Contents

CHEMISTRY
Chpater
No. UNIT - NPC2 Page No.

3. GASEOUS STATE 1
1.0 INTROUDCTION
2.0 MEASURABLE PROPERTIES OF GASES
3.0 GAS LAWS
4.0 THE IDEAL GAS EQUATION
5.0 DALTON'S LAW OF PARTIAL PRESSURES
6.0 GRAHAM'S LAW OF DIFFUSION AND EFFUSION
7.0 KINETIC THEORY OF GASES
8.0 REAL GAS
9.0 LIQUEFACTION OF GASES AND CRITICAL POINTS
EXERCISE-1
EXERCISE-2
NCERT CORNER
ANSWER KEY

4. REDOX 66
1.0 OXIDATION & REDUCTION
2.0 REDOX REACTION
3.0 EQUIVALENT WEIGHT (E)
4.0 NORMALITY
5.0 LAW OF EQUIVALENCE
6.0 APPLICATIONS OF THE LAW OF EQUIVALENCE
7.0 HYDROGEN PEROXIDE (H2O2)
8.0 HARDNESS OF WATER
9.0 STRENGTH OF OLEUM
10.0 CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF
BLEACHING POWDER
EXERCISE-1
EXERCISE-2
NCERT CORNER
ANSWER KEY
 Gaseous State

GASEOUS STATE

1.0 INTRODUCTION
Matter is made up of atoms or molecules. The arrangement of these molecules determines the state of matter.
There are three recognised state of matter : Solid, Liquid and Gas. Matter can change between states when the
temperature or pressure is changed. State changes of matter are physical rather than chemical.

1. 1 Difference between states of matter

Gas Liquid Solid

(i) Assumes the shape and volume Assumes the shape of the Retains a fixed volume and
of its container. part of the container which shape.
it occupies

(ii) Particles can move past one Particles can move/slide past Rigid-particles locked into
another. one another. place.

(iii) Compressible, lots of free space Not easily compressible, little Not easily compressible, little
between particles space. free space between particles. free space between particles.

(iv) Flows easily, particles can move Flows easily, particles can Does not flow easily, rigid-
past one another. move/slide past one another. particles cannot move/slide
one past another

(v) Low density. Intermediate density. High density.

(vi) Very small intermolecular Considerable intermolecular Intermolecular forces are high,
attraction but high kinetic force and kinetic energy. vibrational motion only.
energy.

2.0 MEASURABLE PROPERTIES OF GASES

2.1 Mass
The gases do possess mass. The mass of gas is generally used in the form of number of moles which is
related as
wt. in gm  w
(i) no. of moles = molecular mass of gases n  
 M
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Two other useful formulae to calculate number of moles of gas are –

no. of molecules of given gas  N 

(ii) number of moles = Avogadro ' s number of molecules n  
 NA 

volume of given gas in litres at STP

(iii) no. of moles = 22.4 L
When container contains more than one gas then molecular mass of mixture is termed as effective
molecular mass (EMM) which is intermediate between molecular masses of all the gases present in the
container.

Total mass of all the gases present in the container

Effective molecular mass = Total no. of moles of all gases present in the container

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2.2 Volume
Volume of gas is nothing but volume of the container in which it is present.
Relation between different units of volume
1 m3 = 103 dm3 = 103 litre =10 6 cm3 = 106 ml = 109 mm3.

2.3 Temperature
Degree of hotness or coldness of a body is measured by temperature

C K  273 F  32
100 = 100 =
180
C – Celcius scale, K – Kelvin scale, F – Fahrenheit scale

Note : In all the problems of gaseous state (i.e. in all gas law equations), temperature must be
expressed in kelvin scale. i.e. , t °C + 273 = TK

2.4 Pressure
Force acting per unit area

P=
F
A
Units:
CGS : dyne/cm2
MKS : Newton/m2 (1N/m2 = 1Pa)
Relation : 1 N/m2 = 10 dyne/cm2

Units of pressure:
1 atm = 76 cm of Hg
= 760 mm of Hg
= 760 torr
= 1.01325×105 N/m2
= 101.325 kPa
= 1.01325 bar
= 14.7 lb/In 2 (Psi)
= 10.33 meters of H 2O
Pressure due to fluid column = hdg
h = height of fluid column
d = density of fluid
g = acceleration due to gravity
2.5 Density
Mass per unit volume
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d= v
m
Units
CGS : g/cm3
MKS : kg/m3
Relation : 1 kg/m 3 = 10 –3 g/cm3

Illustration 1. Calculate the mass of mercury in a uniform column 760 mm high and 1.00 cm2 in cross-sectional
area. Is there any change in.
(a) mass and
(b) pressure of column of same height but with 2.00cm2 cross sectional area is taken ?
(density of Hg = 13.6 g/cm3)
Solution. 760 mm = 76 cm
 V = 76 × 1 = 76 cm3

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 Mass = V × d = 76 × 13.6 = 1033.6 g

(a) If area of cross-section is 2cm2 (doubled) then volume is also doubled hence,
 Mass = 76 × 2 × 13.6 = 2067.2 g
(b) This mass would rest on twice the area and so exert the same pressure.

Ah dg
 Barometer : P= where d = density of fluid
A
h = vertical height
g = acceleration due to gravity

 Manometer : Pgas = Patm + hdg

1. How high a column of air would be necessary to cause the barometer to read 76 cm of Hg, if the
atmosphere were of uniform density 1.2 kg/m 3? The density of Hg = 13.6 × 10 3 Kg/m3.
(A) 8613 meters (B) 8613 centimeter (C) 8.613 meter (D) 8613 mm
2. How much pressure will be felt by a gas balloon which is at 100 m depth in a sea from sea level.
(atmospheric pressure = 1 × 10 5 Pa, g = 9.8 m/s 2)
(A) 100 Pa (B) 98 Pa (C) 9.8 × 10 5 Pa (D) 1.08 × 10 6 Pa
3. Calculate the pressure of the gas in cm of Hg in given case (liquid used is Hg)

(A) 20 cm of Hg (B) 10 cm of Hg
(C) 30 cm of Hg (D) 86 cm of Hg
4. Calculate the pressure of the gas in cm of Hg in given case (liquid used is Hg)
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(A) 20 cm of Hg (B) 10 cm of Hg (C) 66 cm of Hg (D) 86 cm of Hg

5. A beaker of circular cross section radius 4 cm is filled with Hg upto height 10 cm. The force exerted by the
mercury on the bottom of the beaker will be : (The density of Hg = 13.6 × 10 3 Kg/m3 , g = 9.8 m/s 2)
(A) 67 N (B) 60 N (C) 33.5 N (D) None of these
6. In given example the pressure of the trapped gas will be :

Pgas

Hg 10 cm

P0 = 75 cm of Hg

(A) 85 cm of Hg (B) 65 cm of Hg (C) 75 cm of Hg (D) None of these

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3.0 GAS LAWS

The gas laws are a set of laws that describe the relationship between thermodynamic temperature (T), pressure
(P) and volume (V) of gases.
3.1 Boyle's law
It states "at a constant temperature (T), the pressure (P) of a given mass (or moles, n) of any gas varies
inversely with the volume (V)".
1
i.e. P  (for given n and T)
V
or, PV = K = constant
For two or more gases at constant temperature
P1V1 = P2V2 = ..... = K
1
Also, density d 
V
Hence P  d
P1 P2
or d  d = ......... = K
1 2

 Graphical representation
T2 > T1

V V
T2 PV
T1
1/ P P P

log P log P

log V log 1/ V

These plots drawn at constant temperature for a gas are called Isotherms.

Illustration 2. The diameters of a bubble at the surface of a lake is 4 mm and at the bottom of the lake is 1
mm. If atmospheric pressure is 1 atm and the temperature of the lake-water and the atmosphere
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are equal, what is the depth of the lake ? (The density of lake-water and Hg are 1 gm/ml and
13.6 gm/ml respectively. Also neglect the contribution of pressure due to surface tension).
Solution. The pressure on the bubble= 1 atm (when it is at the surface)
The pressure on the bubble= P atm (say) (when it is at the bottom)
1
The volume of the bubble=  (0.1)3
6

1 1
P ×  × (0.1)3 = 1 ×  (0.4)3
6 6
or P = 64 atm.
Thus the pressure due to water is 63 atm ( atmospheric pressure = 1 atm)
Now, consider the depth of lake is h cm
 63 × 76 × 13.6 × g = h × 1 × g
or h = 63 × 76 × 13.6 cm = 65116.8 cm.

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 Gaseous State
Illustration 3. A 10 cm volume of air is trapped by a column of Hg, 8 cm long in capillary tube horizontally
fixed as shown below at 1 atm pressure. Calculate the length of air column when the tube is
fixed at same temperature.
(a) Vertically with open end up

(b) Vertically with open end down 10cm 8cm

(fig. 1)
(c) At 45ºC from with open end up

Solution. (a) When the capillary tube is held as vertically open end up (fig.2), The pressure on the air
column = atmospheric pressure + pressure of 8 cm Hg column

8cm

(fig. 2)
= 76 + 8 = 84 cm of Hg.
Let, at this condition the length of the air column = 2
and the length of air column when capillary is horizontally fixed
= 1 = 10 cm and pressure on air column = 1atm.
Let the cross section of the capillary = a cm2
 76 × 10 × a = 84 × 2 × a
76  10
or 2 = = 9.04 cm
84
(b) When the capillary tube is held as vertically open end down (fig.3), the pressure
on the air column
= atmospheric pressure – pressure of 8 cm Hg column
= 76 – 8 = 68 cm of Hg.
Let at this condition the length of air column = 3.
68 × 3 × a = 76 × 10 × a
76  10 8cm
or3 = = 11.17 cm
68

(fig. 3)

(c) When the capillary is held at 45º with open end up, the weight of Hg is partially borne by,
the gas and partially by the Hg. The pressure on the gas due to Hg column
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= 8 × cos 45º
1 8
= 8 × = = cm of Hg
2 2
m
8c

•
º
45

 8 
 total pressure on the gas =  76   cm of Hg.
4

2



Let length of air column at this pressure = 4.
 8  (fig. 4)
 4 × a ×  76   = 10 × a × 76
 2

 10  76 
   4 =   = 9.3 cm
 76  8 2 

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3.2. Charles' law
1
It states "at constant pressure, the volume of a given mass of a gas, increases or decreases by th of its
273.15
volume at 0ºC for every rise or fall of one degree in temperature".
Vt 1
V0 = 1 + 273.15 t (at constant n and P)

 t 
or Vt = V0  1  
 273.15 

V0 (273.15  t)
or Vt =
273.15
0ºC on the Celsius scale is equal to 273.15 K at the Kelvin or absolute scale. i.e. Tt (Temperature in
Kelvin scale) = 273.15 + t
Vt T
 From the above equation we get  t
V0 T0

Vt V0
or 
Tt T0
i.e. The volume of a given gas is proportional to the absolute temperature.
V1 V 2

T1 T2 (at constant P)

 Graphical representation

V
V log V
22.4 L mol–1 =V 0
0 T (K) –273.15º 0 t(ºC) 0 log T

Graphs between V and T at constant pressure are called Isobars.

3.3 Gay-Lussac's law : Dependence of Pressure on Temperature

It states "at constant volume, the pressure of a given mass of a gas is directly proportional to the absolute
temperature of the gas".
P  T or P = KT
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P1 P2
or T  T
1 2

 Graphical representation

V1
V2
P
P

P0

T T
The plots drawn at constant volume for a gas is called as Isochore.

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 Gaseous State

Illustration 4. An iron tank contains helium at a pressure of 3.0 atm at 27ºC. The tank can withstand a
maximum pressure of 10 atm. The building in which tank has been placed catches fire predict
whether the tank will blow up first or melt. (melting point of iron is 1535ºC)
Solution. P1 = 3.0, T1 = 300 K
P1 P2 3.0 P
   2
T1 T2 300 1808

3.0  1808
P2 = = 18.08 atm
300
Since at melting point it is greater than the maximum pressure, therefore it will blow up.

