer)
e r t
Given : 166.00
E xp
[Jee-Main (Sep) 2020]

try
The elevation of boiling point of 0.10 m aqueous CrCl .xNH solution iisstwo times that of 0.05
69.
m aqueous CaCl solution. The value of x is ………….. h
3
e
3
m 100% ionisation of the
2

e r t s Cthat all NH molecules are present

[Assume

inside the coordinationx

E
2
p
complex and CaCl , coordination number of Cr as 6, and 3

y
sphere] [Jee-Main (Sep) 2020]

i s tr
h e m r ts
C xp e
E
i s try
h e m
C e r ts
E xp
s t r y
ts m i
e r C h e
E x p
s t r y
m i
C h e
252
 Liquid Solution

EXERCISE # (JEE-ADVANCED)
1.

e r s e r t s
A 0.004 M solution of Na2SO4 is isotonic with a 0.010 M solution of glucose at same
t
p p
temperature. The apparent degree of dissociation of Na 2SO4 is [JEE 2004]
(A) 25%
E x (B) 50% (C) 75%
E x
(D) 85%

s r y
tbenzoic acid is dissolved in (i) 100 g acetone
s ry
t(K for acetone = 1.7) and (ii)100 g
1.22 giof
m (K for benzene = 2.6). The elevation m i
e e
2. b

C h benzene b
respectively.
h
C in boiling points Tb is 0.17°C and 0.13°C [JEE 2004]
(a) What are the molecular weights of benzoic acid in both the solutions?
(b) What do you deduce out of it in terms of structure of benzoic acid?

ts
3. The elevation in boiling point, when 13.44 g of freshly prepared CuCl 2 are added to one
r
kilogram of water, is [Some useful data, Kb (H2O) = 0.52 kg K mol–1, mol. wt. of
e
CuCl2 = 134.4 gm]
E xp r t s [JEE 2005]
(A) 0.05
s tr y (B) 0.1 (C) 0.16
x p e (D) 0.21

72.5egm
i E
y(k = 14) which leads to dimerization of
4.
h st r
Cphenol and freezing point is lowered bym7 ikelvin. What percent of total phenol is present in
of phenol is dissolved in 1 kg of a solvent f

dimeric form?
Che r
[JEE 2006]
e ts
E xkgpmol ),
–1

a freezing point depression of 2 K is observed. The van’t Hoff factor (i) is ry [JEE 2007]
5. When 20 g of naphtholic acid (C H O ) is dissolved in 50 g of benzene (K = 1.72 K
11 8 2 f

(D)i3s
t
(A) 0.5 (B) 1 (C) 2
h e m
e r t s C
x p
E point, freezing point and vapour pressure of a pure solvent change
Paragraph for Question No. Q.6 to Q.8

r y
tmolecules are added to get homogeneous solution. These are called colligative
Properties such as boiling
s
i
m Applications of colligative properties are very useful rintday-to-day
when solute
s
h e e
C examples is the use of ethylene glycol and water mixturexaspanti-freezing liquid in the radiator
properties. life. One of its

r y E
t water. The mole fraction of ethanol in the
of automobiles.

m
A solution M is prepared by mixing ethanol i sand
mixture is 0.9.
C h e ts
Freezing point depression constant of water   = 1.86 kg mol e r
xp
–1
Given : K fwater

Freezing point depression constant of ethanol   = 2.0rKykgE –1

t
K ethanol mol
is
f

e r t s
Boiling point elevation constant of water  
e m
K bwater
h
= 0.52 K kg mol–1

p elevation constant of ethanolC

x
Efreezing point of water = 273 K
Boiling point  = 1.2 K kg mol
K ethanol
–1

y
b

is r
tStandard freezing point of ethanol = 155.7 K
Standard

h e m Standard boiling point of water = 373 K

C
253
 Liquid Solution
Standard boiling point of ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg

r t s r ts
Vapour pressure of pure ethanol = 40 mm Hg
e e
E x p E p
Molecular weight of water = 18 g mol–1
x
Molecular weight of ethanol = 46 g mol–1
st r y stry
m i i
In answering the following questions, consider the solutions to be ideal dilute solutions and
m
he
6.C The freezing point of the solution M is C
he
solutes to be non-volatile and non-dissociative
[JEE 2008]
(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K
7. The vapour pressure of the solution M is [JEE 2008]
(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg
8.
r ts
Water is added to the solution M such that the mole fraction of water in the solution becomes
e
xp
0.9. The boiling point of this solution is [JEE 2008]
(A) 380.4 K
y E (B) 376.2 K (C) 375.5 K
e r ts
(D) 354.7 K
The Henry’sslaw
i tr constant for the solubility of N2 gas Ein xwater
p at 298 K is 1.0 × 10 atm. The 5

m of N in air is 0.8. The number oftrmoles

9.

h e
mole fraction
s y of N from air dissolved in 10 moles of
Cwater i
2 2
at 298 K and 5 atm pressure is–
–4
(B) 4.0 × 10 e m
h (C) 5.0 × 10
–5 –4
[JEE 2009]
–5

C ts
(A) 4.0 × 10 (D) 4.0 × 10

The freezing point (in °C) of a solution containing 0.1 g of K [Fe(CN) ] (Mol. Wt. 329) ine100 r
10. 3

E
6
xp2011]
tr×y10
–1
g of water (K = 1.86 K kg mol ) is
f [JEE
(A) – 2.3 × 10 –2
(B) – 5.7 × 10 –2
(C) – 5.7 × 10
i s
(D) – 1.2
m solute in 100 g of water,
–2

h e
att1satm pressure is 2°C. C
11. For a dilute solution containing 2.5 g of a non-volatile non-electrolyte
the elevation in boiling point r
x p e Assuming concentration of solute is

r y E
much lower than the concentration of solvent, the vapour pressure (mm of Hg) of the solution

t
–1

(A) 724 is
is: (take K =0.76
b K kg mol ) [JEE 2011]

e m (B) 740 (C) 736

r tsFor this process, the true
(D) 718

12. Ch e
xp
Benzene and naphthalene form an ideal solution at room temperature.
E
statement(s) is(are)
s r
tS y [J-Adv. 2013]
(A) G is positive (B) S
i
is positive (C)
m
system = 0. (D) H = 0
surroundings

h e of 80 g is dissolved in a solvent having density of 0.4 gs

tis
mol , Assuming no change in C r
13. A compound H X with molar weight
e
2

xp 2014]
–1
volume upon dissolution, the molality of a 3.2 molar solution

r E
ychloride-ammonia
[JEE-Adv.
14. If the freezing point of a 0.01 molal aqueous solution of a cobalt (III)
is t
e t
r is
complex (which behaves as a strong s
eletrolyte) is – 0.0558°C, e
h themnumber of chloride (s) in the

E x
coordination sphere of the p
complex C [JEE-Adv. 2015]

is ryK kg mol ]
[K of water =t1.86 –1

m
f

C h e
254
 Liquid Solution
15. Mixture(s) showing positive deviation from Raoult's law at 35°C is (are) [JEE-Adv. 2016]
(A) carbon tetrachloride + methanol (B) carbon disulphide + acetone
(C) benzene + toluene
e r ts (D) phenol + aniline
e r t s
E x p x p
E Here xL and xM represent
y y
16. For a solution formed by mixing liquids L and M, the vapour pressure of L plotted against the
r of M in solution is shown in the followingrfigure.
is t of L and M, respectively, in the solutions.
mole fraction
is tThe correct statement(s) applicable to
he msystem is(are)
mole fractions
h e m
C C
this [JEE Adv. 2017]

PL

e r ts
E xp r ts
s t r y x
M 0
interactions between L-L in x p e
M are m
i
(A) Attractive intermolecular
E
yliquid
pure liquid L and M-M in pure liquid

h
Cx  0e stronger than those between L-M when mixed
The point Z represnts vapour pressure ofspure
i t r in solution.

m of pure liquid L and Raoult's law is obeyed when

(B) M and Raoult's law is obeyed when

h e
C ts
L
(C) The point Z represnts vapour pressure
e r
x 1
(D) The point Z represnts vapour pressure of pure liquid M and Raoult's law is E
L
xpwhen
try
obeyed
x =0x =1
L L

Pure water freezes at 273 K and 1 bar. The addition of 34.5 e

is
methanol to 500 g of water
17.
s
changes the freezing point of thetsolution.
r C h g of

e shown below represent plots of vapour pressure (V.P.)