3.4 Avogadro's Law

It states "equal volumes of any two gases at the same temperature and pressure contain the same number of
molecules".
V  n(At constant P and T)
V1 V2
or, n  n
1 2

3. 5 The combined gas Law

It states "for a fixed mass of gas, the volume is directly proportional to absolute temperature and inversely
proportional to the pressure".
1
Boyle's Law, V  (at constant n, T)
P
Charle's Law, V  T (at constant n, P)

T T PV P1 V1 P2 V2
Therefore, V  or V=K or K or 
P P T T1 T2

1
 Boyle's law V   T , cons tan t P1 V1 = P2 V2
P n cons tan t
graphs are Isotherms
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V1 V
 Charle's law V  T P , cons tan t  T1
= T2
n cons tan t 2
graphs are Isobars

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P1 P
 Gay Lussac's law P  T V , cons tan t  T1
= T2
n cons tan t 2
graphs are Isochor

V V
 Avogadro's law V  n ( T , P constant ) n1 = n 2
1 2

log V 45°
log RT/ P

log n

P1V1 P2 V2
Combined Gas Law :

T1 = T2
 Volume coefficient (v) of a gas
The ratio of increase in volume of a gas at constant pressure per degree rise of temperature to its volume at 0ºC
is the volume coefficient of the gas.
Vt – V0
v = V  t or Vt = V0 (1 + vt)
0

1
For all gases, v =
273

 Pressure coefficient (p) of a gas

The ratio of increase in pressure of the gas at constant volume per degree rise of temperature to its pressure at
0ºC is the pressure coefficient of the gas.
Pt  P0
p = or Pt = P0 (1 + pt)
P0  t

1
For all gases, p =
273
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1. A sample of gas at room temperature is placed in an evacuated bulb of volume 0.51 dm 3 and is found to
exert a pressure of 0.24 atm. The bulb is connected to another evacuated bulb whose volume is 0.63 dm3.
The new pressure of the gas at room temperature will be :
(A) 1.073 atm (B) 1.1073 atm (C) 2.1073 atm (D) 0.1073 atm
2. Volume of a cylinder containing 10 marbles and gas is 1 litre at 2 atm pressure. Now pressure on the
cylinder is increased to 4 atm, at which volume becomes 725 ml. Volume of each marble is
(A) 50 c c (B) 45 c c (C) 60 c c (D) 65 c c
3. A gas occupied a volume of 250 ml at 700 mm Hg pressure and 25°C. What additional pressure is required to
reduce the gas volume to its 4/5th value at the same temperature ?
(A) 225 mm Hg (B) 175 mm Hg (C) 150 mm Hg (D) 265 mm Hg
4. How much should the pressure be increased in order to decrease the volume of a gas by 5% at a constant
temperature ?
(A) 5% (B) 5.26 % (C) 10% (D) 4.26 %

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5. Two glass bulbs A and B are connected by a very small tube having a stop-cock. Bulb A has a volume
of 100 cm3 and contained the gas while bulb B was empty. On opening the stop-clock, the pressure fell
down to 40%. The volume of the bulb B must be
(A) 75 cm3 (B) 125 cm3 (C) 150 cm3 (D) 250 cm3
6. A balloon blown up with 1 mole of gas has a volume of 480 mL at 5ºC. The balloon is filled to (7/8)th of
its maximum capacity then select the correct options :
(A) the balloon will burst at 30ºC.
(B) The minimum temperature at which it burst will be 44.67 ºC.
(C) The minimum temperature at which it burst will be 40.67 ºC.
(D) none of these
7. When the temperature of 23 ml. of dry CO2 gas is changed from 10° to 30°C at constant pressure of 760 mm,
the volume of gas becomes closest to which one of the following ?
(A) 7.7 ml (B) 21.5 ml (C) 24.6 ml (D) 69 ml
8. Here are some plots for a fixed mass of ideal gas:

P1
P2
P3
Volume

Temperature (K)

The correct relationship for pressures P1, P2, P3 is :

(A) P1  P2  P3 (B) P2  P1  P3 (C) P3 > P1 > P2 (D) P3  P2  P1

9. Volume of the air that will be expelled from a vessel of 300 cm 3 when it is heated from 27°C to 37°C at the
same pressure will be :
(A) 310 cm3 (B) 290 cm3 (C) 10 cm3 (D) 37 cm3
10. Which one of the following V, T plots represents the behaviour of one mole of an ideal gas at one atm ?

(A) (B) (C) (D)

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11. A gas cylinder containing cooking gas can withstand a pressure of 14.9 atmosphere. The pressure gauge of
the cylinder indicates 12 atmosphere at 27ºC. Due to a sudden fire in the building the temperature starts
rising. The temperature at which the cylinder will explode :
(A) 1100 C (B) 90 0 C (C) 99.5 0 C (D) None of these
12. A faulty barometer reads a pressure of 750 mm Hg when the actual pressure is 760 mm Hg. The evacuated
part of the barometer is 20.0 mm long. Calculate the actual pressure when the barometer reads 730 mm?
(A) 740 mm Hg (B) 745 mm Hg (C) 735 mm Hg (D) Data is insufficient
13. A chamber of constant volume contains hydrogen gas. When the chamber is immersed in a bath of
melting ice (0ºC) the pressure of the gas is 800 torr. What pressure will be indicated when the chamber is
brought to 100ºC ?
(A) 1193 torr (B) 790 torr (C) 1000 torr (D) 1093 torr

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14. At similar conditions of temperature and pressure three gases He, N 2 and O 2 have same volume. The
correct option regarding their number of atoms will be :
(A) O 2 > N2 > He (B) He > N 2 > O 2 (C) He = N2 = O 2 (D) He < N2 = O 2
15. Calculate volume occupied by 8.8 g CO 2 gas, if 5.6 g CO gas occupies 6.24 L at same temperature and
pressure.
(A) 22.4 L (B) 1.12 L (C) 4.48 L (D) 6.24 L
16. 3.01 × 10 23 molecules of He(g) occupies 10 L at given temperature and pressure. Then volume occupied
by mixture of 0.5gm H 2(g) and 14 gm of N 2(g) (non reacting gases.) will be
(A) 5 L (B) 15 L (C) 2.5 L (D) 20 L

4.0 THE IDEAL GAS EQUATION

An ideal gas is defined to be a system in which there are no inter molecular/interatomic forces. Such a system
can only exist as a gas. Any real system will approach ideal gas behaviour in the limit that the pressure is
extremely low and the temperature is high enough to overcome attractive intermolecular forces.
An ideal gas is a gas to go which the laws of Boyle and Charles are strictly applicable under all conditions of
temperatures and pressures.
From Boyle's law we get,
V  1/P (at constant n and T)
From charles law we get,
V  T (at constant n and P)
From Avogadro's law we get,
V  n (at constant T and P)
Combining the above three equations we get

nT nT
V  or V = R [Where R = ideal gas constant]
P P

or PV = nRT
Ideal gas equation is a relation between four variables and it describes the state of any gas. For this reason, it
is also called Equation of State.

 Dimension of R
PV Pressure  Volume
R= 
nT Mole  Temperature

(Force / Area)  (Area  Length)

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=
Mole  Degree(K)

Force  Length Work or energy

= =
Mole  Degree(K) Mole  Degree (K)

 Physical significance of R
The dimensions of R are energy per mole per kelvin and hence it represents the amount of work (or energy) that
can be obtained from one mole of a gas when its temperature is raised by 1K.

 Units of R
1 atm  22.4 lit
(i) In lit-atm R = = 0.0821 lit-atm mol–1K–1
273 K

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 Gaseous State

1  76  13.6  980 dynecm 2  22400 cm 3

(ii) In C.G.S system R =
273 K
= 8.314 × 107 erg mole–1K–1.

(iii) In M.K.S. systemR = 8.314 Joule mole–1K–1. [107 erg = 1 joule]

8.314  10 7 ergmole1 K –1
(iv) In calories R =
4.184  10 7 erg
= 1.987  2 calorie mol–1K–1.

Illustration 5. At room temperature following reaction goes to completion

2NO + O2  2NO2  N2O4
Dimer N2O4 at 262 K is solid. A 250 ml flask and a 100 ml flask are separated by a stop cock.
At 300 K, the nitric oxide in the large flask exerts a pressure of 1.053 atm and the smaller on
contains O2 at 0.789 atm. The gases are mixed by opening the stop cock and after the end of
the reaction, the flasks are cooled to 220 K. Neglecting the vapour pressure of dimer. Find out
the pressure and composition of gas remaining at 220 K (Assume gases behave ideally).
Solution. For NO gas :-
PV 1.053  250
nNO = = = 1.069 × 10–2
RT 0.0821  300  1000
0.789  100
For O2 gas :- n O2 = = 0.32 × 10–2
0.0821  300  1000

Now, 2NO + O2  N2O4

Mole before reaction (1.069×10 ) (0.32×10–2)
–2 0
Mole after reaction 0.429×10–2 0 0.32 × 10–2
Moles of NO left = 4.29 × 10–3
PNO × V = nRT Given T = 220 K
250  100 350
V = = litre
1000 1000
350
PNO × = 4.29 × 10–3 × 0.821 × 220
1000
PNO (left) = 0.221 atm.
Illustration 6. An open vessel at 27ºC is heated until 3/5th of the air in it has been expelled. Assuming that the
volume of the vessel remains constant. Find
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(a) the temperature at which vessel was heated ?

(b) the air escaped out if vessel is heated to 900 K ?
(c) temperature at which half of the air escapes out ?
Solution. One should clearly note the fact that on heating a gas in a vessel there are the number of moles of
gas which go out, the volume of vessel remains constant.
Let initial moles of air at 300 K be 'n'. On heating 3/5 moles of air are escaped out at
temperature T.

 3  2n
Moles of air left at temperature T =  n  n  =
 5  5
(a) Under simillar conditions of P and V
n1T1 = n2T2
2n
n × 300= × T  T = 750 K
5

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(b) On heating vessel to 900 K, let n1 moles be left again n1T1 = n2T2
1
n1×900 = 300 × n  n1 = n
3

n 2
 moles escaped out = n –  n moles
3 3
(c) Let n/2 moles are escaped out at temperature T then
n1T1 = n2T2
n/2 × T = n × 300
T= 600 K

 Equation Of State : P V = n R T
 w
P V = M RT R = Universal Gas constant = 0.0821 atm litres kelvin–1 mol–1
 PM = dRT = 8.314 joule / kelvin = 2cal kelvin–1 mol–1

d = density of gas

1. A container has SO 2 gas at 2 atm pressure in a vessel of V L capacity, if no. of moles of SO 2 are doubled
in the same container at same temperature and volume. Calculate new pressure in the container.
(A) 1 atm (B) 4 atm (C) 2 atm (D) 8 atm
2. An electronic vacuum tube was sealed off during an experiment at a pressure of 8.2 × 10–10 atm at 27°C. The
volume of the tube was 30 dm3. The number of gas molecules remaining in the tube are :
(A) 6.02 × 1014 (B) 8.2 × 6.02 × 1023 (C) 24.6 × 106 (D) 8.2 × 30 × 6.02 × 1023
3. 4.0 g of argon (at mass = 40) in a bulb at a temperature of T K had a pressure P atm. When the bulb was
placed in hotter bath at a temperature 50° more than the first one, 0.8 g of gas had to be removed to get
the original pressure. T is equal to :
(A) 510 K (B) 200 K (C) 100 K (D) 73 K
4. Nitrogen forms several gaseous oxides. One of them has a density of 1.33 g/L measured at 764 mmHg and
150°C. Write the formula of the compound.
(A) NO (B)N2O (C)NO2 (D) N2O5
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

5. Starting out on a trip into the mountains, you inflate the tires on your automobile to a recommended pressure
of 3.21 × 105 Pa on a day when the temperature is –5.0°C. You drive to the beach, where the temperature is
28.0°C. Assume that the volume of the tire has increased by 3%. What is the final pressure in the tires?
(A) 350 Pa (B) 3500 Pa (C) 3.5 × 105 Pa (D) None of these
6. In a container m g of a gas is placed. After some time some gas is allowed to escape from container. The
pressure of the gas becomes half and its absolute temperature 2/3 rd. The amount of gas escaped is

2 1 1 1
(A) m (B) m (C) m (D) m
3 2 4 6
7. A 0.5 dm3 flask contains gas A and 1 dm3 flask contains gas B at the same temperature. If density of
1
A = 3.0 g dm–3 and that of B = 1.5 g dm–3 and the molar mass of A = of B, then the ratio of pressures
2
exerted by gases is :
(A) PA / PB = 2 (B) PA / PB = 1 (C) PA / PB = 4 (D) PA / PB = 3

12
 Gaseous State

8. An open container of volume 3 litre contains air at 1 atmospheric pressure. The container is heated from
initial temperature 27°C or 300 K to t°C or (t + 273) K. The amount of the gas expelled from the
container measure 1.45 litre at 17°C and 1 atm. Find temperature t. (in °C)

(A) t = 327°C (B) t = 300°C (C) t = 313°C (D) None of these

9. A vessel contains 1.7 g NH3 gas and 5.1 g H2S gas. The value of effective molar mass of this gaseous mixture at
27oC will be

(A) 34 (B) 27.2 (C) 25.5 (D) 68

10. A mixture of Ar (40) and N2 gases has a density of 1.40 g L–1 at N.T.P. Hence, mole fraction of N2 approximately
in the mixture is :

(A) 0.3 (B) 0.7 (C) 0.4 (D) 0.5

5.0 DALTON'S LAW OF PARTIAL PRESSURES

Dalton's law of partial pressure states "at a given temperature, the total pressure exerted by two or more non-
acting gases occupying a definite volume is equal to the sum of the partial pressures of the component gases."
PTotal = p1 + p2 + p3 + ...... (At constant V and T)
 n1 n2 n3  RT nRT
=     .....  RT = (n1 + n2 + n3 + ......) 
V V V  V V
Where n = n1 + n2 + n3 + ...... = Total moles, V = Total volume
RT
PTotal = p i 
V
 ni
Dalton's law of partial pressure is applicable only to non-reacting gases.
If the two non-reacting gases A and B having nA and nB number of moles respectively are filled in a vessels of
volume V at temperature T, Then
PV = (nA + nB) RT ....(i)
Partial pressure may be calculated as
pAV = nART, pBV = nBRT
Total pressure (pA + pB) V = (nA + nB)RT .....(ii)
from (i) and (ii)
P = pA + pB
pA n A RT / V nA
 = = xA (mole fraction of A)
P (n A  n B )RT / V n A  nB
pA = xA × P, similarly pB = xB × P
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

Partial pressure of a component = Mole fraction × total pressure.

It has been observed that gases are generally collected over water and therefore are moist.
Pdry gas = P moist gas – Pwater vapour

Moist
(Gas + water vapour)

The pressure exerted by water vapour is constant with water at a particular temperature is called as aqueous
tension, which varies directly with the temperature and becomes 760 mm at 100ºC.

13
JEE-Chemistr y

Partial pressureof water in air

Relative Humidity (RH) =
Vapour pressureof water
Pressure of dry gas = Pressure of moist gas – aqueous tension.

5.1 AMAGAT'S LAW OF PARTIAL VOLUME

According to this law at constant temperature and pressure, the total volume of mixture of gases which don't
react is equal to the sum of partial volumes of each component present in mixture.
VT = V1 + V2 + V3 +. . . . . . .

Partial Volume
Partial volume of any component is defined as the volume occupied by that particular component measured
under the given condition of pressure and temperature.
PV = nRT  V  n
Let us consider a three non-reacting gases A, B and C are present in a container which have no. of moles nA,nB
and nC respectively. For each gas partial volume is
 RT   RT   RT 
VA = nA  , VB = n B   and VC = n C  
 P   P   P 

Total volume
 RT   RT 
VT =VA + VB + VC = (nA + nA +nA)   = nT  
 P   P 

Illustration 7. A vessel of 2 lit capacity contains hydrogen at 380 mm pressure at 27ºC. 16gm of O2 is added
to the container then find the total pressure and partial pressure where R = 0.0821Latm
mol–1k–1.
Solution. For H2 gas :
380 1
GivenV= 2L and p H2 =  atm
760 2
p H 2 V  n H 2 RT ; 1 = n H 2 × 0.0821 × 300
10000 1
nH 2 = 
821  300 24.6
16 1
Moles of O2 = 
32 2
1 nH 2
Partial pressure of H2 gas (p H 2 )  = ×P
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

2 n H2  n o2

1
1 24.6  P
 or P = 6.65 atm
2 1 1

24.6 2
Illustration 8. 1 mole of N2 and 3 moles of H2 are mixed in 8.21 lit container at 300 K to form NH3. If
equilibrium average molecular mass was found to be 34/3 gram then find partial pressure of each
component.
Solution. N2 + 

3H2  2NH3
Initially 130
at equilibrium (1 – x) 3 (1 – x) 2x
Total moles = 1 – x + 3 – 3x + 2x = (4 – 2x) moles

14
 Gaseous State

34
Given Average molecular mass =
3
34 28(1  x)  2(3  3x)  17(2x)
=
3 (4  2x)
34
(4 – 2x) = 34  4 – 2x = 3  x = 1/2
3
So total no. of moles = 3
nRT 3  0.821  300
PV = nRT  P = = = 9 atm
V 8.21
1–x 0.5
p N2  P   9 = 1.5 atm
3 3
3 – 3x 1.5
pH 2  P   9 = 4.5 atm
3 3
1
Illustration 9. At constant temperature of 273K, Vs P are plotted for 2 ideal gases A and B as shown. Find
V
out the number of moles of gas A and B.
1
Solution. PV = nRT, P= nRT

sB
V

ga

sA
ga
1 1
= P 1
V nRT
V
Comparing by equation :
y = mx + c 45º 60º
c = 0 P

1
m = (m = tan )
nRT
1 1
tan  = nA =
nRT RT tan 
1 1
nA =  nA =
0.0821  273  tan 45 º 22.4
1 1
nB = =
RT tan 60º 22.4 3
Illustration 10. A 500 ml bulb is filled with CH4 at a pressure of 1 atm and oxygen at a pressure of 4 atm at

27ºC. The mixture is then exploded, when the reaction CH4 + 2O2  CO2 + 2H2O ()
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

occurs. Calculate the pressure if the final temperature is 27ºC. Aqueous tension at 27ºC is
26.7 mm.
Solution. Partial pressure of CH4, ( p CH 4 )= 1 atm

Partial pressure of O2, ( p O 2 ) = 4 atm

1  0.5 0.5
 moles of CH4 present, ( n CH 4 ) = =
RT RT
4  0.5 2
 moles of O2 present ( n O 2 ) = =
RT RT
CH4(g) + 2O2(g) = CO2(g) + 2H2O()
0.5 2
Initially
RT RT

15
JEE-Chemistr y

1 0.5
Finally
RT RT
2 1 1
After the reaction, moles of residual O2 = – =
RT RT RT
0.5
After the reaction, moles of CO2 produced =
RT
1.5
Hence total no. of moles of O2 and CO2 =
RT
1.5 RT
 total pressure due to O2 and CO2 = × = 3 atm
RT 0.5
 pressure exerted by the entire gaseous components
26.7
= 3 + = 3 + 0.03513 = 3.0513 atm
760

Illustration 11. A sample of butane gas C4H10 of unknown mass is contained in a vessel of unknown volume
V at 25ºC and a pressure of 760 mmHg. To this vessel 8.6787 g of neon gas is added in such
a way that no butane is lost from the vessel. The final pressure in the vessel is 1920 mm Hg
at the same temperature. Calculate the volume of the vessel and the mass of butane.
Solution. Partial pressure of C4H10 (p1) = 760 mm Hg
By Dalton's law of partial pressure, Ptotal = p1 + p2
1920 = 760 + p2 or p2 = 1160 mm Hg
p2 = x2 × ptotal
where x2 = mole fraction of Ne
p2 1160 8.6787
x2 = P = = 0.60 ; Moles of Ne = = 0.43
total 1920 20.2
n2 0.43
x2 = n  n ; 0.60 =  n1 = 0.28
1 2 0.43  n1
Molecular weight of C4H10 = 48 + 10 = 58
so, amount of C4H10 = n1 × 58 = 16.24 g
again for C4H10
760
PV = n1RT ; T = 273 + 25 = 298 K, P = atm = 1 atm
760

n1 RT 0.28  0.0821  298

V = = = 6.85 L
P 1
Illustration 12. A mixture of CO and CO2 is found to have a density of 1.50 g/litre at 30ºC and 730 mm.
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

Calculate the composition of mixture.

Solution. For mixture, P = (730/760) atm,
T = 303 K, d = 150 g litre–1
d
 PV = nRT = (w/M) RT  P(w/VM) RT  P = RT
M
730 1.50
 = × 0.0821 × 303
760 M
 M = 38.85
Let n1 moles of CO and (100 – n1) moles of CO2 are present in 100 moles.
n1  28  (100  n1 )  44
 Average molecular weight (M) = = 38.85  n1 = 32.19
100
 mole % of CO = 32.19, and mole % of CO2 = 67.81.

16
 Gaseous State
6.0 GRAHAM'S LAW OF DIFFUSION AND EFFUSION
 Diffusion
The process of mixing of gases by random motion of the molecules is called diffusion.
 Effusion
When gas is confined to a container at high pressure than in the surrounding atmosphere it will escape from a
small hole which is opened in the container until the pressure outside and inside have been equalised. This
process is called effusion.
The difference between diffusion and effusion is that in the former case, the gas spontaneously passes through
a porous partition while in the case of effusion, the gas is passed out through a small orifice or hole by applying
some external pressure.
Graham's law of diffusion states "under the same conditions of temperature and pressure, the rates of diffusion
of different gases are inversely proportional to the square roots of their molecular masses or their densities."

1 1 r1 M2 d2
Mathematically , r  or or,, r = M1 = d1
M d 2

Where r1 and r2 are the rates of diffusion of gases 1 and 2.

M1 and M2 are their molecular masses.
d1 and d2 are their densities.

 Effect of volume on rate of diffusion

Volumeof gasdiffused
Rate of diffusion =
Time taken for diffusion
V
or r =
t
Let V1 be the volume of gas 1 and V2 be the volume of gas 2, then
V1 V
r1 = r = 2
t1 2 t2

r1 M2 Vt
 = = 12
r2 M1 V2 t1

(i) Comparison of times taken for the same volume of two gases :
Let the times of diffusion for the same volume of two gases be t1 and t2 respectively. Then
r1 V / t1 d2 M2 r1 t 2 d2 M2
    
r2 = V / t 2 d1 M1 or r2 t1 d1 M1
(ii) Comparision of the volumes of the gases that diffuse in same time :
Let V1 and V2 be the volume of two gases that diffuse in same time t. Then,
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

r1 V1 / t d2 M2 r1 V1 d2 M2
    
r2 = V2 / t d1 M1 or r2 V2 d1 M1

 Effect of pressure on rate of diffusion

Rate of diffusion is proportional to the pressure of the gas in the container.
1
r  P; again, r 
M

P r1 P1 M2
or r  or 
M r2 P2 M1
6.1 Limitations of this law
(i) The laws of diffusion and effusion are applicable only when the pressure difference is very small.
(ii) Correctly speaking the rate of diffusion and effusion are not constant throughout the time interval, but
these rates may be assumed constant for a small time interval.

17
JEE-Chemistr y

Illustration 13. The pressure in a bulb dropped from 2000 to 1500 mm of mercury in 47 minutes when the
contained oxygen leaked through a small hole. The bulb was then completely evacuated. A
mixture of oxygen and another gas of molecular weight 79 in the molar ratio of 1 : 1 at a total
pressure of 4000 mm of mercury was introduced. Find the molar ratio of the two gases remaining
in the bulb after a period of 74 minutes.
P kp
Solution. r r
M M
p t
dp kp dp kdt
f
dp k

dt

M

dt

M
  p 
pi M0
 dt

p1 kt 2000 k k
 n p   n   47   6.12  103
2 M 1500 M M
k = 3.462 × 10–2

2000
n  6.12  10 3  74
p 2 (O 2 )
(2000) 3.462  10 2
n   74
p(unknown) 79

PO2
= 1.523 : 1
P(unknown)

Illustration 14. One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse through a pinhole, whereas one mole
of an unknown compound of xenon with fluorine at 1.6 atm takes 57 s to diffuse through the
same hole. Determine the molecular formula of the compound.
Solution. Rate of diffusion, r  p
p
r  1 / M or r  M
1/ 2
r2 p 2  M1 
or 
r1 p1  M 2 

1
Again, r 
t
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

1/ 2
t1  p 2  M1 
or t 2 =  p1  
 M 2 

2
 p2 t2 
or M2 =   M
 p1 t 1  1
2
 1.6 57 
M2 =    × 28 = 252 g mol–1
 0.8 38 
Let the molecular formula of the unknown compound be XeFn.
Mxe + nMF = 252
or 131 + 19 n = 252
25 2  1 31
n= = 6.36  6
19
Hence, the molecular formula of the gas is XeF6.
18
 Gaseous State
Illustration 15. At 1200ºC, mixture of Cl2 and Cl atoms (both in gaseous state) effuses 1.16 times as fast as
krypton effuses under identical conditions. Calculate the fraction of chlorine molecules dissociated
into atom M (Kr) = 83.8 g mol–1.
Solution. 

Cl2  2Cl

r(Cl2 and Cl mix) M(Kr) 83.8

= 1.16 = M (Cl  Cl) = M av
r (Kr ) av 2

83.8
 Mav = = 62.28 g mol–1
(1.16)2


Cl2   2Cl
Initial mole 1 0
After dissociation (1 – x) 2x
(x = degree of dissociation)
Total moles after dissociation = 1 – x + 2x = (1 + x)
(1 – x)M(Cl2 )  2x M (Cl)
 = 62.28
(1  x)

(1 – x)  71  2x  35.5
= 62.28
1x
(1 – x  x)71
= 62.28
1x
1 62.28
= = 0.88
1 x 71
1 + x = 1.14
x = 0.14
 % dissociation = 14%
Alternately, following formula can also be used to determine degree of dissociation when
there is equilibrium mixture.
m(normal)  m(average) 71 – 62.28
x = = = 0.14
m(average) 62.28

Illustration 16. A 10 liter container consist of 1 mole of gas at 300 K. It is connected to another container having
volume 40 liter and is initially at 300 K. The nozzle connecting two containers is opened for a
long time and once the movement of gas stopped, the larger container was heated to a
temperature of 600 K. Calculate
(a) Moles and pressure of gas in both the containers before heating.
(b) Moles and pressure in two containers after heating. (assume that initially the larger container
is completely evacuated.)
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

Solution. (a) Before heating : (1 – x) (x)

PV = nRT
10 lit
40 lit
(1  x)R  300 x  R  300 300K

10 40 1mole
300K
x = 0.8 moles
(I) (II)
x  R  T 0.8  R  300
Pressure =  = 0.492 atm
V 40
(b) After heating :
(1  x1 )R  300 x1  R  600

10 40
x1 = 0.67 moles, Given T1 = 600 K
x1  R  T1 0.67  .0821  600
Pressure =  = 0.821 atm
V 40

19
JEE-Chemistr y
Illustration 17. A mixture containing 1.12 litre D2 and 2.24 litre of H2 at NTP is taken inside a bulb connected
to another bulb through a stop cock with a small opening. The second bulb is fully evacuated.
The stop cock is opened for a certain time and then closed. The first bulb is now found to contain
0.10 g of D2. Determine the % by weight of the gases in second bulb.
Solution. At STP

D 2  1.12 lit.at STP  0.2 g  0.05 mole

Before diffusion  in I bulb
H 2  2.24 lit.at STP  0.2 g  0.1 mole 

(I) (II)

When these moles are placed in the bulb, the partial pressure of gas will be different because
Vand T are constant. Also P  n
PD2 0.05 1
Thus, = =
PH2 0.10 2

After diffusion D2 left in I bulb = 0.1 g

or D2 diffuses from I into II (bulb) = 0.2 – 0.1 = 0.1 g
Now for diffusion of D2 and H2

rD2 MH2 PD2

 
rH 2 M D2 PH2

w D2 t H2 M D2 PD2
 t w  M P
D2 H2 H2 H2

0.1 t 4 1
    
t w H2 2 2

 w H 2 = 0.14 g

 Wt. of gases in II bulb = wt. of D2 + wt. of H2

= 0.10 g + 0.14 g = 0.24 g
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

0.10
 % D2 by wt. = × 100 = 41.66 %
0.24

% H2 in bulb II = 58.33%

 Dalton's law of partial pressure :

Ptotal = PA + PB + ....... ; Pwet gas = Pdry gas + PH O vapour ( i.e. aq. tension.)
2

PA , PB are partial pressures ; PA = mole fractionA  Total pressure

Partial pressure
and % of gas in mixture =  100 .
Total pressure
 Amagat's Law :
The total volume of a mixture of gases is equal to the sum of the partial volumes of the constituent
gases, at same Temperature & Pressure.