Use the freezing point depression constant of water
–1

x p
as 2 K kg mol . The figures
E
s tr y
Among the following, the option representing change in the freezing point is

m i s
Ch e e r t
E x p
(B) y
(A)
i str
h e m
C e r ts
E xp
s tr y
t s m i
e r C h e
(C)
E x p (D)

s t r y
m i
C h e
255
 Liquid Solution
18. Liquids A and B form ideal solution over the entire range of composition. At temperature T,
equimolar binary solution of liquids A and B has vapour pressure 45 Torr. At the same

e r t s e r t s
temperature, a new solution of A and B having mole fractions xA and xB respectively, has

E x p x p
vapour pressure of 22.5 Torr. The value of XA/XB in the new solution is ____.
E
r y r y
(given that the vapour pressure of pure liquid A is 20 Torr at temperature T) [JEE Adv. 2018]
s t s t
i
mplot given below shows P – T curves (where m i
19.
heThe
h e P is the pressure and T is the temperature) for
C of NaCl in these solvents. NaCl completely
C two solvents X and Y and isomolal solutions
dissociates in both the solvents. On addition of equal number of moles of a non-volatile solute
S in equal amount (in kg) of these solvents, the elevation of boiling point of solvent X is three
times that of solvent Y. Solute S is known to undergo dimerization in these solvents.
If the degree of dimerization is 0.7 in solvent Y, the degree of dimerization in solvent
X is ____.
er ts [JEE Adv. 2018]

Exp 1 2 3 4
t s
760 y
tr e r
is 1. Solvent X xp
m y E
Pressure (mmHg)

Che s r
t Y
3.iSolvent
2. Solution of NaCl in solvent X

h e m4. Solution of NaCl in solvent Y

C ts
(mmHg)

er
Exp
istry
m
367
360
362

368

s Che
er t Temperature (K)

xp
On addition of equal number of moles of a non-volatile solute S in equal amount (in kg) of
E
ry
these solvents, the elevation of boiling point of solvent X is three times that of solvent Y.
st
i
Solute S is known to undergo dimerization in these solvents. If the degree of dimerization is 0.7
m
Che
in solvent Y, the degree of dimerization in solvent X is ____.
e r ts
On dissolving 0.5 g of a non-volatile non-ionic soluteE
p
tox39 g of benzene, its vapor pressure
20.
s y of freezing point of benzene (in K)
trdepression
decreases from 650 mm Hg to 640 mm Hg. The
m i
h
upon addition of the solute is_____
C e
molal freezing point depression constant of benzene are 78tgs
[JEE Adv. 2019]
(Given data: Molar mass and the
p e r
–1
mol and 5.12 K kg mol , respectively) –1

E x
s y
tBrat 25°C. Two such
21.
s of A have the total
Liquids A and B form ideal solution for all compositions of A and
tfractions i
m pressure of 0.3 and 0.4
e r h e
pvapor pressure of pure liquidCB in bar ? [JEE Adv. 2020]
solutions with 0.25 and 0.50 mole vapour
bar, respectively. What isxthe
E
i stry
h e m
C
256
 Liquid Solution
ANSWER KEY

r ts EXERCISE # (JEE-MAIN)
r ts
p e (4) 6. pe(4)
1. (1) 2. (2)
x
(1)E 10.
3. 4. (4) 5. (2)
x
(4) E13.
7. (4)
8. (3) 9.
s ry
t (2) 17. (3)
(4) 11. (4) 12.
r y
19.st (3)
(1) 14. (4)
15.
i
(1)m 23.
(3) 16. 18.
(4)em
(3)
i 20. (2) 21. (1)
22.
he (3)
C (3) 30. (2) 31. (4)
29.
24. (3) 25.
h
32. C (1)
26.
33.
(1)
(4)
27.
34.
(3)
(1)
28.
35.
(3)
(1)
36. (4) 37. (3) 38. (1) 39. (4) 40. (1) 41. (2) 42. (2)
43. (4) 44. (3) 45. (3) 46. (4) 47. (3) 48. (1) 49. (2)
50. (3) 51. (1) 52. (2) 53. (2) 54. (1) 55. (3) 56 (1)

e r ts
EXERCISE # (JEE-ADVANCED)
E xp r t s
1. (C)
s t y
r that benzoic acid remains as it is in acetone
x p e
2.
i
(a)122, (b) It means
(C) m
y E
while it dimerises in benzene

he(degree of asso = 70%) t r

3.
4. C35% i s
7. m (B)
e
5. (A) 6. (D)
C h 8. (B) 9.
(1)rts
(A)
10. (A) 11. (A) 12. (B,C,D) 13. (8) 14.
e
19.xp(0.05)
15. (A, B) 16. (A,C) 17. (C) 18. (19)
y E
20. (1.02) 21. (0.20)
i s tr
h e m
er t s C
E xp
s t r y
m i s
Ch e e r t
E xp
i s try
h e m
C e r ts
E xp
s t ry
t s m i
e r C h e
E x p
s t r y
m i
C h e
257
 Liquid Solution
HINT AND SOLUTIONS

r t s EXERCISE # (JEE-MAIN)

e r t s
1.
pe x
thexnumber of solute particles in a solution, higher
p
Elevation in boiling point is a colligative property which depends upon the number of solute
particles. Greater E E
s tr y s tr y the extent of elevation in

i
boiling point.
m Na SO 2Na + SO em
i
Che Ch 2 4
+
4
2–

2. Benzene-methanol shows a positive deviation from Raoult's law

3. Tf  iK f m ; Kf depends on nature of solvent.

e r ts
 2Na xp
4. Na SO 2 4

y E + SO +

er ts4
2–

1
is t r 0 0
xp
1– m
e 
ry E
h t
2
CVant Hoff factor (i) =      
 2i.
 1m
s
e
1 2
1
Ch er ts
p
o o

x
5. P = P XB P = 75 torr
B B B

E
try
78 / 78 1 1 1
s
XB = = = PB = 75 × = 50 torr.
(78 / 78)  (46 / 92) 1  0.5 1.5 1.5
m i
s C h e
r t
6.
p=e1000.
Total millimoles of solute = 480 × 1.5 + 520 × 1.2 = 720 + 624 = 1344.
Total volume = 480E +x
y mixture = 1344
trfinal
Molarity iofsthe
520

e m r ts
= 1.344 M.

Ch e
1000

E x p
tr y
is of solution and does depend on nature of solute.
7. Equimolar solutions in the same solvent have same boiling and same freezing points because

m
Che
colligative properties depends on concentration

e r ts
P –P
0
n 760 – P 0.1
E x p
 
y
s s

r
8. ;
nN 9.9  0.1
t
0

s
P 760
P = 752.4 torr
ts m i
s

e r C h e
According to Raoult'sE x p
9.
r y
P =iPst+ P = P x + P x
law

m
o o o
or 290 = P × (0.6) + 200 × (1 – 0.6)
e
A B A B B A

h
C 290 = 0.6 × P + 0.4 × 200
or o
A or P = 350 mm. o
A

258
 Liquid Solution
10. Isotonic solutions have same osmotic pressure.
1 = C1 RT , 2 = C2 RT

er ts
For isotonic solution, 1 = 2
e r ts
 C = C . Exp E x p
s y
1.5t/r60
1 2

s r y
tof the substance]
mi 5.25 / M
m i
e e
or = [where M = molecular weight

Ch V
1.5 5.25
V
C h
or = or M = 210.
60 M

11. Ptotal = PºA XA +PºB (1–XA)= 520 × XA + 1000 ×(1–XA) = 760

520XA + 1000 –1000XA = 760 ;
e t s
r 50% moles of A
480X A = 240

 X = 0.5 So, mixture p

E x contains
r ts
y
A

str 178.2 /18 xpe

i
P =ePmx = 17.5 × y E
12.
C h A
0
A
178.2 18
A
i
= 17.325
str
180 em


Ch ts
18

p er
Pº + 3Pº = 550 × 4 .....(i) Ex
1 3
ry
13. P = Pº X +Pº X = Pº × + Pº × = 550 
t
total A A B B A B A B
4 4
is
5 m
Pº + 4Pº = 560 × e
1 4
Similary, 560 = Pº × + Pº ×
5
r ts 5
A
C h B .....(ii)  A B

eq. (ii) – eq.(i)

x p e
r y E
t
Pº = 560 × 5 – 550 × 4= 600
is Pº = 400.
B

h e
so,
m A

r ts
C The solution is non-ideal, showing +ve deviation from Raoult’s e
xp Law.
E
try
14.

m is
 2Na (aq.)+ SO e(aq.)
Na SO (s) 
h ts
+ 2–

T = i K m = 3 1.86 0.01 =C
H2O
15.
r
2 4 4

 f f 
0.0558 K. 
xpe
r y E
is t
s m
16. P =X Pº +X Pº
t
T Heptane Heptane Octane Octane

105 + er 45
C h e
p
0.25 0.307
x
=  
0.557
47.127 + 24.80 r =y
E 0.557

i s t 71.92  72 kPa

h e m
C
259
 Liquid Solution

17. AxBy  xA y  yBx –


1– 
e r t s x y
er ts
Exp
i = 1 –  + x  + y  = 1 +  (x + y – 1)
Exp
So,  =
 try
s
i 1

stry
m i x  y 1

mi
he w he
C T = i × K × m ; 6 = 1 × 1.86 × 62 C4
18. f f

w = 800 g

19. 1 = 2
i1C1 = i2C2
er ts
5  1000
= 1× Ex
p
1 1000
ts
1×
342  100 ry M  100
t per
m i s Ex
e
M = 68.4
h
g/ mol
stry
C mi
= 5.55 × 10 m Ch
e
ts
0.01
r
–4

e
20. m=

xp
60  0.3
E
21. Tf = i × Kf × m ; 1.91 = i × 1.86 × 1
istry
hem
s C
1.91
i= = 1.027
r t
e = 2.7 %
 i = 1 +  = 1.027

p
1.86
  = 0.027,
Ex
y
% dissociation

is t r
h e m r ts
e
0 0
22. Since P =X P +X P
C p
s A A B B

⇒ Ex300 = 0.5 × P + 0.5 × P ……..(2)

1 2
ry
0 0 0 0
⇒ 250 = × P + × P ……. (1)
s t
A B A B

i
3 3
Pm
e
0 0

h
On solving eq. (1) and (2) we get = 450 mm Hg P = 150 mm Hg
C ts
A B

e r
0.85 1000
E xp
23. T = i × K × m ;
f f 0.23 = i × 1.86 ×
s try
 i = 1 + 2  = 2.47 s
t
136.3 125
m i
i = 2.47
e r = 73.5 % Ch e
  = 0.735,
E x p
% dissociation

r
T = i × Kis×tm ;
y w
24.
h e
f
m f 2.8 = 1 × 1.86 ×
62 1
Cw = 93.3 g
260
 Liquid Solution

12
P 0 – Ps n M
 0.1 
25.
P 0

er
nN
ts
;
12 108

er ts
Exp M 18
Exp
M  20
s try stry
i
m  (M) mi
26. he
C nM  n
Che
 
1–  ⇒ i = 1 – + = 0.9
n n

Given ; n  0.2   = 0.18 n
0.9
e r ts
⇒ i = 1 – 0.18 n +
E xp : n = 1.55
0.18 n
= 0.9
r ts
s tr y n
xpe
m i E
X P + X P = 0.5 × 119 + 0.5 × 37 = 78try
Ph=e
27.
C s b
0
B t

m
t
0

is
P =X P =Y P
t t t
0

C t
he s

r ts
⇒ 18.5 = Y × 78 ⇒ Y = 0.237
xpe
E
t t

Tf = 273 – 268 = 5 K istry

28.

hem
Tf = i × Kf × m ;
r t s ⇒
w
C
pe
5 = 1 × 1.86 ×
32  10
w = 860.2 g Ex
st r y
m iconcentration of particles = iC
29.
Ch e
Effective
er ts
C H OH(aq) = 1× 0.5 = 0.5 M
Exp
ry
2 5

Mg (PO ) (aq) = 5 × 0.1 = 0.5 M

3 4 2
ist
KBr(aq) = 2 × 0.25 = 0.5 M
hem
KBr(aq) = 4 × 0.125 = 0.5CM
er ts
Exp
30. Hmixing = 0 (zero) 
stry
ts
A – A, B – B and A – B interactions are identical
mi
er Che
31. 1 = iCRT ;
E xp ⇒ 10.8 = i × 0.1 × 0.082 × 298

try
⇒ i = 4.42 (experimental)

m is
⇒ i = 5 (expected)
h e
C ) (SO )  Fe + NH + 2SO
Fe(NH 4 2 4 2
2+
4
+
4
2–

261
 Liquid Solution
32. M1V1 + M2V2 = M3V3

s s
0.5 × 750 + 2 × 250 = M3× 1000
M3 = 0.875 M
er t er t
Exp Exp
r
P  Pistn
y stry
m
0
185  183
1.2
100 em
M i
e  
S
33. =

C h Ch58
P N
S 183

M = 64 g mol–1
1.5 3.5
34. Ps = Xb PB0 + Xt Pt0 = × 74.7 + × 22.3 = 22.41 + 15.687 = 38.097
5 5
Pb = Xb Pb0 = Yb Ps

e r ts
⇒
Y = 0.589 Ex
p
22.41 = Yb × 38
t s
⇒
y e r
r in benzene due to intermolecularxHp– bonding.
tassociated
b

35.
i s
Acetic acid is
m E
e ry
CPh– P  n ; 760 – P  0.1mist
he 0.1
0

760 C9.9
ts
s s
36.
nN
r
0

e
P
Ps = 752.4 torr
Exp
istry
37. Solubility  Partial pressure of gas
hem
0.01 500
 ;
e r ts S = 0.015 g L–1 C
S 750
Ex p
s ry
t M + 2 X
i
m1 –  ts
38. MX
e r
2

Ch e
xp
 2
E
try
i=1+2  =2
 = 0.5
mis
39. Tf = i × Kf × m
Che ts
er
xp
0.2  1000
E
0.45 = i × 5.12 ×
60  20

stry
i = 0.527 = 1 –

;
ts
 = 0.945
mi
2
e r Che
E x p
t r y
will also beis
40. [Co(H O) Cl ]. 3H
2 3 O produces least number of particles in solution so, dression in freezing
3 2

e m least and freezing point will be maximum.

Ch
262
 Liquid Solution
41. Pgas = KH Xgas
KH  Solubility 
T  KH 
er ts er ts
Exp Exp
X = 0.4 try
stry
42.
m isP = Y P
A

10m
= 7 ×e
i
Che h
O 3
PAO
C
P = XA A A A s Pa
0.4×7×103 = YA × 104 PBO = 12 × 103 Pa
YA = 0.28 Ps = XA PAO + XB PBO
YB = 0.72 = 0.4×7×103 + 0.6×12×103 = 2.8×103 + 7.2×103 = 104
43.  Tb = Kb × m
er ts
1 y E
2
xp r ts
e
K = =2
tr
b

s
T i= K × m Exp

h em try
s
f f

C K = 2 =1 mi
h e
C ts
f

r
2
 K = 2K
xpe
E
b f

44. Tf for diluted milk = 0.2

istry
Tf for pure milk = 0.5
hem
t
 Tf diluted  iK f m diluted

e r s C
x p
 Tf pure  iK f m pure
E
0.2 m m ry2
 i;st 
0.5 m s
1 1

h e m m 5
C Assume that Solution is dilute so molality = molarity xp
2 2

er t
r y E
ist
M 2m
 1
M 5m
2
m
heof pure milk.
C
So 3 cups of water are added to 2 cups
er ts
45. For dimerisation
Exp
1  1 
stry
i = 1 +    1 = 1 + 0.8   1 = 0.6
n 
ts 2 
mi
er Che
 Tf = i × Kf × m
W / 122E
xp
2 = 0.6 × 5 × ry  1000
ist 30
h m
=e2.44
CW

263
 Liquid Solution

46. K2[HgI4]  2K+ + [HgI4]2

i = 1 + (n – 1) = 1 + (3–1) × 0.4 = 1 + 2 × 0.4

er ts er ts
 T  =  T  Exp p
i.e.: i = 1.8

Ex
47.

stMry
f X f Y

stry
K M i=K
mi
e 4m 12 e
f X f Y

C =h A MY
Ch
MY = 3 A
48. Let amount of water (ing) separated as ice is x
Tf = i × Kf × m

e r ts  x = 64 62 1000

xp
 10 = 1 × 1.86 ×

Since on mixingrtwoy E 62  (250 – x)

liquids A and B change in volume after e r tsis zero, therefore binary
49.
i st E x p mixing

h e
solutionmis an ideal solution. t ry
C P = P X  P X = (400 × 0.5) m s
+i(600 × 0.5) = 500 Torr
e
0 0

Ch
T

ts
A A B B

e r
xp
P X 400  0.5 0

E
A A
Mole fraction of A is vapour phase = = = 0.4

try
P 500 T

m i s
e
50. P = K × mole fraction of gas.
gas H

 P = Kts1  X 
r C h
e
i.e. P = K · X
gas H gas gas H

p
H2 O

P  K  K .XEx
gas

s t ry H H H2O

 i
 
e ymc r ts
h
C For Z, K is maximum e
xp
m x

E
try
H


m i s
C h e ts
r
O O

e
51. P = 450 mm of Hg P = 700 mm of Hg

xp
M N

That is 'N' is more volatile liquid as compare to 'M' so,

r y E
x y
is t

s m
N N
x y
e r t h e
p C
M M

x y
E x

r y
M M
or
x y
i
N
st N

h e m
C
264
 Liquid Solution

52. 1 = 2 × 4

er s
i1C1RT = i2C2RT × 4
t er ts
C = 6 × 10 M Exp
2 × C1 = 3 × 0.01 × 4
Exp
y y
–2
1

i s tr istr
e m
53. h T = i k m hem
C f f
C
= 3 × 4 × 0.03 = 0.36 K

P n
54. 

ts
P 0
nN

er
xp
P 0.01

35 0.01  20
y E er ts
0.01 str xp
P 
m i  35 = 0.017 mm
y E
C h e 20.01
istr
e m
55. T = K × m Ch er ts
xp
b b

( Tb )A (K b )A  m 1
E
try
 =
( Tb )B (K b )B  m 5
mis
s Che
e r t
56.  = CRT
E x p
 
s
60 i180 r
 0.6 1.5 
 y
t × 0.08206 × 300
= 
h e m0.1 r ts
C xp e
  = 4.92 atm.
E
istry
57. (2)
Since total pressure of solution h is e m than vapour pressur of CS
Sol.
C deviation from ideal behaviour.
greater 2
r ts
and acetone which
e
xp
indicates solution is showing positive

r E
y of pure solvent.
t
58. (2)

s m is
Sol. Due to presence of solute vapour pressure of solution will be less than V.P.

e r t h e
C
So, vapour move from higher pressure to lower pressure.

E xp
Sol. order of B.P. tzr>y
59. (1)

m is z < y < x
y>x

heof inter molecular forces : z > y > x

order of V.P.
Corder
265
 Liquid Solution
60. [1.75 or 1.76]
NTA Ans. (1.74 to 1.76)
0.2
= 2
er ts
n2
er ts
p p
Sol. × 1000
10
Ex 3600
Ex
try
n = 0.03
s stry
mi
w = 0.03 × 58.5 g
mi
Che = 1.75 or 1.76
NTA ans 1.74 to 1.76 Che
61. 2.17 or 2.18
NTA Ans. (2.18 to 2.23)
Sol. Tf = 2 × 0.5 = 1
T = 273 –1 = 272 K
e r ts
V=
0.1 0.08  272
E xp r t s
1
s tr y x p e
= 2.176
m i y E
h e
= 2.18 L
CNTA Ans. (4) is t r
e m
h vapour pressure of solution will be less than vapour
Csolute) ts
62.

er
xp
Sol. On adding glucose (non volatile

E
pressure of pure solvent. So some vapours will condense to maintain this vapour pressure.

is try
63. (2)
h e mto osmosis.
e r t s
Sol. When raw mango is kept in a concentrated salt solution it
C
shrinks due

E xp
r y Law :
Sol. AccordingstotHenry’s
64. (2)

Km
i s
h e
C  solubility  1 at a particular pressure.
P= .X
e r t
p
H gas.