20
 Gaseous State

 Graham's law of Diffusion or Effusion :

1 1 P
r  or r  r  [For gases effusing at different pressures]
d M M
r is rate of diffusion of any gas.
r1 d2 M2 volume / time M2
= = ; =
r2 d1 M1 volume / time M1
d is density at some temperature.
moles diffused dis tan ce travelled in a narrow tube Pr essure drop I
r = = =
time taken time taken Pr essure drop II

1. Equal weights of ethane and hydrogen are mixed in an empty container at 25oC. Fraction of total pressure
exerted by hydrogen is :

(A) 1 : 62 (B) 1 : 1 (C) 1 : 16 (D) 15 : 16

2. Equal masses of hydrogen gas and oxygen gas are placed in a closed container at a pressure of 3.4 atm.
The contribution of hydrogen gas to the total pressure is :

(A) 1.7 atm (B) 0.2 atm (C) 3.2 atm (D) 3.02 atm

3. A 1 : 1 mixture (by weight) of hydrogen and helium is enclosed in a one litre flask at temperature 0 oC.
Assuming ideal behaviour, the partial pressure of helium is found to be 0.42 atm, then concentration of
hydrogen would be

(A) 0.0375 (B) 0.028 (C) 0.0562 (D) 0.0187

4. A flask contains 36% nitrogen, 39% oxygen and 25% hydrogen by volume. If the total pressure of the mixture of
gases is 500 mm, the partial pressure of oxygen is

(A) 120 mm (B) 145 mm (C) 195 mm (D) 210 mm

5. 190.0 ml of N2 was collected in a jar over water at some temperature, water level inside and outside the jar
standing at the same height. If barometer reads 740 mm Hg and aqueous tension at the temperature of
the experiment is 20 mm Hg, the volume of the N 2 gas at 1 atm pressure and at the same temperature
would be :
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

(A) 185.0 mL (B) 180.0 mL (C) 195.0 mL (D) 200 mL

6. Consider the following apparatus. Calculate the partial pressure of helium after opening the valve. The temperature
remains constant at 16°C.

(A) 0.164 atm

(B) 1.64 atm

(C) 0.328 atm

(D) 1 atm

7. The rate of diffusion of a gas having molecular weight just double of molecular weight of nitrogen gas, is 56 ml
per second. The rate of diffusion of nitrogen will be

(A) 56 ml/sec (B) 28 ml/sec (C) 112 ml/sec (D) 79.19 ml/sec
21
JEE-Chemistr y

8. 50 ml of hydrogen diffuses out through a small hole from a vessel in 20 minutes. Time needed for 40 ml of
oxygen to diffuse out is

(A) 12 minutes (B) 64 minutes (C) 8 minutes (D) 32 minutes

9. Two grams of H2 diffuses from a container in 10 minutes. How many gram of oxygen would diffuse through the
same container in the same time under similar conditions
(A) 0.5 gms (B) 4gms (C) 6gms (D) 8gms
10. The time taken for a certain volume of gas to diffuse through a small hole was 2 min. Under similar conditions
an equal volume of oxygen took 5.65 min to pass. The molecular mass of the gas is
(A) 32.0 (B) 11.33 (C) 4.0 (D) 80.
11. A mixture of H2 and He in 1 : 1 mass ratio is allowed to diffuse through a porous pot. The mole ratio of H2 to
He in the initially effused mixture will be
(A) 2 : 2 (B) 2 2 :1 (C) 1 : 2 (D) 1 : 1
12. Calculate relative rate of effusion of O2 to CH4 through a container containing O2 and CH4 in 3 : 2 mass ratio.

3 2 3 3
(A) (B) (C) (D) none of these
4 4 2 2 2
13. Xml of H2 gas effuses through a pin hole in a container in 5 s, the time taken for the effusion of the same
volume of the gas specified below under identical conditions is
(A) 10 s : He (B) 20 s : O2 (C) 25 s : CO (D) 55 s : CO.
14. SO2 and He are kept in a container at partial pressures P1 and P2. Athin perforation is made in the wall of the
container and it is observed that the two gases effuse out at the same rate. The ratio P1 : P2 will be
(A) 16 : 1 (B) 1 : 16 (C) 1 : 4 (D) 4 : 1
15. There are 100 persons sitting at equal distances in a row XY. N2O gas (laughing gas) is released from the side
X and tear gas (mol. mass = 176) from side Y at the same moment and at the same pressure. The person who
will have a tendency to laugh and weep simultaneously is
(A) 34th from side X (B) 67th from side X (C) 76th from side X (D) 67th from side Y

7.0 KINETIC THEORY OF GASES

The theoretical model for all the experimental gas laws can be analys with the help of kinetic theory of
gases which is based on following assumptions :
(a) All the gases consists of very small molecules or atoms whose volume is negligible compared to volume
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of container (in case volume of container is very small, then this assumption will be violated)
(b) There is no interaction between gaseous particles (the interaction may appreciably affected under certain
conditions of temperature and pressure).
(c) The gaseous molecules are under a continuous state of motion which is unaffected by gravity (the
random straight line motion is known as brownian motion)
(d) Due to the continuous motion, collision between gaseous molecules with the wall of cantainer occurs.
The collision with the wall of container are responsible for pressure exerted by the gas on the wall of
container.
(e) The molecule moves with different speed, however the speed of each molecule keep on changing as the
collision occur.
(f) All the collision occuring are considered to be perfectely elastic which implies that there is no loss of
energy.
(g) The average kinetic energy of gas will depends on absolute temperature only.

22
 Gaseous State
 Translational kinetic energy of n moles
1 3 3
Mu2 = PV = nRT
2 2 2

 Average translational kinetic energy per molecule

3 RT 3
= = KT
2 N0 2

 R 
Where K    is called Boltzmann's constant.
 N0 
Its numerical value is 1.38 × 10–16 erg K–1 molecule–1
Thus average K.E. is proportional to absolute temperature.
If T = 0 K (i.e., – 273.15ºC), then average KE = 0
Thus, absolute zero (0 K) is the temperature at which molecular motion ceases.

7. 1 Different types of molecular velocities

1
PV = MU 2rms
3
(i) Root mean square velocity (Urms) : It is defined as the square root of the mean of the squares of
the velocities possessed by all the molecules present in the given sample of gas
U12  U 22  ...U 2n
Urms =
N

3PV 3RT 3P
 Urms (root mean square velocity) =  
M M d
Where d is the density.
If N1 molecules have velocity u1 and N2 molecules have velocity u2, then
N1 u12  N 2 u22
urms =
N1  N 2
(ii) Average velocity (Uav) : It is given by the arithmetic mean of the different velocities possessed by
the molecules of the gases at a particular temperature.
U1  U 2  .......U n
uav =
N
8RT
uav (average velocity) =
M
(iii) Most probable velocity (ump) : It is defined as the velocity possessed by the maximum number of
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molecules of a gas at a given temperature.

2RT
ump (most probable velocity) =
M
If P and T both are given, use equation in terms of temperature i.e. use

3RT 3PV
urms = and not
M M
To have velocity in ms–1 (MKS) take R = 8.314 J mol–1K–1, M in kg.
If density is in kg m–3 and P in N m–2, velocity will be in ms–1.
Relation between rms velocity, average velocity and most probable velocity.
3RT 8RT 2RT 8
urms : uav : ump = : :  3: : 2 = 1.2248 : 1.1284 : 1
M M M 
urms = 1.2248 ump
uav = 1.1284 ump
ump = 1.0854 uav
23
JEE-Chemistr y
7.2 Distribution of molecular speeds
(a) The speed of a molecule of a gas changes continuously as a result of collisions with other molecules
and with the walls of the container. Thus, the net result is that we cannot speak of the speed of
individual molecule; hence must consider the statistical averages of the speeds of the whole collection
of gas molecules.

(b) The manner in which the molecules of a gas are distributed over the possible speed ranges, from zero
to very high values, was first investigated by Maxwell using the theory of probability. His results are
expressed as the law of distribution of molecular speeds, one form of which is
3/ 2
 m  mu2
2
dN = 4N   e

2 KT u du
 2 KT 
(c) The above expression gives the no. of molecules dN having speeds between U and U + du in terms
of total no. of molecules, N present in the gas m is mass of single gas molecule and T is the absolute
temperature of gas.
1  dNu 
(d) The Maxwell distribution of speeds is customarily plotted with the fraction   as the ordinate
N  du 
and u as the abscissa.
T 2 > T1
1  dN  1  dN  T1
 =   T2
N  du  du  du 
1 dN
1 dN N dU
So, the term, represents the fraction of molecules in the speed
N du
range of u to u + du per unit interval of speed. Roughly speaking, u U1 U2
this gives the probability of finding a molecule with a speed between
u and (u + du). The distribution of two temperatures is shown in the
fig.
(e) The curve at any temperature is parabolic near the origin, since the factor u2 is dominant in this region,
the exponential function being approximately equal to unity. At high values of u, however, the
exponential factor dominates the behaviour of the function, causing it to decrease rapidly in value. As
a consequence of the contrasting behaviour of two factors, the product function passes through a
maximum at a speed known as the most probable speed (umps). Thus, the most probable speed is the
speed possessed by the maximum fraction of the molecules.

(f) It can be seen from the given figure, that the fraction of molecules having either very low speeds or
very high speeds are small in numbers. The total area under the curve gives the total no. of molecules
in the collection i.e. the no. of molecules comprising of all speeds. The area under the curve between
any two speeds, for example, U1 and U2, gives the total no. of molecules having speed between these
two values.
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(g) The given figure illustrates the distribution of speeds at two temperatures T1 and T2. Since the total
no. of molecules is the same at both temperatures, increases the K.E. of the molecules, it follows that
fraction of molecules having lower speed range decreases whereas fraction of molecules having higher
speed range increases on increasing the temperature.

(h) Also the curve at the higher temperature T2 has its Umps shifted to a higher value compared with that
corresonponding fraction of molecules has decreased. But at the same time for the T1 curve near
whereas umps has become broader at the higher temperature indicating the more molecules possess
speeds near to most probable speed.

 Collision frequency & Mean Free Path

d1  d 2  ......  d n
Mean free path  =
n

24
 Gaseous State

Average velocity / R M S velocity kT

 = collision number or frequency =
2   2P

k = Boltzman constant ;  = collision diameter .