E x
K
s t r y
i
H

Option (2) : Since molarity ofC

em
Option (1) : Since ‘’ Gas highest value of K so it has lowest solubility.
h
H

ts
is 55.5
e r
So mole fraction of  =
55.5
E xp
55.5  55.5
s try
t s 1
m i
e r = = 0.5
C h e
p
2
Px

r y E= 0.5 × 0.5 k bar
=K ×X
H 

is t
e m = 250 bar.
h (3) : Solubility of gas decreases with increase in temperature.
COption
266
 Liquid Solution
Option (4) : Since molality is 55.5
55.5

r ts er ts
So, mole fraction of  =
55.5  55.5
Pp=e p

x K X
E = 2 × 10 × 0.5 k bar Ex H 

stry stry –5

mi = 10 bar.
mi –2

Che C h e
65. (1)
Sol. Relative lowering of V.P. =
10 10 10
 P  100  P  200  P  10, 000
 0   10 180 :  0   10 180  0   10 :

ts
 P A   P    P  
180
r
B C
100 18
 P   P x  p
e
200 18 10, 000 18
 P 
    y  E
 P tr  P  er ts
P 
0
A
is
0
B
0

Exp
m
C

h e stry
66. C177 mi
Sol. If both solutions are isotonic Ch
e
er ts
 Molarity of A = Molarity of B
Exp
try
0.73 / M A 1.65 / M B
250
× 1000 =
1000
× 1000
mis
s Che
t
MA 0.73
 = 1.77 = 177 × 10–2

M B 0.25 1.65
per
E x
y
So correct answer is 177.
t r
is(600)
NTAm
67.
Che P  1  P  3
Ans.
er ts
Sol. 550 = o o

Exp
try
A B
4 4
2200 = P  3PBo o
…(i)
is
…(ii) em
A

Ch ts
2800 = PAo  4PBo
er
xp
1 4
560 = P   PBo 
E
o

y
A

r
5 5
PB  600, PA  400
o o

ist
r ts em
68. (167)
E x p e Ch
Sol. Osmotic pressure y
t r
For NaCl ii=s2 so
=  = i × C × RT

 e=m

Ch i × C × RT C = conc. of NaCl
NaCl NaCl NaCl

267
 Liquid Solution
0.1 = 2 × CNaCl × RT
0.05
CNaCl =
er t
RTs Cglucose = conc. of glucose
er ts
Exp
For glucose i = 1 so
Exp

ry
Glucose = i × Cglucose × RT
st stry
mi
0.2 = 1 × Cglucose × RT
mi
Che CGlucose =
0.2
Che
NaCl = No. of moles NaCl
RT
 NaCl in 1 L = CNaCl × VLitre
0.05
= glucose = No. of moles glucose
RT

ts
0.4
 glucose in 2 L = Cglucose × VLitre =
er RT

Exp
VTotal = 1 + 2 = 3L
r ts
stry xpe0.05
i
so Final conc. NaCl =
m y E
e
3RT

Ch istr 0.4
m
Final conc. glucose =
e
Ch
3RT
 Total = NaCl + glucose
er ts
= [o × CNaCl + Cglucose] × RT
Exp
try
 2  0.05 0.4 
=
 3RT

3RT 
  RT
mis
s Che
t
0.5
=
per3
atm = 0.1666 atm

Ex
= 166.6 × 10–3 atm
 
stry 167.00 × 10–3 atm
mi
Che
so x = 167.00
e r ts
E xp
tryof non electrolyte
69. (05.00)

i s
m so the molality of given solution of
Sol. 0.05 m aqueous CaCl solution = 0.15 molal solution
2

Since the elevation in boiling point ise

C h double
r ts
complex = 0.3 m
xpe
Hence the complex must be producing three ions in the solution, so its
ry E
i st
s m
formula = [Cr(NH ) Cl]Cl
t e
3 5 2

so x = 5
p e r C h
E x
s t r y
m i
C h e
268
 Liquid Solution

EXERCISE # (JEE-ADVANCED)

1.
er t s
(obs ) Na2SO4 = glucose
er ts
10 1  2Exp Exp
or
4try1
 or 10 = 4 + 8
stry
mis 10  4 mi
 he % of h=e
C   = 8 = 0.75 C 75%

2. (i) In first case,

Wt. of solute 1000
Tb = Kb × m = Kb × ×
Mol. wt. of solute wt. of solvent

ts
1.22
or 0.17 = 1.7 ×
e r
xp
M 100 10 –3

y E er ts
tracid exists as a monomer in acetone Exp
or M = 122 g/mole

is
Thus the benzoic
In m
(ii) e r y
h
C T = K × Wt.of solute × m1000
second case,
is t
e
Ch wt. of solvent ts
b b
Mol.wt.of solute
e r
1.22
E xp
trythat benzoic acid
or 0.13 = 2.6 × or M` = 224
M`100  10 –3

m is
e
Double molecular weight of benzoic acid (244) in acetone solution indicates
exists as a dimer in acetone.
r t s C h
i (vante
3. T = i K m
b b
E x p Haff factor) of CuCI = 3
2

s t r y 13.44

m
b
i
T = 3 × 0.52 ×
134.4  1
= 0.156 = 0.16.
s
Ch e er t
xp
4. T = i × K × molality
E
f f

try
72.5
7 = i × 14 ×
94  1
; i = 0.648
m i s

C h e ts
i = 0.648 = 1 – ; = 0.704
e r
xp
2

ry E
t
20 1000
5. T = i × K × molality
f f 
s
2 = i × 1.72 ×
172
×
50
m is
t
r 2 = 4i 
e h e
x p
E  i = 1/2 = 0.5 C
  
s t

r y
m i
C h e
269
 Liquid Solution
0.1 2000 1000
6. Tƒ = Kƒ . m =2× × 1000 = = = 4.83
0.9  46 414 207
T’ƒ = Tƒ – 4.83
e r t s e r t s
T’ = 155.7 – 4.83 xp
E E x p
y y
ƒ

is t
T’ = 150.9r K
ƒ
i s t r
7.
he mvapour pressure
Total
he m
C Cnon-volatile as given in the question)
P = Pº X (considering solute to be
A A

P = 40 × 0.9 = 36 mm Hg
0.1 520
8. Tb = Kb . m = 0.52 × × 1000 = = 3.20
0.9  18 9 18

e r ts
Tb = 373 + 3.20
T = 376.2 K b

xp
9. P =K × x
ts
N2 H

E
N2

y
× 0.8r×
per
10 ist
1
x
–5
x = 5 = 4 × 10 per mole
m solubility is 4 × 10 . E
N2 5

h e st r y
C i
–4
In 10 mole

e m
Ch0.1 = 2.3 × 10 er ts
xp
–2
10. T = i × K × m
f = 4 × 1.86 ×
f
329  0.1
E
 Tf = 0 – 2.3 × 10–2 = – 2.3 × 10–2 ºC.
istry
hem
11.  Tb = 2ºC ;
egr t s ma = 2.5 g C
x p
Ky= E
m = 100 solvent

t r
is Psolution = ?
0.76 K. kg. mol b
–1

m ts
ChTe= K × m x p er
E
b b

2 = 0.76 × m     m=
2
i stry
he m 20.76
P0  P
= m × MM × 10–3 C
760  P
er ts –3

xp
= × 18 × 10

E
P P 0.76
36 796
s tr y
760 – P =
760
P  

ts
760 =
760
P
m i
e e
r P = 760  796  torrC= h725.6 torr  724 torr
E xp 

s tr y  760 

= –m
G e
i
12.
h
C ve, S = + ve Always for solution formation.
system

270
 Liquid Solution

Ssurr. = 0 No heat exchange between solution and surrounding.

H = 0
s s
For ideal solution.
r t
eof solution = 1L = 1000 mL e r t
p p
13. 3.2 M = 3.2 moles of solute present in 1L of solution.
x x
E × density = 1000 mL × 0.4 g/ mLr=y400Eg =0.4 kg
y
Volume of solute = volume

is t r
Mass of solute = Volume
ist
he m 3.2  8 m h e m
C Molality =
0.4 C
14. Tf = Kf × i × m
0.0558 = 1.86 × i × 0.01
i=3

e r ts
Given complex behaves as a strong electrolyte
 = 100 %
E p by complex)
xgiven ts
tr y
n = 3 (number of particles
p e r
 complexis E x
h e m is [Co(NH ) Cl]Cl 3 5 2

t r ycomplex = 1
C number of Cl ions in –
the co-ordination
m is
sphere of the
e
h and (carbon disulphide + acetone) do not having any
15. (carbon tetrachloride + methanol)
C er ts
attraction forces.
E xp to L,
16. From the graph it is clear that there is +ve deviation from Raoult law with
s try respect

m i
therefore option A is correct. When X 
e
 1, then Z will have value equal to P (Vapour 0

h
L

iss
L

pressure of pure L ) so, option C

e r t also correct. C
34.5 p
T  K  m = 2  Ex  2 1.5 = 3
y 46
2
17. f

s t
f
r
i point of ethanol + water solution = 273 – 3 = 270 K s
h e m r t
e
So, freezing
C 1
P = × P + × P (Given P E
1 1
x pTorr)
ry
0 0 0
18. X =X = ; = 20
t
A B T A B A

s
2 2 2
90 = 45 × 2 = P + P ……….(1) ; m P = 70 i
e
0 0 0
A B

C h B

r ts
22.5 = X P + (1– X ) P ……….(1)
A A
0
A
0

xp e
E
B

22.5 = X ×20 + (1– X ) 70 = 70 –50 X

s tr y
i
A A A

; ts e m
r X
47.5 19 1 X
e
 19
h
A
X = = ; X =
p C
A B

x
50 20 20
E 1=2×K ×m ; K 2
B

2 = 2 × K ×t mry ;
is
b(x )
19.
m
b(x) b(y)

Che
K b (y)

271
 Liquid Solution

     
Tb(x)  1– 1  K b(x) m ; Tb(y)  1– 2  K b(y) m
 2  2 

er ts er ts
2S
x p
E  /2 ;

 S2
i = 1 –  +  /2 = 1–  /2 Exp
1 –
s r y
t 1–   K s tr y
he
i
mT  2  ; 1
 h
mi
 e3  0.65
C 1–C  
b(x )
3 =  b(x ) 1

Tb( y)  0.7   2 2
1–  K b( y)
 2 
 = 0.05

P – Ps n 0.5
e r ts
650 – 640
xp
  
s
20.
Ps
y E
N Msolute  0.5 640
er t
= 64 tr p
M
m
solute
is Ex
h e 0.5 1000
 1.025 str
y
CT = iK m = 1 × 5.12 ×
f f
64  39
m i
Ch e
er ts
E xp
Sol. Let P and P are vapour pressure of pure A and B liquid respectively try
21. (0.20)

is
 

m
A B

When X = 0.25
s C h e
t
A

P = P X + P X 

p e r 

+x
T A A B B

0.3 = 0.25 P E
y
 

r
0.75 P ......(1)
When Xis=t0.5
A B

h e mP = P X + P X
A

r t s
C 0.4 = 0.5 P + 0.5 P e
 

......(2) Ex
p
T A A B B

try
 

s
A B

From equation (1) & (2)

m i


C h e ts
r
P = 0.2 bar
e
B

3
P  bar 

Exp
ry
A

t
5

s m is
er t h e
E xp C
s tr y
m i
C h e
272
 Surface Chemistry

EXERCISE # (JEE-MAIN)
1.
r t s r ts
Which one of the following characteristics is not correct for physical adsorption?
e e[AIEEE 2003]
x p Exp
y onE y
is r
t increases with increase in temperature ist
(1) Adsorption solids is reversible
r
he m
(2) Adsorption
he m
C (3) Adsorption is spontaneous C
(4) Both enthalpy and entropy of adsorption are negative.

2. The disperse phase in colloidal iron () hydroxide and colloidal gold is positively and

r ts
negatively charged, respectively. Which of the following statements is NOT correct?
e
E x p t s [AIEEE 2005]
(1) Coagulationr iny
p e r
ithestsols has no effect x
both sols can be brought about by electrophoresis

m
e sulphate solution causes coagulation y E
C(3)hSodium tinr both sols
(2) Mixing
i s
m the gold sol more readily than the iron ( )
C e
(4) Magnesium chloride solutionhcoagulates, s
e r

t
hydroxide sol.
E xp
i s try
The volume of collodial particle V as compared to the volume m
3.
s
C

C h e of a solute particle in a true

solution V could be :
e r t [AIEEE 2005]
xp~ 10
S

E
23 –3 3
(1) ~ 1 (2) (3) ~ 10 (4) ~ 10

s t r y
m i model of adsorption of a gas on a solid surface : s [AIEEE 2006]
4. Ine
ert does not depend on the
Ch(1) the rate of dissociation of adsorbed molecules fromxthepsurface
langmuir’s

r y E
surface covered
i s t
(2) the adsorption at a single site one
h m
ts
the surface may involve multiple molecules at the same
C e r
time
(3) the mass of gas striking a given area of surface is proportional to the pressureEofx
p
s t r y of the gas
the gas

ts m i
(4) the mass of gas striking a given area of surface is independent of the pressure

e r C h e
E x p
5.
y
tr of their protective powers is
Gold numbers of protective
The correctis
colloids A, B, C and D are 0.50, 0.01, 0.10 and 0.005, respectively.

m order [AIEEE 2008]

C(1)hCe< B < D < A (2) A < C < B < D (3) B < D < A < C (4) D < A < C < B
273
 Surface Chemistry
6. In context with the industrial preparation of hydrogen from water gas (CO +H2), which of the

s s
following is the correct statement? [AIEEE 2008]
r t e r t
xpeocclusion with Pd p
(1) CO is removed by absorption in aqueous Cu Cl Solution
x
2 2

(2) H is removedE
r y through
r y E
istoxidized to CO with steam in the presenceisofta catalyst followed by absorption of
2

(3) COis

he m 2

h e m
CO in alkali
2

2
C differences in their densities
C (4) CO and H are fractionally separated using
7. Which of the following statements is incorrect regarding physiosorptions ?
[AIEEE 2009]

ts
(1) More easily liquefiable gases are adsorbed readily.
e r
xp
(2) Under high pressure it results into multi molecular layer on adsorbent surface.

y E e r t s
tr p
(3) Enthalpy of adsorption (H ) is low and positive.
i s x
adsorption

e m
(4) It occurs because of van der Waal’s forces.
r y E
C h i st
e m
8.
Chisotherm which of the following is correct?
According to Freundlich adsorption
[AIEEE 2012] er
ts
E xp
(1)
x
p 
0

is try
m
h e m
(2)
x
p 
1

e r t s C
xp
m

y E
m istr
x 1/n
(3) p 

h m
(4)eAll the above are correct for different ranges of pressure r t s
C xp e
E
i s tryNa , Al and Ba for arsenic sulphide sol
+ 3+ 2+

m
9. The coagulating power of electrolytes having ions

C h e ts
r
increases in the order : [JEE(Mains) 2013]
3+ 2+ + + 2+ 3+
xp e
E
(1) Al < Ba < Na (2) Na < Ba < Al
2+
(3) Ba < Na < Al + 3+ 3+ +
(4) Al < Na < Ba
s t
2+
r y
ts m i
e r C e
h acid solution (0.06N) in a flask.
10.
x
3 gram of activated charocoal p
E and the strength of the fitrate was found to be 0.042 N. The amount
was added to 50 mL of acetic

s ry
tadsorbed (per gram of charcoal) is :
After an hour it was filtered

m i
e
of acetic
C(1)h18 mg
acid
(2) 36 mg (3) 42 mg
[JEE(Main)-2015]
(4) 54 mg
274
 Surface Chemistry
11. Match the catalysts to the correct processes : [JEE(Main)-2015]

s s
Catalyst Process

er t e r t
(A) TiCl
Exp 3 (i) Wacker process
E xp
(B) PdCl
s try 2
r y
(ii) Ziegler - Natta polymerization
s tprocess
m i
(C) CuCl
m i
(iii) Contact
e e
2

Ch (D) V O 2 5
Ch(iv) Deacon's process
(1) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i) (2) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
(3) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i) (4) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv)

ts
12. The following statements relate to the adsorption of gases on a solid surface. Identify the
e r
xpin surface energy appears as heat rts
incorrect statement among them : [JEE(Main)-2015]

y E e
tradsorption p
(1) On adsorption decrease

m i s E x
e y
(2) Enthalpy of is negative

C(3)hOn adsorption, the residual forces onm r

ist are increased
the surface
(4) Entropy of adsorption is negative e
Ch e r ts
13. Under ambient conditions, which among the following surfactants will form micelles
E xp in
aqueous solution at lowest molar concentration ?
is ry
t[JEE(Main)-2015]
h e m 

s
– –

C
+
(1) CH –(CH ) –COO Na
t
(2) CH (CH ) (CH ) Br
N
r
3 2 8 3 2 11 3 3

x p –e 
–

E
+
(3) CH –(CH ) –OSO Na
3 2 13 (4) CH (CH ) (CH ) BrN

yof log(x/m) versus log p in a Freundlich adsorption isotherm, which of the

3 3 2 15 3 3

is t r
m s [JEE(Main)-2016]
14. For a linear plot

h e
C (1) 1/n appears as the intercept e r t
xp as the slope.
following statements is correct? (k and n are constants)

E
ryk and 1/n appear in the slope term.
(2) Only 1/n appears

i s tBoth
m
(3) log (1/n) appears as the intercept. (4)

C h e ts
15. The Tyndall effect is observed only when following conditions are satisfied: [JEE-Main 2017]
p e r
E x
(a) The diameter of the dispersed particles is much smaller than the wavelength of the ligh used.

t r yalmost similar in
(b) The diameter of the dispersed particle is not much smaller than the wavelength of the light used.
s
s m
(c) The refractive indices of the dispersed phase and dispersion medium
t i are
magnitude.
(d) The refractive indicesp
r
ofethe dispersed phase andC
h e
E x dispersion medium differ greatly in
magnitude.
s
(1) (a) andi(d)
r y
t (2) (b) and (d) (3) (a) and (c)
h e m (4) (b) and (c)

C
275
 Surface Chemistry
16. Adsorption of a gas follows Freundlich adsorption isotherm. In the given plot, x is the mass of

s s
x
r t r
the gas adsorbed on mass m of the adsorbent at pressure p.
e t is proportional to
e[JEE-Main 2019]
m