Z1 = 2 2 uN * [collisions made by one molecule]

1
Z11 = 2
*2 [bimolecular collisions]
2  uN

Illustration 18.(a) Calculate the pressure exerted by 1023 gas molecules, each of mass 10–25 kg, in a container
of volume 1× 10–3 m3 and having root mean square velocity of 103 ms–1.
(b) Also calculate total kinetic energy and
(c) temperature of the gas.
Solution (a) By kinetic theory

1 mNu2 1  10 25  10 23  (10 3 )2

P= = = 3.33 × 106 N m–2
3 V 3  10 3

1 2 
(b) Total KE =  mu  × N
2 

1 1
= × 10–25 × (103)2 × 1023 = × 104 = 0.5 × 104 J
2 2

3 10 23 1023
(c) Also total KE = nRT, where n (mole) = =
2 NA 6.023  10 23

3 10 23
0.5 × 104 =   8.314  T
2 6.023  10 23

0.5  10 4  2  6.023
 T= = 2415 K
3  8.314
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Illustration 19.A gas bulb of 1 litre capacity contains 2.0 × 1021 molecules of nitrogen exerting a pressure of
7.57 × 103 Nm–2. Calculate the root mean square velocity of the gas molecules.
Solution No. of gas molecules = 2 × 1021
6.023 × 1023 molecules of nitrogen weight = 28 g

28  2  10 21
2 × 1021 molecules of N2 weights = g = 0.093 g
6.023  10 23

Mass 0.093 0.093  10 –3

 Density =  g/L= = 0.093 kg/m3
Volume 1 103

3RT 3PV 3P 3  7.57  10 3

urms = = = = Urms = = 494.16 m/s
M M d 0.093

25
JEE-Chemistr y

 Kinetic theory of gases

1 1
PV = m N u2 = M u2 (For 1 mole)
3 3
 Types of velocities
u12  u 22  ......  u 2N
u2 = ; u = root mean square speed .
N

3R T 3PV 3P
u = = = ;
M M d

u1  u 2  ......  u N 8RT
Average speed = =
N M

2RT
most probable speed =
M
most probable : average : r. m. s. = 1 : 1.13 : 1.22 
8
 Relationsh ip between three
types of speeds
= 2 : : 3 

urms > uav > ump
3 R 3
 Average kinetic energy of a single molecule = . .T = kT
2 N 2
k = Boltzman constant = 1.3806  10 16 erg deg 1 .
3
 Total kinetic energy for one mole of a gas = RT .
2
3
 kinetic energy of n moles of a gas = n  RT
2
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1. A gas distributes itself uniformly into the entire space available because of
(A) repulsive forces between molecules (B) attractive forces between molecules
(C) ceaseless random motion of molecules (D) random collisions amongst the molecules
2. The postulates of the kinetic molecular theory of gases include all those that follow except
(A) no forces exist between molecules (B) molecules are point masses
(C) molecules are in random motion (D) molecules are repelled by the walls of the container
3. Which of the following does not determine the total translational kinetic energy of an ideal gas
(A) Temperature (B) Amount of the gas
(C) Number of moles of gas (D) Pressure of the gas
4. At what temperature will the total K.E. of 0.30 mol of He be the same as the total K.E. of 0.40 mol Ar at 400
K?
(A) 533 K (B) 400 K (C) 346 K (D) 300 K

26
 Gaseous State
5. Which of the assumptions of the kinetic-molecular theory best explains the observation that a balloon collapses
when exposed to liquid nitrogen (which is much colder than a cold winter day) ?
(A) Gas molecules move at random with no attractive forces between them.
(B) The speed of gas molecules is proportional to their kelvin temperature
(C) The amount of space occupied by a gas is much greater than the space occupied by the actual gas molecules
(D) Collisions with the walls of the container or with other molecules are elastic.
6. At 298 K, which of the following gases has the lowest average molecular speed ?
(A) CO2 at 0.20 atm (B) He at 0.40 atm (C) CH4 at 0.80 atm (D) NO at 1.00 atm
7. A comparison is made at standard temperature and pressure (S.T.P.) of 0.50 mol H2(g) and 1.0 mol He(g). The
two gases will
(A) have equal average molecular translational kinetic energies
(B) have equal molecular speed
(C) occupy equal volumes
(D) have equal effusion rates
8. At what temperature the average speed of helium molecule will be the same as that of oxygen molecule at
527°C
(A) 100 K (B) 200 K (C) 273 K (D) 400 K
9. If for two gases of molecular masses MA and MB at temperatures TA and TB, TA MB = TB MA, then which of the
following properties has the same magnitude for both the gases
(A) Pressure (B) Density (C) Molar K. E. (D) rms velocity
10. Which of the following statements are correct at a fixed temperature?
(A) The translational K.E. of all molecules in a gas is the same.
(B) The translational K.E. varies from molecule to molecule.
(C) The average translational K.E. of a molecule is greater in heavier gas than the lighter one.
(D) The average translational K.E. of a molecule is the function of pressure.
11. The most probable speed of 8 g of H2 is 200 ms–1 , total kinetic energy (neglact rotational and vibrational
energy) of H2 gas is :
(A) 480 J (B) 240 J (C) 120 J (D) none of these
12. If URMS of a gas is 30 R1/2
ms at 27°C then the molar mass of gas is :
–1

(A) 0.02 kg/mol (B) 0.001 kg/mol (C) 0.003 kg/mol (D) 1 kg/mol

13. The root mean square velocity of hydrogen is 5 times than that of nitrogen. If T is the temperature of the
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gas, then :

(A) TH 2  TN 2 (B) TH 2  TN 2 (C) TH 2  TN 2 (D) TH2  7 TN2

14. Distribution of fraction of molecules with velocity is represented in the fig. Velocity corresponding to point X is
Fraction of
molecules

Velocity

2RT 3RT 8RT

(A) (B) (C) (D) None
M M M

27
JEE-Chemistr y

15. At a definite temperature (T), the distribution of velocities is given by the curve. The curve indicates that the
velocities corresponding to points A, B and C are :

(A) most probable, average and root mean square

(B) average, root mean square and most probable
(C) root mean square, average and most probable
(D) most probable, root mean square and average

16. Let the most probable velocity of hydrogen molecules at a temp. t°C is Vo. Suppose all the molecules dissociate
into atoms when temp is raised to (2t + 273)°C, then the new r.m.s velocity is
(A) 2 / 3 VO (B) 2 Vo (C) 2 3 V0 (D) 6 V0

8.0 REAL GAS

An ideal gas is a hypothetical gas whose pressure, volume and temperature behaviour is completely described
by the ideal gas equation. Actually no gas is ideal or perfect in nature. All gases are real gases.
Real gases do not obey the ideal gas laws exactly under all conditions of tamperature and pressure.
Real gases deviates from ideal behaviour because of mainly two assumptions of "Kinetic theory of gases".
(i) The volume of gas particle is negligible compared to volume of container (while the real gas particle have
some significant volume).
(ii) There is no interaction between gaseous particles (while attraction forces exist between real gas particles).
 Deviation from Ideal behaviours
Compressibility factor
The extent to which a real gas departs from the ideal behaviour may be expressed in terms of
compressibility factor (Z), where Z is

Vm PVm
Z=  [Vm = molar volume]
Vm (ideal) RT

When Z > 1, Vm > 22.4 lit at STP ; When Z < 1, Vm < 22.4 lit at STP
Plots of compressibility factor vs pressure
(i) For an ideal gas Z = 1 and is independent of temperature and pressure.
(ii) Exceptional behaviour of H2 and He :
for these gases Z > 1. For such gases repulsive forces predominants.
(iii) Effect of pressure :
At very low P, PV  RT i.e. Z  1
At low P, PV < RT i.e. Z < 1
At moderate P, PV  RT i.e. Z  1
At high P, PV > RT i.e. Z > 1
(iv) For the gases which are easily liquefied (e.g. CO2) Z dips sharply below the ideal line in the low
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pressure region.
(v) Effect of temperature : An increase in temperature shows a decrease in deviation from ideal behaviours
i.e. PV approaches unity or Z approaches unity with increase in temperature.

T4
H2
T 1> T 2 > T 3> T 4 T3
He
N2 T2
CH 4 T1
1.0 ideal gas Z = 1
Z CO 2 1.0
ideal gas

Z <1
Z
0 100 200 300 0 200 400 600
P P

28
 Gaseous State
 Boyle's temperature
The temperature at which a real gas behaves like an ideal gas over an appreciable range of pressure is
known as Boyle's temperature (TB). It means that at this temperature, the value of PV remains constant
for an appreciable range of pressure, i.e. Boyle's Law is obeyed. Mathematically we may express the Boyle
 (PV )
temperature or Boyle point as the temperature where = 0 when P  0.
P
So to use ideal gas equation for real gas, we will use some correction factor for volume as well as for pressure.

8.1 Volume Correction

In the ideal gas equation, PiVi = nRT, Vi represents the ideal volume where the molecules can move freely.
In real gases, a part of the total volume is occupied by the gas molecules. Hence the free volume Vi is
the total volume V minus the volume occupied by the gas molecules.
i.e. Real volume of gas = Actual volume of container – volume occupied by N molecules in motion.
Vi = V – b for one mole of gas
d
excluded
Vi = V – nb for n mole of gas volume
Where b is termed the 'excluded volume' or 'co-volume'.
It is constant and characteristic for each gas.
4 3
b =  r  × 4N
3 
[where r = radius of gas molecule, N = Avogadro's number] d
Illustration of excluded volume
8. 2 Pressure Correction
In order to take account the effect of intermolecular forces of attraction, let us consider a molecule A is
the midst of the vessel.

A • •
• • •
• • • B

• • •
• •

This molecule is surrounded by other molecules in a symmetrical manner and is being attracted uniformly
on all sides by the neighbouring molecules with the result that this molecule on the whole experiences no
net force of attraction.
Now, consider a molecule B near the side of the vessel, which is about to strike one of its sides, thus
contributing towards the total pressure of the gas. There are molecules only on one side of the vessel, i.e.
towards its centre, with the result that this molecule experiences a net force of attraction towards the centre
of the vessel. This results in decreasing the velocity of the molecule, and hence its momentum. Thus, the
molecule does not contribute as much force as it would have, had there been no force of attraction. Thus,
the pressure of a real gas would be smaller than the corresponding pressure of an ideal gas.
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Van der Walls noted that the total force of attraction on any molecule about to hit a wall is proportional
to the concentration of neighbouring molecules, n/V. However, the number of molecules about to hit the
wall per unit wall area is also proportional to the concentration n/V. Therefore, the force per unit wall area,
or pressure, is reduced from that assumed in the ideal gas wall by a factor proportional to n2/V2. Letting
a be the proportionality constant, we can write
P (actual) = P(ideal) – n2a/V2
or P (ideal) = P(actual) + n2a/V2
'a' is a constant which depends upon the nature of the gas, V is the volume of 1 mole of gas.
Combining the two corrections, for 1 mole of gas
 a 
 P  2  (V – b) = RT
 V 
 n2 a 
For n mole of gas  P  2  (V – nb) = nRT
 V 

29
JEE-Chemistr y
 The constants 'a' and 'b
Van der Waals constant for attraction 'a' and volume 'b' are characteristic constants for a given gas.
(i) The 'a' values for a given gas are measure of intermolecular forces of attraction. More are the
intermolecular forces of attraction, more will be the value of a.
(ii) For a given gas van der Waals constant of attraction 'a' is always greater than van der Waals constant
of volume 'b'.
(iii) The gas having higher value of 'a' can be liquefied easily and therefore H2 and He are not liquefied
easily.
(iv) Unit of 'a' is lit2 mole–2 atm or cm4 mole–2 dyne.
(v) Unit of 'b' is lit mole–1 or cm3 mole–1.
(vi) At low pressure, volume correction for 1 mole of gas is negligible,  b = 0
The gas equation can be written as
 a  PVm a
 P  2  V = RT or Z = = 1 –
 V  RT Vm RT
where Vm = molar volume
where Z is known as the compressibility factor.
(vii) At higher pressures, the pressure correction for 1 mole of gas is negligible
a
 = 0
V2
or (P + 0) (V– b) = RT or P (Vm – b) = RT
PVm Pb
or PVm = RT + Pb or, Z = = 1 +
RT RT
 The van der Walls constants for some common gases
Gas a (dm6 atm mol–2) b (dm3mol–1)
Ammonia 4.17 0.0371
Carbon dioxide 3.59 0.0427
Chlorine 6.49 0.0562
Helium 0.034 0.0237
Hydrogen 0.024 0.0266
Hydrogen chloride 3.67 0.0408
Methane 2.25 0.0428
Nitrogen 1.39 0.0319
Oxygen 1.36 0.0318
Sulphur dioxide 3.71 0.0564
Water 5.44 0.0305
9.0 LIQUEFACTION OF GASES AND CRITICAL POINTS
The phenomenon of converting a gas into liquid is known as liquefaction. The liquefaction of a gas takes place
when the intermolecular forces of attraction become so high that exist in the liquid. A gas can be liquefied by :
(a) Increasing pressure : An increase in pressure results in an increase in attraction among molecules.
(b) Decreasing temperature : A decrease in temperature results in a decrease in kinetic energy of molecules.
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9.1 Andrews Isotherms

The essential conditions for liquefaction of gases were discovered by Andrews (1869) as a result of his
study of P–V–T relationship for CO2.The types of isotherms are shown in figure.
F

48 ºC
35.5ºC
Pressure

O 31.1ºC
Gas
vapour
+ liquid 21.5ºC
D E
13.1ºC
C B A
Volume
Fig : Isotherms for carbon dioxide
showing critical region
 Observations from figure
(a) At low temperatures : For the curve ABCF, as the pressure increases, volume of the curve decreases
(curve A to B).