Exp Exp
stry stry
mi mi
Che Che

1 1
(1) P 4 (2) P2 (3) P (4) P 2

e r ts
17.
E xpsulphide sol, which one of the following
For coagulation of arsenious
t s
r [JEE-Main 2019]
salt solution will be most

s t r y p e
x (4) NaCl
PO i
effective ?
(1) Nam (3) BaCl E
y
Che tr
(2) AlCl
s
3 4 3 2

i
mof heterogeneous catalytic reaction ?
h e
18.
C
Which of the following is not an example
e r ts
xp
(1) Ostwald's process (2) Combustion of coal [JEE-Main 2019]
E
try
(3) Hydrogenation of vegetable oils (4) Haber's process
is
m [JEE-Main 2019]
s h e
t sols, respectively C
19. Haemoglobin and gold sol are examples of :

e r
xp charged sols, respectively
(1) negatively and positively charged

y E
(2) positively and negatively
r
s t
i charged sols
(3) negatively charged sols

h m
(4)epositively
r ts
C xp e
r y E
20.
(2) Gem stone mi(3) Paint
An example of solid sol is :
s t [JEE-Main 2019]
(1) Hair cream
Ch e (4) Butter
ts
e r
p of the
21. Among the colloids cheese (C), milk (M) and smoke (S), the correct combination
E x
s t r y 2019]
i
dispersed phase and dispersion medium, respectively is :- [JEE-Main

e t s
rin liquid; S : solid in gasCh
(1) C : solid in liquid; M : liquid in liquid; S : gas in solid
e m
x p
(2) C : liquid in solid; M : liquid
(3) C : solid in liquid;E
s y M : liquid in solid; S : solid in gas
trsolid;
M : solid in liquid; S : solid in gas

m i
(4) C : liquid in

C h e
276
 Surface Chemistry
22. Given [JEE-Main 2019]
Gas H2 CH4 CO2 SO2
Critical
er ts 33 190 304 630
er ts
Exp
Temperature/K
Exp
s ry ry
On the basis of data given above, predict which of the following gases shows least adsorption
t st
mi on a definite amount of charcoal ?
mi [JEE-Main 2019]

Che (1) CO2 (2) H2

Che
(3) SO2 (4) CH4

23. The hardness of a water sample (in terms of equivalents of CaCO3) containing 10–3 M CaSO4 is:
(molar mass of CaSO4 = 136 g mol–1) [JEE-Main 2019]
(1) 50 ppm (2) 90 ppm (3) 10 ppm (4) 100 ppm

ts
24. Among the following, the false statement is : [JEE-Main 2019]

e r
(1) Latex is a colloidal solution of rubber particles which are positively charged

E xp
(2) Lyophilic sol can be coagulated by adding an electrolyte.
r t s
s tr y x p e
(3) It is possible to cause artificial rain by throwing electrified sand carrying charge opposite to

m i
the one on clouds from an aeroplane.
y E
C h e i s t r
(4) Tyndall effect can be used to distingush between a colloidal solution and a true solution.

h e m
C x ts
25. Adsorption of a gas follows Freundlich adsorption isotherm. x is the mass of the gas adsorbed
versus log p is shown in the given graph. eris
pm
x
on mass m of the adsorbent. The plot of log
m
E x
proportional to :
s t r y 2019]
[JEE-Main

m i
s C h e
e r t
E x p
s tr y
m i sp
Ch e 2 3
2
e r t 3

p
3 2
(1) p (2) p (3) p (4)

E x
t ry
is expressed in terms of equivalents of CaCO is :
26. 100 mL of a water sample contains 0.81 g of calcium bicarbonate and 0.73 g of magnesium

m
Chise162 g mol and magnesium bicarbonate
bicarbonate. The hardness of this water sample 3

ts
–1 –1

r
(molar mass of calcium bicarbonate is 146 g mol )

(4) 1000 ppm xp

e
[JEE-Main 2019]
(1) 10,000 ppm (2) 100 ppm (3) 5,000 ppm
r y E
is t10 mL of this solution
tofs water in a round watch e m Hexane evaporates and a
3

r
27. 0.27 g of a long chain fatty acid was dissolved in 100 cm of hexane.

p e
xdistance
was added dropwise to the surface C h glass.

r y E
is t
monolayer is formed. The from edge to centre of the watch glass is 10 cm. What is the

e m
height of the –3
monolayer ? [Density of fatty acid = 0.9 g cm ; =3] [JEE-Main 2019]

C(1)h10 m–2
(2) 10 m–4
(3) 10 m –8
(4) 10 m –6

277
 Surface Chemistry
28. The aerosol is a kind of colloid which: [JEE-Main 2019]

s s
(1) gas is dispersed in liquid (2) solid is dispersed in gas

e r t (4) gas is dispersed in solid ert

p xp
(3) liquid is dispersed in water
E x E
10 mLiof s s try0.24 cm on a polar substrate. If
rysurfactant solution forms a monolayericovering
t1mM
m m
2
29.

hethe polar head is approximated as cube, whathise

C (1) 0.1 nm (2) 2.0 pm
C its edge length?
(3) 1.0 pm
[JEE-Main 2019]
(4) 2.0 nm

30. A gas undergoes physical adsorption on a surface and follows the given Freundlich adsorption

ts
x
isotherm equation = kp0.5
e r [JEE-Main 2019]

xp with :
m
Adsorption of the gasE
y e r t s
trp and decrease in T
increases

i s (2) Decrease xinp

e m
(1) Decrease in
r E
y in p and increase in T
p and increase in T
h (4)tIncrease
C (3) Increase in p and decrease in T
m i s
e
Ch is : e r ts
31. The correct option among the following
p
[JEE-Main 2019]
(1) Brownian motion in colloidal solution is faster if the viscosity of the solutionE is x
ry
very high.

is tarea.
h e m
(2) Colloidal medicines are more effective because they have small surface

r ts
(3) Addition of alum to water makes it unfit for drinking.
e C
E xp
(4) Colloidal particles in lyophobic sols can be precipitated by electrophoresis.

s t r y
m i is a: s
32.
e
Peptization

Ch(1) process of converting precipitate into colloidal solutionxper t [JEE-Main 2019]

r y E
t
(2) process of converting a colloidal solution into precipitate

m issolution
he to form colloidal solution
(3) process of bringing colloidal molecule into
(4) process of converting solubleCparticles e r ts
E xp2019]
33. Among the following, the INCORRECT statement about colloids is:
s t r y
[JEE-Main

t s m i the true solution at the

e
(1) The osmotic pressure of a colloidal solution is of higher order than

p e r C h
same concentration.
x
E of colloidal particles is between 1 and 1000 nm.
t r y
(2) The range of diameters
s
i
mare larger than small molecules and have high molar mass.
e
(3) They can scatter light.

C h
(4) They
278
 Surface Chemistry
34. A mixture of gases O2, H2 and CO are taken in a dosed vessel containing charcoal. The graph

s s
that represents the correct behaviour of pressure with time is : [Jee Main (Jan. 2020)]

er t er t
Exp Exp
stry stry
i i
(1) (2)

he m h e m
C C
(3) (4)

35.
e r t s
The flocculation value of HCl for arsenic sulphide sol. is 30 m mol L–1. If H2SO4 is used for the

E x p
flocculation of arsenic sulphide,
t s
the amount, in grams, of H SO in 250 ml required for the
r
2 4

s y
trof H SO = 98g/mol)
above purpose is ___________.
x e
p [Jee Main (Jan. 2020)]
m i y E
h e
(molecular mass 2 4

CThe hardness of a water sample containing st r

i 10 M MgSO expressed as CaCO equivalents
e m –3

Ch
36.
ts
4 3

e r
xp
(in ppm) is ______.
(molar mass of MgSO is 120.37 g/mol)
4
ry
[Jee Main (Jan. E 2020)]

Which of the following is used for the preparation of colloids ? m is t

37.
s C h e [Jee Main (Jan. 2020)]
(1) Bredig’s Arc Method
e r t (2) Ostwald Process
(3) Mond Process
E x p (4) Van Arkel Method

Amongstithes ry statements regarding adsorption, those that are valid are :

tfollowing
38.
h m
(a)eH becomes less negative as adsorption proceeds. r ts (Sep) 2020]
C e
p gas.
xnitrogen
[Jee-Main
E
trtheysurface of the adsorbent increases.
(b) On a given adsorbent, ammonia is adsorbed more than

m i s
e
(c) On adsorption, the residual force acting along

C h r ts
e
(d) With increase in temperature, the equilibrium concentration of adsorbate increases.
(1) (a) and (b) (2) (c) and (d) (3) (d) and (a)
E
(4) (b) and (c)
xp
s t r y(Sep) 2020]
39. Tyndall effect is observed when:
t s m i
[Jee-Main

e e
r phase is greater thanCthathof the dispersion medium.
p
x particles is much smaller than the wavelength of light used.
(1) The refractive index of dispersed
E
trofydispersed particles is similar to the wavelength of light used.
(2) The diameter of dispersed
i s
mdiameter of dispersed particles is much larger than the wavelength of light used.
(3) The diameter

C h
(4) e
The
279
 Surface Chemistry
40. Match the following :

s s
(i) Foam (a) smoke [Jee-Main (Sep) 2020]

e r t er t
(ii) Gel
Exp
(b) cell fluid
Exp
str
(iii) Aerosol
y (c) jellies
stry
m i
(iv) emulsion (d) rubber
mi
Che (e) froth
Che
(f) milk
(1) (i)-(d); (ii)-(b); (iii)-(e); (iv)-(f) (2) (i)-(b); (ii)-(c); (iii)-(e); (iv)-(d)
(3) (i)-(d); (ii)-(b); (iii)-(a); (iv)-(e) (4) (i)-(e); (ii)-(c); (iii)-(a); (iv)-(f)

e r ts
xp
41. Indentify the correct molecular picture showing what happens at the critical micellar
concentration (CMC)E
y of an aqueous solution of a surfactant ( rpolar
e t s head ; non-polar
is tr E x p [Jee-Main (Sep) 2020]
h e m
tail ;  water).
t r y
C m i s
Ch e
e r ts
E xp
i s try
(1) (B) (2) (C) (3) (A)
h e m(4) (D)

e r t s C
E xp Freundlich adsorption isotherm. If x is the mass of the gas
rym of the adsorbent, the correct plot of x versus p is :
42. Adsorption of a gas follows

adsorbedions tmass
h e m r t s
e
m
C xp
ry E [Jee-Main (Sep) 2020]

i s t 200 K
200 K
h e m (2) x 250 K
ts
x 250 K
C
(1)
m 270 K m 270 K
e r
E xp
y
p p

i s t r
s m
270 K 270 K
x
200 Ker
250 K
t x
e
h 200 K 250 K
C
(3) (4)
m
x p m
p y E
is t r p

h e m
C
280
 Surface Chemistry
43. Kraft temperature is the temperature : [Jee-Main (Sep) 2020]

t s
(1) above which the aqueous solution of detergents starts boiling.
r
e solution of detergents starts freezing. xper ts
x p
(2) below which the aqueous
E E
r y t r y
ist is
(3) above which the formation of micelles takes place.

he(4)m
h e m
below which the formation of micelles takes place.
C C
44. For Freundlich adsorption isotherm, a plot of log (x/m) (y-axis) and log p (x-axis) gives a
straight line. The intercept and slope for the line is 0.4771 and 2, respectively. The mass of gas,
adsorbed per gram of adsorbent if the initial pressure is 0.04 atm, is _______ × 10 –4g.

e r ts
xp
(log 3 = 0.4771) [Jee-Main (Sep) 2020]

y E e r t s
tradsorbed, x, per unit mass of adsorbate,Em,xpwas measured at various pressures,
The mass ofsgas
i
m
45.

h e s t ryline with slope equal to 2 and the intercept

C p. A graph between log
x
and log p
m
gives aistraight
m
xCh
e
e r ts
xp
equal to 0.4771. The value of at a pressure of 4 atm is : (Given log 3 = 0.4771)
m
E
i s try (Sep) 2020]
[Jee-Main

h e m
e r t s C
E xp
s t ry
m i s
Ch e e r t
E xp
i s try
h e m
C e r ts
E xp
s t r y
t s m i
e r C h e
E x p
st r y
m i
C h e
281
 Surface Chemistry

EXERCISE # JEE-ADVANCED
1.
e r t s
Rate of physisorption increases with
er ts [JEE 2003]

E x p
(A) decrease in temperature
x p
E area
(B) increase in temperature

s r y
t of gases on solid surface is generally exothermic
(C) decrease in pressure
s r y
t because
(D) decrease in surface

m i m i
e
Ch (A) enthalpy is positive
2. Adsorption
e
Ch(B) entropy decreases
[JEE 2004]

(C) entropy increases (D) free energy increases

3. Lyophilic sols are [JEE 2005]

(A) Irreversible sols (B) They are prepared from inorganic compound

e r ts (D) Self-stabilizing
xp
(C) Coagulated by adding electrolytes
Among the following,Ethe
y e r t s solution at the lowest
tr at ambinent condition is :
4. surfactant that will form micelles in aqueous

is E x p
m
molar concentration [JEE 2008]

h e r
(B)tCH
s y(CH ) OSO Na
C(C) CH (CH ) COO Na i(D) CH (CH ) N (CH ) Br
+ – – +
(A) CH (CH ) N (CH ) Br
m
3 2 15 3 3 3 2 11 3
–

Ch
+
e + –

ts
3 2 6 3 2 11 3 3

e r
xp
5. Among the electrolytes Na SO , CaCl , Al (SO ) and NH Cl, the most effective coagulating
E
2 4 2 2 4 3 4

tClry
agent for Sb S sol is : [JEE 2009]
s
2 3

(D)iNH
(A) Na SO
2 4 (B) CaCl 2 (C) Al (SO ) 2

h e m
4 3 4

Silver (atomic weight = 108 g mols) has a density of 10.5C

r t –1 –3

me
6. g cm . The number of silver atoms
on a surface of area 10 xp
E
–12 2 x
can be expressed in scientific notation as y × 10 . The value of x is:

s tr y
i statement(s) pertiaining to the adsorption of a gas on a solids surface is (are)
[JEE 2010]

e m r t
Ch(A) e
7. The correct
Adsorption is always exothermic
(B) Physisorption may transform into chemisorption at E x p [JEE 2011]

tr y
(C) Physisorption increases with increasingstemperature
high temperature

m i but chemisorption decreases with

increasing temperature
h e
C than physisorption, however it is very slow eduerttos
(D) Chemisorption is more exothermic
higher energy of activation.
E x p
s tr y [JEE 2012]
i
8. Choose the correct reason(s) for the stability of the lyophobic colloidal particles.
(A) Preferential adsorption of ions onstheir surface from the solution.
m
ofe
r t e
hthe solution.
(B) Preferential adsorptionp
x C
Edifferent particles having opposite charges on their surface.
solvent on their surface from

s r y
tdifference between the fixed layer and the diffused layer of opposite charges
i
(C) Attraction between

h e m
(D) Potential
Caround the colloidal particles.
282
 Surface Chemistry
9. The given graph / data I, II, III and IV represent general trends observed for different

s s
physisorption and chemisorption processes under mild conditions of temperature and pressure.

er t er t
Exp Exp
Which of the following choice (s) about I, II, III and IV is (are) correct.
[JEE 2012]

stry stry
mi mi
Che Che
(i) (ii)

er ts
Exp r ts
stry xpe
mi y E
C
(iii)
h e i
(iv)
s t r
e m
Ch er ts
(A) I is physisorption and II is chemisorption
Exp
(B) I is physisorption and III is chemisorption
istry
(C) IV is chemisorption and II is chemisorption
hem
e r t s C
p
(D) IV is chemisorption and III is chemisorptions

Methylene blue,y
x
Eits aqueous solution, is adsorbed on activated charcoal at 25° C. For this
10.
i s r
tcorrect statement is
from

h e m
process, the
r t s
[JEE(Advanced)-2013]

C (A) The adsorption requires activation at 25°C.

xp e
r y E
s
(B) The adsorption is accompanied by a decreases in
i t enthalpy.

e m
(C) The adsorption increases with increase of temperature.
h
(D) The adsorption is irreversible.C e r ts
11. When O is adsorbed on a metallic surface, electron transfer occurs from the metal
Exp to O .
y
2 2

The TRUE statement(s) regarding this adsorption is(are)

is t r
[JEE(Advanced)-2015]
(A) O is physisorbed
e r t s e m
hof O is increased
(B) heat is released
p C
2

(C) occupancy of of O x
r y E2 is increased (D) bond length 2

i s t
h e m
C
283
 Surface Chemistry
12. The qualitative sketches I , II and III given below show the variation of surface tension with
molar concentration of three different aqueous solutions of KCl, CH3OH and CH3(CH2)11OSO3–

er ts r ts
Na+ at room temperature. The correct assignment of the sketches is –
e
[JEE. Adv. 2016]

Exp Exp
stry stry
mi mi
Che Che
(A) I : KCl II : CH3OH III : CH3(CH2)11OSO3– Na+
(B) I : CH3(CH2)11OSO3– Na+ II : CH3OH III : KCl
(C) I : KCl II : CH3(CH2)11OSO3– Na+ III : CH3OH
(D) I : CH3OH
e r tsII : KCl III : CH3(CH2)11OSO3– Na+
The correct statement(s) x
E p properties is(are) t s
rK and 126 K, respectively.
13. about [JEE. Adv. 2017]
(A) The criticalry e
s t
i of ethane will be more than thatyof Enitrogen p
x on same amount of activated
temperatures of ethane and nitrogen are 563

h m
e at a given temperature
The adsorption
t r
Ccharcoal m i s
e
hparticles does not depend on the size of the particles but
(B) Adsorption is accompanied by decrease in enthalpy and decrease in entropy of the system
(C) Brownian motion of colloidal C e r ts
depends on viscosity of the solution
E xpgas is
try
(D) Cloud is an emulsion type of colloid in which liquid is dispersed phase and
dispersion medium
is
mwhich behaves as a strong
s C
Molar conductivity (  ) of aqueous solution of sodium stearate,h e
14. m

e r t
xthep correct representation of micelle formation in the solution ?
electrolyte, is recorded at varying concentrations (C) of sodium stearate. Which one of the
E
yconcentration (CMC) is marked with an arrow in the figures) [JEE 2019]
following plots provides
r
is t
(critical micelle

e m CMC s
r t
Ch x p e
E
(A) 
CMC
i s try
m
m (B) m

C h e ts
e r
c c
E xp
s t r y
CMC
t s m i
(C) 
e r (D) 
C h e
p
m

x
m

r y E CMC

is tc c

h e m
C
284
 Surface Chemistry

ANSWER KEY

r ts EXERCISE # JEE-MAIN
r ts
2 e 3 pe
1. 2 2.
xp 3. 4 4.
x 5. 2

y E 9.y E2
6. 3
tr
is 12. 3
7. 3 8. 4
tr
is 14. 2
10. 1

m em
Che4
11. 2 13. 4 15. 2
16. 17. 2 18. Ch
2 19. 2 20. 2
21. 2 22. 2 23. 4 24. 1 25. 1
26. 1 27. 4 28. 2 29. 2 30. 3
31. 2 32. 1 33. 1 34. 4
35.
r ts
[0.37] NTA Ans. 0.36 to 0.38
36. 100 37. 1 38. 1
4 pe
39. 3 40.
E x 41. 4 42.
r
1
ts 43. 3

s y
t45.r (48) NTA Ans. (6) xp e
44. 48.00
mi y E
C h e is t r
EXERCISEe#m
Ch JEE-ADVANCED
r ts
1. A 2. B 3. D 4. A 5. e
xpB C
E
6. 7 7. ABD 8. AD 9. AC
C is
try 10.
11. BCD 12. D 13. AB 14.
h em
er ts C
Exp
stry
mi
Che er ts
Exp
istry
hem
C er ts
Exp
stry
ts mi
er Che
Exp
istry
hem
C
285
 Surface Chemistry