30
 Gaseous State
At point B, at constant pressure, liquefaction commences and the volume decreases rapidly (because
gas is converted to liquid with higher density).
At point C, liquefaction is complete. The line CF represents the variation of V with P of the liquid state.
The steepness of the line CF indicates that the liquid cannot be easily compressed. Thus AB, represent
gaseous state, BC represent liquid and vapour in equilibrium. CF represent liquid state.
The pressure corresponding to the line BC is there vapour pressure of the liquid.
(b) At higher temperatures : Similar type of curve as in case (a) is obtained but the width of the
horizontal portion is reduced. The pressure corresponding to this portion is higher than at lower
temperatures.
(c) At high temperatures : (like 48ºC), the isotherms are like those of ideal gas.
(d) At temperature (31.1 ºC) : The horizontal portion is reduced to a point.
The isotherm at TC is called critical isotherm.
dP
At point O, = 0.
dV
The point O is called the point of inflection.
Critical temperature (TC) : The maximum temperature at which gas can be liquefied by the application
of pressure alone i.e. the temperature above which a liquid cannot exit is called the critical temperatureTC.
8a
TC =
27Rb
Critical pressure (PC) :The minimum pressure required to liquefy the gas at the temperature TC is called
the critical pressure PC.
a
PC =
27b2
Critical volume (VC) :The volume occupied by one mole of the gas at critical temperature, TC and critical
pressure, PC is called the critical volume (VC) of the gas.
VC = 3b
(i) Therefore the value of critical compressibility factor in terms of vander wall’s constants is given by
a a a
 3b
PC VC 27b2 9b 9b
Z = = = =
RTC 8b 8Ra 8a
R
27Rb 27Rb 27b
PC VC a 27b 3
Z = = × = = 0.375
RTC 9b 8a 8
PC VC
(ii) If we compart the value of RT = 0.375, with the experimental values, it has been found that the
C
agreement is very poor.
 Boyle temperatures in terms of van der Waals constant
a
TB =
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Rb
 Critical constants of gases
Gas PC (atm) Vm,c (cm3mol–1) TC (K)
He 2.26 57.9 5.2
Ne 26.9 41.7 44.4
H2 12.8 65.5 33.3
O2 50.1 78.2 154.8
N2 33.5 90.1 126.2
CO2 72.8 94.0 304.2
H2O 218.0 55.6 647.3
NH3 111.5 72.5 405.0
CH4 45.6 98.7 190.6

31
JEE-Chemistr y
 Virial Equation Of State For 1 Mole Of Gas
PV 1 1 1
z = RT = 1 + B + C 2 + D 3 + ...... (B, C, D... are temp. dependent constant)
V V V
a 
B = second virial coefficient = b 
RT  gas dependent
C = third virial coefficient = b2 . 

Illustration 20. Calculate the pressure exerted by 5 mole of CO2 in one litre vessel at 47ºC using van der waal's
equation. Also report the pressure of gas if it behaves ideal in nature.
Given that a = 3.592 atm lt2 mol–2, b = 0.0427 L/mol. Also, if the volume occupied by CO2
molecules is negligible, then calculate the pressure exerted by one mole of CO2 gas at 273 K.
Solution Vander waal's equation
 n2 a 
 p  2  [V – nb] = nRT
 V 
n CO2 = 5, V = 1 litre, T = 320 K, a = 3.592, b = 0.0427

 3.592 
  P  25  [1 – 5 × 0.0427] = 5 × 0.0821 × 320
 1 
 P = 77.218 atm
For ideal behaviour of gas, PV = nRT
 P × 1 = 5 × 0.0821 × 320
 P = 131.36 atm
 a 
For one mole  P  2  [V – b] = RT
 V 

RT a
 P = – 2
V V

0.0821  273 3.592

 P = –
22.4 (22.4)2
 P = 0.9922 atm
The volume occupied by 1 mole at 273 K is 22.4 litre if b is negligible.

Illustration 21. Two moles of ammonia gas are enclosed in a vessel of 5 litre capacity at 27ºC. Calculate the
pressure exerted by the gas, assuming that
(i) the gas behaves like an ideal gas (using ideal gas equation).
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(ii) the gas behaves like a real gas (using van der Waal’s equation)
Given that for ammonia, a = 4.17 atm litre2 mol–2 and b = 0.037 litre mol–1.
Solution Given,
n = 2 moles
V = 5 litres
T = 27ºC = (27 + 273) K = 300 K
a = 4.17 atm litre2 mol–2
b = 0.037 litre mol–1
Also, we know that
R = 0.0821 litre atm K–1 mol–1
(i) If the gas behaves like an ideal gas, we have
PV = nRT
nRT 2  0.0821  300
 P = = = 9.85 atm
V 5

32
 Gaseous State

(ii) If the gas behaves like a real gas, we apply van der Waal's equation i.e.
 an2 
 P    (V – nb) = nRT
 V 

nRT an 2 2  0.0821  300 4.17  (2)2

or P = – = – = 9.33 atm.
V  nb V2 5  2  0.037 (5)2

Illustration 22. 1 mole of CCl4 vapours at 77ºC occupies a volume of 35.0 L. If vander waal's constants are
a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region. (b) high pressure region.
Solution (a) Under low pressure region, V is high
 (V – b)  V

 a  a PV a
 P  2  V = RT  PV + = RT   = 1
 V  V RT RTV

PV  a  20.39
Z= = 1   = 1 – = 0.98
RT  RTV  0.0821  350  35
(b) Under high pressure region, P is high,

 a 
P  2  P
 V 
 P (V – b) = RT  PV – Pb = RT
PV Pb
 = 1
RT RT

PV Pb  PV P 1
Z = = 1 +   1, or  
RT RT  RT RT V 

b 0.1383
Z= 1 + =1 + = 1 + 0.004 = 1.004
V 35

 B 
Illustration 23. One way of writing the equation of state for real gases is PV = RT 1   ... where B is a
 V 
constant. Derive an approximate expression for B in terms of van der Waal’s constants a and b.
Solution. According to van der Waal's equation

 a 
 P  V 2  [V – b] = RT
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RT a
or P = 
(V  b) V 2
Multiply by V, then

RTV a
PV = –
(V  b) V

 V a 
or PV = RT  
 V  b VRT 
1
 b a 
or PV = RT  1    
 V VRT 

33
JEE-Chemistr y
1 2
 b b b
 1  V  = 1 + V +  V  + ....
 b a 
 PV = RT 1   ... 
 V VRT 
  a  1 
PV = RT 1   b   .  ...
  RT  V 
a
 B = b –
RT

Illustration 24.The critical temperature and pressure of CO2 gas are 304.2 K and 72.9 atm respectively. What
is the radius of CO2 molecule assuming it to behave as vander Waal’s gas ?
Solution. TC = 304.2 K PC = 72.9 atm
8a a
TC = PC =
27Rb 27b2
8a
TC 8a 27b2 8b
 P = 27Rb = × =
C a 27Rb a R
27b2
RTC 1 0.082  304.2
or b =   = 0.04277 lit mol–1
8PC 8 72.9
4 3
b = 4 NA × r = 42.77 cm3
3
4 3
 4 × NA × r = 42.77
3
3  42.77  10 23
or r3 =
16  6.023  3.14
or r3 = 0.424 × 10–23 = 4.24 × 10–24
or r = (4.24)1/3 × 10–8 cm = 1.62 × 10–8 cm
 radius of CO2 molecule = 1.62 Å

 Vander Waals equation of state

 a 2
 P 2 .n  (V  n b) = n R T .
 V 
a , b are Vander Waals constants ; different for each gas
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unit of a  atm L2 mol 2 ; S.I. unit  Pa m6 mol 2

unit of b  L mol 1 ; S.I. unit  m3 mol 1
greater the value of 'a' more easily the gas is liquefiable ;
greater the value of 'b' greater the molecular size ,

 Real gases : Deviation from ideal behaviour

The curve for the real gas has a tendency to coincide with that of
an ideal gas at low pressures when the volume is large. At higher
pressures, however deviations are observed.

 Compressibility factor
PV volume observed
z = =
nRT volume ideal

34
 Gaseous State

Z t=0°C
H2
N2
CH4
Ideal gas
1.0 CO2

0
100 200 300
p/101.325 kPa

 Boyle Temperature
a
TB =
bR
 Inversion Temperature
2a
Ti =
bR
 Interpretation Of Deviation From Vander Waals Equation
PV a
(i) At low pressure z = = 1
RT VR T
PV Pb
(ii) At high pressure z = = 1+
RT RT
PV a
(iii) At extremely low pressure z = = 1 ; Pb =
RT V
 Critical Phenomenon : Critical Temp , Critical pressure , Critical volume

8a a
Tc = ; Pc = ; Vc = 3 b
27 Rb 27 b 2

1. A gas behaves like an ideal gas at :

(A) high pressure and low temperature (B) low pressure and high temperature
Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

(C) high pressure and high temperature (D) low pressure and low temperature
2. Which of the following gases follows non-ideal behaviour ?
(A) N2 gas having density 1.25 g L–1 at S.T. P.
(B) 2.8 g CO gas in 0.1 L flask exerting a pressure of 24.63 atm at 300 K
(C) 1.6 g CH4 in 0.5 L flask at 273 K exerting a pressure of 4 atm
(D) 0.1 g H2 gas at S.T.P. occupies volume of 1.12 L.
3. Under which of the following sets of conditions is a real gas expected to deviate from ideal behaviour?
(I) High pressure, small volume
(II) High temperature, low pressure
(III) Low temperature, high pressure
(A) only I (B) only II (C) only III (D) I and III both

35
JEE-Chemistr y
4. Positive deviation of real gases from ideal behaviour takes place because of

PV PV
(A) molecular interactions and 1 (B) molecular interactions and 1
nRT nRT

PV PV
(C) finite size of molecules and 1 (D) finite size of molecules and 1
nRT nRT
5. For a hypothetical gas containing molecules as point masses and having non-zero intermolecular forces, which
of the following is correct
(A) The gas will show positive deviation from ideal behaviour

PV
(B) The compressibility factor 1
nRT
(C) The gas is more compressible than the ideal gas under equivalent conditions
(D) The gas is difficult to be compressed compared to ideal gas.
6. The compressibility of a gas is less than unity at STP. Therefore
(A) Vm > 22.4 L (B) Vm < 22.4 L (C) Vm = 22.4 L (D) Vm = 44.8 L
7. Four different identical vessels at same temperature contains one mole each of C2H6, CO2, Cl2 and H2S at
pressures P1, P2, P3 and P4 respectively. The value of vander Waals constant ‘a’ for C2H6, CO2 , Cl2 and H2S is
5.562, 3.640, 6.579 and 4.490 atm. L2. mol–2 respectively. Then
(A) P3 < P1 < P4 < P2 (B) P1 < P3 < P2 < P4
(C) P2 < P4 < P1 < P3 (D) P1 = P2 = P3 < P4
8. A gas has non-zero value of force of attraction between the molecules but has the molecules to be point
masses. The van der Waal’s equation for the gas will be
(A) PV = nRT + nbP (B) P (V – nb) = nRT

an 2
(C) PV = nRT (D) PV = nRT –
V
9. At which one of the following temperature – pressure conditions, the deviation of a gas from ideal behaviour is
expected to be minimum ?
(A) 550 K and 1 atm (B) 350 K and 3 atm (C) 250 K and 4 atm (D) 450 K and 2 atm
10. Which of the following is (are) true for real gases. (‘C’ represents some constant value, ‘R’ represents molar gas
constant).
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(A) Lim (PV)  C at constant temperature (B) Lim (PV)  C at constant temperature
P 0 V 0

 PV   PV 
(C) Lim  T (D) Lim   R
P0
 RT  V 0
 RT 
11. At Boyle temperature, the value of compression factor Z (= pVm/RT = Vreal/Videal) has a value of one over a
wide range of pressure. This is due to the fact that in the van der Waals equation
(A) the constant a is negligible and not b
(B) the constant b is negligible and not b
(C) both the constant a and b are negligible
(D) the effect produced due to the molecular attraction compensates the effect produced due to the molecular
volume

36
 Gaseous State
12. For the non-zero volume of molecules having no forces of attraction, the
II
PV III
variation of compressibility factor Z  with pressure is given by the graph PV IV
RT z I
RT
(no. of moles of gas = 1 mole)

Pressure
(A) I (B) II (C) III (D) IV
13. A graph is plotted between PVm (along Y-axis) and P (along X-axis) at 27° ( Vm being the molar volume of an
ideal gas). The intercept of the graph at Y-axis is (R = 0.082 atm L K–1 mol–1)
(A) 22.4 atm L mol–1 (B) 24.6 atm L mol–1 (C) 24.6 atm L K–1 mol–1 (D) none of these

14. At low pressure, for 1 mole of gas if RT = 2 a.P , then the volume occupied by a real gas is :

2RT 2P RT
(A) (B) (C) (D) none of these
P RT 2P
15. The compressibility factor for nitrogen at 330 K and 800 atm is 1.90 and at 570 K and 200 atm is 1.10. A
certain mass of N2 occupies a volume of 1 dm3 at 330 K and 800 atm. Calculate volume occupied by same
quantity of N2 gas at 570 K and 200 atm :
(A) 1 L (B) 2 L (C) 3 L (D) 4 L

  
16. If the slope of ‘Z’ (compressibility factor) v/s ‘P’ curve is constant  slope  atm 1  at a particular
 492.6 
temperature (300 K) and very high pressure, then calculate diameter of the molecules.
(Given : NA = 6.0 × 1023, R = 0.0821 atm. lit mol–1 K–1)
(A) 7.5 Å (B)5 Å (C) 2.5 Å (D) 1.25 Å
17. The correct order of temperature of a vander waal’s gas is :
(I) Boyle’s temperature (II) Critical temperature (III) Inversion temperature
(A) III > I > II (B) I > II > III (C) II > I > III (D) I > III > II
18. At 273 K temp, and 9 atm pressure, the compressibility for a gas is 0.9. The volume of 1 milli-moles of gas at
this temperature and pressure is :
(A) 2.24 litre (B) 0.020 mL (C) 2.24 mL (D) 22.4 mL
19. For a real gas following vander waal’s select the correct realtionship.