Hint and Solutions

e r t s EXERCISE # JEE-MAIN
e r ts
1.
x p x p
Since the physical adsorption process is exothermic, the physical adsorption occurs readily at
E E
y
low temperature and decreases with increasing temperature. (Le Chatelier’s principle).

s r y
t they will coagulate each other being +ve ands r
t– ve charged.
2.
m i
On mixing,
m i
3. he
C C h
For true solution the diameter range is 1 to 10 e
Å and for colloidal solution diameter range is 10
to 10,000 Å.
3
Vc (4 / 3)rc3  rc 
    Ratio of diameters = (10/1)3 = 103 Vc / Vs = 103.
Vs (4 / 3)rs  rs 
3

ts
5. The adsorption of a gas is directly proportional to the pressure of gas.

e r
xp
6. CO is oxidised to CO2 with steam in the presence of a catalyst followed by absorption of CO 2
in alkali.
y E e r ts
is tr
CO + H2 Steam
 CO2 + 2H2 
KOH
 K2CO3
E xp
e m y
catalyst

h adsorption is exothermic process so Hsoftr

7.
C Since
m i 
adsorption is always negative.

Ch e
8.
x
 P where n 1
1/ n

e r ts
xppower
m
E
for negatively charged solution. So, order of coagulating power : Na < Batr<yAl .
9. According to Hardy Schulze rule, greater the charge on cation, greater is its coagulating
is
+ 2+ 3+

h e m
10.
=r t s
Initial mmoles of CH COOH = 0.06 × 50
Final mmoles of CH COOHe
3
C
Hence, mass of CH COOH
E
3
p 0.042 × 50
x adsorbed per gram of charcoal
y× 50 ×10 × 60 ×10 = 18 mg
3

i s tr
(0.06 - 0.042) -3 3

m
=

h e 3
e r t s
11. C TiCl xp

Ziegler-Natta polymerisation
E
try
3
PdCl 
Wacker process
i s
2
2 
m
CuCl Deacon's process
VO 2 5 
Contact process
C h e ts
er
12.
xp
Adsorption takes place due to the presence of residual forces on the surface. After adsorption,
E
these are decreased.
st r y
t s m i
13.
r isotherm Ch
Longer hydrophobic chain, lesser CMC
e e
14.
E x
According to the Freundlich padsorption
x
= kP
is try
1/n
m
h e m
C
286
 Surface Chemistry
x x
log = logK + logP
m m

e r ts er ts
34. (4)
E x p Exp
s r y
t Ans. 0.36 to 0.38 stry
35.
i
[0.37] NTA
m of H needed for flocculation of 1L solution i
m= 30 mmole
Sol. e
C h Moles +

C30h e
Moles of H+ needed for 250 ml solution = = 7.5 mmole
4
7.5
Moles of H2SO4 needed = mmole
2
7.5
ts
Weight of H2SO4 = × 98 × 10–3 gm
e
2
r
E xp= 0.3675 gm
r ts
str y xpe
i
36. (100)

e
–3
m to 10 M CaCO
Sol. 10 M MgSO
r y E
h t
4

CEquivalent –3
3
m is
10 100e
C1000h 10 = 100 pm
–3
 cons. of CaCO in ppm =
ts
6

er
3

Exp
try
37. (1)
Sol. Bredig's arc method is used for preparation of colloids.
mis
s Che
38. (1)
er t
Sol.
xp
(a) as adsorption proceeds, extent of adsorption decreases
E
stry
So H becomes less negative

mi
(b) (TC) NH3 > (TC) N2

Che So adsorption of NH3 is more than N2

er ts
xp
(c) as adsorption forces along adsorbent surface decreases.
E
try
(d) On increasing temperature extent of adsorption decreases.
39. (3)
mis
Sol.
he ts
Tyndall effect is observed when the diameter of dispersed particles is similar to the wavelength
C
of light used.
er
40. (4)
Exp
Sol. Foam - Froth
stry
Gel  Jellies
ts mi
er
Aerosol  Smoke
Che
Exp
Sol  Cell fluids

stry
Solid sol  rubber
i
41.
hem
(4)
Sol.
C Polar ends interacts with water where as non polar ends moves away from water.
287
 Surface Chemistry
42. (1)
x
Sol.
m
= k P1/n
er ts er ts
x
 as T  xp
E Exp
m
s ry
tcurve is (1) stry
m i mi
43. he e
So correct

C (3)
Ch
Sol. (i) Micelles formation take place only above a particular temperature called as kraft
temperature (Tk)
(ii) Concentration above which micelle formation become appreciable is critical micells
concentration.
44. (48.00)
er ts
Sol.
x 1
 KP n
E xp r ts
m
str y xpe
x 1
m i y E
h e
log    log P + log K
m n
Cslope 1 = 2 istr
h e m
n C er ts
intercept = log K = 0.4771
Exp
try
K=3

mass of gas adsorbed per gm of adsorbent –

x
mis
s
m
Che
x
er t
m
Exp
= 3 × (0.04)2 = 48 × 10–4

45.
try
(48) NTA Ans. (6)
s
mi
ts
x
e
1
 KP n
Sol.
Ch er
xp
m
x 1
log   = log K + log P
ry E
m n
ist
In the curve of log   VS log P em
x
m C h r ts
xpe
E
1
y
Slope = =2
n
istr
ts m
Intercept = log K = 0.4771

er Che
xp
K=3
at
E
P = 4 atm

istryx
= KP n
1

hem m

C = 3 × (4)2 = 48

288
 Surface Chemistry

EXERCISE # JEE-ADVANCED
1.
e r ts e r ts
Physical adsorption is exothermic process so its rate decreases with increase in temperature.

x p x p
Ein bond formation between the gases andrysolidEsurface which decreases the
2.
r y
In adsorption there
entropyis st be negative.
sotto make it spontaneous the enthalpy changeimust
he m h e m
C
3. C
In lyophilic sols the dispersed phase have great affnity (attraction) towards dispersion medium.
So they are self stabilizing.

4. Longer the hydrophobic part of the molecule easy will be the formation of micelle. (Longest

ts
hydrocarbon chain)
e r
E xpagent for Sb S is Al (SO ) because ofrhigh t s
try e
5. Most effective coagulating 2 3 2 4 3 charge.

is E x p
e m r y
Ch 10.5 ist
108 3
6. Volume of one mole of silver atoms = cm /mole

volume of one silver atom = Ch

em1 cm
ts
108
r
3
×
10.5 6.022 10 23

p e
[neglecting the void space] Ex
ry
4 108 3 1 –23
so, R =  × = 1.708 × 10
3 10.5 6.022 10 23

is t
3
R = 0.407 × 10 cm –23 3

h e m
3
R = 0.407 × 10 m –29 3

e r t s C
Area of each silver atom
E xmp)
y
–29

r
2 3 2/3
 
t
R = × (0.407 × 10

m s
i of silver atoms in given area. = 10 12

s
10 8

e r t
7 x

Chx = 7
so, number = = 1.6 × 10 = y × 10
e
29
 
3 2/3

p
(0.407 10 m ) ( 2)

E x
r y
m ist
Che
7. (A) H = –ve for adsorption

(B) fact
e r ts
(D) chemical bonds are stronger than vander waal’s forces so chemical adsorptionpis more
E x
exothermic.
s tr y
tscommon ions m i
e r C h e
xduepto attraction
8. (A) due to preferential adsorption of
E
ryoppositely charged particles around any colloidal particles will decrease the
(C) due to repulsion not
(D) The layertof
is
menergy of system as a whole.
C h e
potential

289
 Surface Chemistry
9. In physisorption on increasing temperature at constant pressure, adsorption decreases while in

s s
chemical adsorption on increasing temperature due to requirement of activation energy

e r t e r t
E x p E x p
adsorption will increase at same pressure. So, I is physisorption while II is chemisorption.

s y
tr enthalpy change (which is high) during
III is physical adsorption as on increasing temperature,
y
trchemical adsorption (due to bond
extent
s
of adsorption is decreasing .

m i
IV is representing
m i
Che C h
formation) So, is valid for chemical adsorption.eSo, answer is (A) and (C)

10. As the adsorption of methylene blue over activated characoal is physisorption (Reference :
NCERT), it is accompanied by decrease in enthalpy.

e r ts
xpprocess.
11. (A) As electron transfer is involved, so chemisorption is taking place.

y E er t s
tr of O accomodate the incoming electron pas they are partially filled.
(B) Adsorption is exothermic
(C) The *isorbitals E x
h e m  2p 2

t r yincreases.
As electron enters antibonding MO, bondslength
C (D)
m i
Ch e
ts
So, answer is (B,C,D

er
E xp
i s try
h e m
e r ts C
E xp
s tr y
m i s
Ch e e r t
E xp
i stry
h e m
C er ts
E xp
s t r y
ts m i
e r C h e
E x p
s t ry
m i
C h e
290