8a a
(I) TC  (II) VC  3b (III) PC 
27Rb 27Rb 2
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(A) (I) and (III) (B) (II) and (III) (C) only (I) (D) (I) and (II)
20. For a gas obeying the van der Waals’ equation, at the critical state

 P    2P   P    2P 
(A)both  V  and  V 2  are zero (B) both  V  and  V 2  are not zero
 TC   TC  TC   TC

 P    2P   P    2P 
(C)  V  is zero but  2  is non-zero (D)  V  is non-zero but  2  is zero
  Tc  V  TC  TC  V  TC
21. Select the incorrect statement:
(A) a real gas above its critical temperature can not be liquified at any pressure.
(B) an ideal gas can be liquified below its circtical temperature.
(C) a real gas below its critical temperature can be liquified by applying pressure.
(D) critical temperature is a maximum temperature at which real gas can be liquified.
37
JEE-Chemistr y
22. NH3 gas is liquefied more easily than N2. Therefore,
(A) vander Waal’s constant a and b of NH3 > that of N2
(B) vander Waal’s constant a and b of NH3 < that of N2
(C) a (NH3) > a (N2) but b (NH3) < b (N2)
(D) a (NH3) < a (N2) but b (NH3) > b (N2).
23. The van der Waals’s constants for gases A, B and C are as follows
Gas a(L2atm mol–2) b (Lmol–1)
A 0.024 0.027
B 4.17 0.037
C 3.59 0.043
Based upon the above data, which of the following statements is correct?
(i) The gas B has the highest critical temperature
(ii) The gas A has minimum departure from the ideal behaviour
(iii) The gas C has largest molecular volume
(A) (i) (B) (i) and (ii) (C) (ii) and (iii) (D) all the three

Node-6\Target-2020-21\1.JEE(M +A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2\1.Gaseous State\Th.

38
 Gaseous State

SINGLE CORRECT
1. A gas is found to have a formula [CO]x. If its vapour density is 70 the value of x is
(A) 2.5 (B) 3.0 (C) 5.0 (D) 6.0
2. V versus T curves at constant pressure P1 and P2 for an ideal gas are shown in Fig. Which is correct

(A) P1 > P2 P1
(B) P1 < P2 P2
v
(C) P1 = P2
(D) All T
3. A football bladder contains equimolar proportions of H2 and O2. The composition by mass of the mixture
effusing out of punctured football is in the ratio (H2 : O2)

(A) 1 : 4 (B) 2 2 : 1 (C) 1 : 2 2 (D) 4 : 1

4. Calculate the ratio of rate of effusion of O2 and H2 from a container containing 16gm O2 and 2gm H2
(A) 1 : 8 (B) 8 : 1 (C) 1 : 4 (D) 4 : 1
5. The number of effusion steps required to convert a mixture of H2 and O2 from 240 : 1600 (by mass) to
3072 : 20 (by mass) is
(A) 2 (B) 4 (C) 5 (D) 6
6. A rigid container containing 10 gm gas at some pressure and temperature. The gas has been allowed to escape
(do not consider any effusion or diffusion) from the container due to which pressure of the gas becomes half of
rd
its initial pressure and temperature become  2 3  of its initial. The mass of gas (in gms) escaped is

(A) 7.5 (B) 1.5 (C) 2.5 (D) 3.5

7. For the reaction
2NH3(g)  N2(g) + 3H2(g),
what is the % of NH3 converted if the mixture diffuses twice as fast as that of SO2 under similar conditions.
(A) 3.125 % (B) 31.25 % (C) 6.25 % (D) 62.5 %
8. A gaseous reaction,
3A  2B
is carried out in a 0.0821 litre closed container initially containing 1 mole of gas A. After sufficient time a
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

curve of P (atm) vs T (K) is plotted and the angle with x-axis was found to be 42.95°. The degree of
association of gas A is [Given : tan 42.95 = 0.8]
(A) 0.4 (B) 0.6 (C) 0.5 (D) 0.8
9. At STP, the order of root mean square speed of molecules H2, N2, O2 and HBr is :
(A) H2 > N2 > O2 > HBr (B) HBr > O2 > N2 > H2
(C) HBr > H2 > O2 > N2 (D) N2 > O2 > H2 > HBr
10. Four particles have speed 2, 3, 4 and 5 cm/s respectively. Their rms speed is :

 27   54 
(A) 3.5 cm/s (B)   cm/s (C) 54 cm/s (D)  2  cm/s
 2   

11. If the average velocity of N2 molecules is 0.3 m/sec. at 270C, then average velocity of 0.6 m/sec will be at :
(A) 273 K (B) 927 K (C) 1000 K (D) 1200 K

39
JEE-Chemistr y
12. The average velocity of an ideal gas molecule at 270C is 0.3 m/sec. The average velocity at 9270C will be :
(A) 0.6 m/sec (B) 0.3 m/sec. (C) 0.9 m/sec. (D) 3.0 m/sec.
13. The ratio between total translational kinetic energies of 16 g of O2 and 28 g of N2 respectively at 300 K will be
(A) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) 4 : 7
–1
14. A cylinder contains 100 g of an ideal gas (Mol. wt. = 40 g mol ) at 27°C and 2 atm pressure. In transportation
the cylinder fell and a dent was created. The valve present cannot keep the pressure greater than 2 atm. Hence,
10 g of gas got leaked out. The volume of the container before and after dent is :
(A) 30.8 L, 27.7 L (B) 27.7 L, 30.8 L (C) 30.8 L, 30.8 L (D) 27.7 L, 27.7 L
15. The distribution of molecular speeds for CO2 at different temperatures is given below, which of the following is
incorrect ?

(A) It represents Maxwell’s distribution curve

(B) Temperature of C2 graph is more than that of C1 1 dN Cl
(C) The average velocity of molecules in C2 graph is more than C1 N du C2

1
(D) Velocity  , therefore, molecular mass of molecules in C1 > C2 . Molecular speed
M
16. For two gases P and Q with molecular weights Mp and MQ it is observed that at a certain temperature T the
mean velocity of P is equal to the root mean square velocity of Q, Thus the root mean square velocity of P and
Q will be equal if
(A) P is lowered to a temperature T2 (T2 < T) and Q is maintained at temperature T
(B) P is at a temperature T and Q at a temperature T2 where T > T2
(C) both P and Q are raised to higher temperature
(D) both P and Q are placed at lower temperature
17. Calculate the number of moles of gas present in the container of volume 10 L at 300 K. If the manometer
containing glycerin shows 5 m difference in level as shown diagram.

(Given : d glycrin = 2.72 g/mL; dmercury = 13.6 g/mL)

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

(A) 0.94 mole (B) 0.49 mole (C) 0.64 mole (D) none of these
18. A gaseous mixture containing He, CH4 and SO2 was allowed to effuse through a fine hole then find what molar
ratio of gases coming out initially? If mixture contain He, CH4 and SO2 in 1 : 2 : 3 mole ratio,

(A) 2 : 2 : 3 (B) 6 : 6 : 1 (C) 2 : 2 : 3 (D) 4 : 4 : 3

19. The values of vander waals' constant 'a' for the gases O2, N2, NH3 and CH4 are 1.360, 1.390, 4.170 and 2.253
L atm mol–2 respectively. The gas which can most easily be liquefied is :
(A) O2 (B) N2 (C) NH3 (D) CH4
20. Correct option regarding a container containing 1 mol of a gas in 22.4 litre container at 273 K is
(A) If compressibility factor (z) > 1 then 'P' will be less than 1 atm.
(B) If compressibility factor (z) > 1 then 'P' will be greater than 1 atm.
(C) If 'b' dominates, pressure will be less than 1 atm.
(D) If 'a' dominates, pressure will be greater than 1 atm.

40
 Gaseous State
21. Graph depicting correct behaviour of ideal gas & H2 gas will be (neglect a)

(A) (B) (C) (D)

22. Two container each containing liquid water are connected as shown in diagram.

Given that vapour pressure of H2O(l) at 300 K & 350 K are 22 mm of Hg and 40 mm of Hg. The final pressure
in each container if valve is opened while keeping the containers at the given temperature is
(A) 22 mm of Hg (B) 40 mm of Hg (C) 31 mm of Hg (D) 62 mm of Hg
23. Fraction of molecules (’) are related with velocity according to relation.
3 9
 '   v 2  3v  {1  v  3}
4 4
then find most probable speed?
(A) 0 (B) 1 (C) 2 (D) 3
MORE THAN ONE OPTION CORRECT
24. Select the correct observation for a 8.21 lit container, filled with 2 moles of He at 300 K.,
(A) It has pressure 6 atm
(B) If it is an open rigid container, its pressure increases to 8 atm on heating to 400 K.
(C) If it is closed non-rigid (like thin skin balloon), its volume increases to 16.42 lit. on heating to 600 K
(D) When connected with another similar empty container maintained at 150 K while maintaining original

2
container at 300 K, pressure reduces to atm.
3
25. Select the correct option(s):
(A) Pressure in container-I is 3 atm before opening the valve.
(B) Pressure after opening the valve is 3.57 atm.
(C) Moles in each compartment are same after opening the valve.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

(D) Pressure in each compartment are same after opening the valve.
26. A container fitted with frictionless massless piston consist of five valves–I, II, III, IV and V. These valves
open automatically if pressure exceed over 1.5, 2.2, 2.5, 4.4 and 4.8 atm respectively. Under the given
initial conditions (mentioned in given diagram) system is in state of equilibrium. Piston is now pressed in
downward direction very slowly.
[Note: Consider the diameter of valve tube negligible and temperature remain constant.]
Select the correct option(s):
(A) Valve –II will be opened first 15cm
(B) As the piston crosses the valve which will be
40cm

Valve-I
P= 1 atm
45cm

30cm
50cm

opened first, the remaining number of moles in

60cm

Valve-II
5 Valve-III T= 300 K
container are .
3 Valve-IV
Valve-V
(C) Valve–V will be the second valve which open 10cm

(D) Number of moles will zero as piston crosses Valve–V Base area= 821 cm2

41
JEE-Chemistr y
27. An open ended mercury manometer is used to measure the pressure exerted by a trapped gas as shown in the
figure. Initially manometer shows no difference in mercury level in both columns as shown in diagram.

After sparking 'A' dissociates according to following reaction

2A(g)  3B(g) + 2C(g)
If pressure of Gas "A" decreases to 0.8 atm. Then
(Assume temperature to be constant and is 300 K)
(A) total pressure increased by 1.3 atm
(B) total pressure increased by 0.3 atm
(C) total pressure increased by 22.3 cm of Hg
(D) difference in mercury level is 228 mm.
28. Select the correct statement :
(A) The value of compressibility factor ‘Z’ for H2 gas is greater than one at room temperature and pressure
(B) The real gas behaves as an ideal gas at Boyle’s temperature in a wide range of pressure at a low pressure.

8a
(C) For a real gas following van der Waal’s equation of state, the expression of critical temperature is
27R.b

P.b
(D) At low pressure, the compressiblity factor ‘Z’ = 1+ for a van der Waal’s gas.
RT
29. The graph of P vs. V is given at different temperatures and, n1, n2, n3 are number of moles

The correct relationship are :

(A) If n1 = n2 = n3 then T1 > T2 > T3 P
(B) If n1 = n2 = n3 then T1 < T2 < T3 T1, n3
T2, n2
(C) If T1 = T2= T3 then n1 > n2 > n3 T3, n1
(D) If T1 = T2= T3 then n3 > n2 > n1 V
30. Two vessels having equal volumes contains H2 and He at 1 and 2 atm respectively at same temperature. Select
the correct statements :

rHe
(A) urms (H2) = urms (He) (B) rH2 
2

(C) urms(H2) = 2 urms (He) (D) rH2  8 rHe

31. Which of the following statements on critical constants of gases are correct ?
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

Tc
(A) Larger P the value of a gas, larger would be the excluded volume.
c

(B) Critical temperature (Tc) of gas is greater than its Boyle temperature (Tb)

 p 
(C) At the critical point in the van der Waals’ gas isotherm  V   0
 m Tc
(D) All are correct
32. A gas described by van der Waals’ equation :
(A) behaves similar to an ideal gas in the limit of large molar volumes
(B) behaves similar to an ideal gas in the limit of large pressures.
(C) is characterised by van der Waals coefficients that are dependent on the identity of the gas but are indepen-
dent of the temperature.
(D) has the pressure that is lower than the pressure exerted by the same gas behaving ideally.
42
 Gaseous State
33. Select the incorrect statement(s):
(A) At Boyle's temperature a real gas behaves like an ideal gas irrespective of pressure.
(B) At critical condition, a real gas behaves like an ideal gas.
(C) On increasing the temperature four times,collision frequency (Z11) becomes double at constant volume.
(D) At high pressure Vander Waal's constant 'b' dominates over 'a'.
34. Which of the following statement(s) are true about Z vs P graph for a real gas at a given temperature.

behaviour of most
P real gases at ordinary
tempertaure

(A) dZ dP  0 as P  0 for most real gases

(B) dZ dP = –ive as P  0 for most real gases

(C) dZ dP  0 at a pressure where repulsive and attractive forces are comparable.

(D) dZ dP = +ive for real gases at extremely high pressure.

35. Choose the correct alternative (more than one may be correct) (B.M.C.= Bimolecular collision)
(at constant V) (n- is constant throughout)

(A)  is constant

(B) BMC made by 1 molecule per second is directly proportional to P .

(C) BMC for all the molecules per unit volume is directly proportional to T 3/2.
(D) none of these

V
B
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

C
36. A

T
With reference to above graph, which of the following is/are incorrect.

(A) PA = PB = PC (B) Pressure first increases then decreases

(C) PC > PA (D) PB < PA

43
JEE-Chemistr y

[Note: * Mark Represents Multiple Choice Questions]

Comprehension Based Questions
Paragraph -1 (2 questions)
For two gases A and B, P v/s V isotherms are drawn at T K as shown. TA & TB are critical temperatures of A
& B respectively

1. Which of following is true?

(A) TA < T < TB (B) TA > T > TB (C) TA > TB > T (D) none of above
2. The correct statement(s) is/are
(I) Pressure correction term will be more negligible for gas B at T K.
(II) The curve for gas 'B' will be of same shape as for gas A if T > TB
(III) Gas 'A' will show same P v/s V curve as of gas 'B' if T > TA
(A) III only (B) II and III (C) II only (D) All
Comprehension-2 (Q. No. 3 to 5)
On the recently discovered 10th planet it has been found that the gases follow the
relationship PeV/2 = nCT where C is constant and other notation are as usual (V
in lit., P in atm and T in Kelvin). A curve is plotted between P and V at 500 K &
2 moles of gas as shown in figure

3. The value of constant C is

(A) 0.01 (B) 0.001 (C) 0.005 (D) 0.002
4. Find the slope of the curve plotted between P Vs T for closed container of volume 2 lit. having same moles of
gas

e 2
(A) (B) 2000 e (C) 500 e (D)
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

2000 1000e
5. If a closed container of volume 200 lit. of O2 gas (ideal gas) at 1 atm & 200 K is taken to planet. Find the
pressure of oxygen gas at the planet at 821 K in same container

10 20
(A) (B) (C) 1 atm (D) 2 atm
e100 e50
Comprehension-3 (Q. No. 6 to 7)
A gaseous reaction,
2A(g)  3B(g) + C(g)
whose extent of dissociation depends on temperature is performed in a closed container, it is known that extent
of dissociation of A is different in different temperature range. With in a temperature range it is constant.
(Temperature range T0 – T1, T1 – T2, T2 – T). A plot of P v/s T is drawn under the given condition. Given :
tan55 = 1.42, tan50 = 1.19, tan60 = 1.73

44
 Gaseous State

6. If  Ti Ti 1 is the degree of dissociation of A then in the temperature range Ti  Ti + 1

(A)  T T is lowest (B)  T T is highest (C)  T  T = 1 (D)  T  T = 0

0 1 0 1 2  2 

*7. If initially 1 mole of A is taken in a 0.0821 l container then [R = 0.0821 atm lit / k]

(A)  T T = 0.19 (B)  T T = 0.095 (C)  T  T  0.42 (D)  T1  T2  0.73

0 1 0 1 1 2

Comprehension-4 (Q. No. 8 to 9)

Grahm’s Law of Diffusion. The phenomenons of spontaneous intermixing of gases against the law
of gravitation is known as diffusion. If diffusion occurs through small orifice of the container, then it is known
as effusion.

PA
The rate of effusion is defined as,  
2  RTM

where P is partial pressure of the gas

A is area of cross-section of the orifice of the container

M is the molar mass of the gas Rate of diffusion

Vol. effused Moles effused Pr essure drop dis tan ce travelled

   
Time Time t time

Answer the following questions on the basis of write up :

8. 1 mole of gas A and 4 moles of gas O2 is taken inside the vessel, which effuse through the small orifice of the
vessel having same area of cross-section and at the same temperature, then the correct % of effused volume
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

of gas A and O2 initially respectively is ? (Assume that the gas A does not react with O2 gas and molar mass
of gas A is 2 g)

(A) 50%, 50% (B) 60%, 40% (C)30%, 70% (D)10%, 90%.

9. 1 mole of gas “X” and 2 moles of gas “Y” enters from the end “P” and “Q” of the cylinder respectively. The
cylinder has the area of cross-section A, shown as under.

The length of the cylinder is 150 cms. The gas “X” intermixes with
gas “Y” at the point A. If the molecular weight of the gases X and Y
is 20 and 80 respectively, then what will distance of point A from Q ?

(A) 75 cms (B) 50 cms (C)100 cms (D)90 cms.

45
JEE-Chemistr y
Comprehension-5 (Q. No. 10 to 12)
Deviation of real gas from ideal behavior is given by plot of Z Vs P.

H2
N2
CH4
Z Ideal gas
CO2

For ideal gas Z =1, for real gas Z > 1 or Z < 1

10. Correct order for liquification is :
(A) H 2  N 2  CH 4  CO 2 (B) CO 2  CH 4  N 2  H 2

(C) H 2  CH 4  N 2  CO 2 (D) CH 4  H 2  N 2  CO 2
11. For which case, Vander Waal constant ‘a’ is maximum :
(A) H2 (B) N2 (C) CH4 (D) CO2
12. For which gas slope is positive at high pressure :
(A) H2 (B) N2 (C) CH4 (D) All of these
Comprehension-6 (Q. No. 13 to 15)
Van der Waal’s equation for calculating the pressure of a non ideal gas is

 an 2 
 P  2  (V  nb)  n RT
 V 

van der Waal’s suggested that the pressure exerted by an ideal gas, Pideal, is related to the experimentally
measured pressure, Preal by the equation

an 2
Pideal  Preal 
V2
 
observed correction
pressure term
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

Constant a is measure of intermolecular interaction between gaseous molecules that gives rise to nonideal
behaviour depends on how frequently any two molecules approach each other closely. Another correction
concerns the volume occupied by the gas molecules. In the ideal gase equation, V represents the volume of the
container. However, each molecule does occupy a finite, althogh small, intrinsic volume, so the effective
volume of the gas becomes (V – nb), volume occupied by n moles of the gas.

Having taken into account the corrections for pressure and volume, we can rewrite the ideal gas equation as
follows :

 an 2 
 P   (V  nb)  nRT
 V2 
corrected corrected
pressure volume

46
 Gaseous State
13. At relatively high pressure, the van der Waal’s equation of state reduces to :

(A) PV = RT – a/V (B) PV = aRT/V2

(C) P = RT – a/V2 (D) PV = RT + Pb
14. For non-zero value of force of attraction between gas molecules for large volume, gas equation will be :

n 2a
(A) PV  nRT  (B) PV  nRT  nbP
V

nRT
(C) P  (D) PV  nRT
Vb

15. The van der Waal’s constant ‘a’ for CO2 gas is greater than that of H2 gas. Its mean that the :

(A) strength of van der Waal’s force of CO2 gas is less than that of H2 gas
(B) strength of van der Waal’s force of CO2 gas is equal to that of H2 gas

(C) CO2 gas can be more easily liquified

(D) H2 gas can be more easily liquified

Comprehension-7 (Q. No. 16 to 18)
Andrew observed the critical phenomenon for CO2 gas. The critical temperature is the temperature at which or
below which gas can be liquified by applying pressure. Pressure and volume corresponding to critical temperature
are critical pressure and volume respectively. For critical phenomenon, on solving vander waal equation we get:

8a a
TC  VC = 3b PC 
27Rb 27b 2

Boyle temperature is the temperature at which real gas behaves like an ideal gas in wide range of pressure :

a
TB 
Rb
16. Relation between Boyle temperature (TB) and critical temperature is :
(A) TC = TB (B)TC < TB (C)TC > TB (D)None of these
17. Critical temperature of SO3 is greater than CO2. Which statement is wrong regarding this concept
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

(A) SO3 can be liquified more easily than CO2

(B) Vander Waal constant ‘a’ is larger for SO3 than CO2
(C) SO3 show less deviation than CO2 from ideal gas behaviour
(D) SO3 can be liquified at the critical temperature of CO2.
18. Compressibility factor (Z) for critical phenomenon is given by :
(A) 1 (B) 0.375 (C)1.2 (D)0.225
Comprehension-8 (Q. No. 19 to 21)
A gaseous mixture comprising of equal moles of H2/O2/M (M mass = 128) was subjected to series of effusion.
What will be the number of effusion steps required so as to change the composition to
19. One in which lightest : Heaviest gas is 4096:1. What will be the composition of this mixture (w.r.t. all the gases).
(A) 4, 4096:16:1 (B) 6, 4096×64:64:1 (C) 4, 2048:8:1 (D) 5, 4096:16:1

47
JEE-Chemistr y
20. One in which H2:O2 is 4096:1. What will be the composition of this mixture (w.r.t. all the gases)
(A) 4, 4096:16:1 (B) 6, 4096×64:64:1 (C) 4, 2048:8:1 (D) 5, 4096:16:1
21. Is it possible to obtain through successive effusion only a mixture comprising of H2:O2:M in the ratio 512 : 8 : 1.
If yes, after how many effusion steps
(A) Yes, step 3 (B) Yes, step 5 (C) Yes, step 2 (D) Not possible
Comprehension-9 (Q. No. 22 to 23)

378
8 mole of a mixture of N2, NO2 and N2O4 has a mean molecular mass of . On heating to a temperature
8
378
at which N2O4 dissociated completely (N2O4  2NO2), the mean molecular mass becomes .
9
22. The ratio of number of moles of N2 : NO2 : N2O4 in original mixture is
(A) 3 : 4 : 1 (B) 2 : 5 : 1 (C) 3 : 5 : 2 (D) 4 : 2 : 1
23. The ratio of number of moles of N2 and NO2 after heating is
(A) 1 : 1 (B) 3 : 9 (C) 2 : 7 (D) 1 : 2
Match the column
24. On the basis of the kinetic theory of gases (for an ideal gas)
Column-I Column-II

1m
(A) Pressure exerted by the gas (P) p= Nv 2rms
3V

3
(B) Molar translational K.E. (Q)  RT
2

(C) Average translational K.E.  Tn , n = ? (R) n=–1

(D) u 2rms dn at constant pressure, (S) n=1

d = density, n = ?
25. Column-I Column-II

 a 
(A) If force of attraction among the (P)  P  2  (Vm  b)  RT
 Vm 
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

gas molecules be negligible

a
(B) If the volume of the gas molecules be negligible (Q) PVm  RT 
Vm

(C) At STP (R) PVm = RT + Pb

(D) At low pressure and at high temperature (S) PVm = RT
*26. Column – I Column – II
(A) Hydrogen gas (P = 200 atm, T = 273K) (P) Compressibility factor  1
(B) Hydrogen gas (P ~ 0, T = 273 K) (Q) Attractive forces are dominant
(C) CO2(P = 1 atm, T = 273 K) (R) PV = nRT
(D) Real gas with very large molar volume (S) P(V – nb) = nRT

48
 Gaseous State

Very Short Answer (1 Mark)

1. What is triple point of a substance ?
Ans. It is the point at which solid, liquid and vapour of a substance are in equilibrium with each other. For
example, triple point of water is the temperature at which ice, water and its vapour coexist.
2. HCl is gas while HF is liquid at room temperature, why ?
Ans. HF molecules are associated with intermolecular H-bonding, therefore, it is liquid whereas HCl is gas because
less Vander Waal’s forces of attraction.
3. What is boiling point of water at (i) higher altitudes, (ii) in pressure cooker ?
Ans. (i) < 100°C (ii) > 100° C.
4. Why is air denser at lower level than at higher altitudes ?
Ans. Heavier air will come down and lighter air goes up. Air at lower level is denser since it is compressed by mass
of air above it.
5. What is dry ice ? Why is it so called ?
Ans. Solid CO2 It is because solid CO2 is directly converted into gaseous state (sublimes) and does not change
into liquid, so it is called dry ice.
6. A rubber balloon permeable to hydrogen in all its isotopic forms is filled with deuterium (D2) and then placed
in a box containing pure hydrogen. Will the balloon expand or contract or remains as it is ?
Ans. Balloon will expand because rate of diffusion of H 2 is greater than that of D2 .
7. What type of graph would you get when PV is plotted against P at constant temperature ?
Ans. A straight line parallel to pressure axis.
8. Name and state the law governing the expansion of gases when they are heated or cooled at constant
pressure.
Ans. Charle’s Law.
9. At a certain altitude, the density of air is 1/10th of the density of the earth’s atmosphere and temperature
is –10°C. What is the pressure at that altitude ? Assume that air behaves like an ideal gas, has uniform
composition and is at S.T.P. at the earth’s surface.
P1 V1 P2 V2 P1 V1 T2
Ans. T1

T2 or P2  T V .
1 2

1 P1 T2  d2  760  263  1 
But d  . Hence P2        73.2 mm.
T1 d  273
V  1  10 

10. How much time it would take to distribute one Avogadro’s number of wheat grains, if 1010 grains aree
distributed each second ?
Ans. Number of years
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

6.023  10 23
 10
 1,908,00 years.
10  365  24  60  60
11. A chamber of constant volume contains hydrogen gas. When the chamber is immersed in a bath of melting
ice (0°C), the pressure of the gas is 1.07  10 2 kPa. What pressure will be indicated when the chamber is
brought to 100°C ?
Ans. T1  273  0  273 K

p1  1.07  10 2 kPa  107 kPa

T2  273  100  373 K p2  ?

Since volume remains constant, therefore, according to Gay Lussac’s law.
p1 p2 pT
1 2 (107 kPa)  (373 K )

T1 T2 or T2  p 
(273 K )  1.462  10 2 kPa.
2

49
JEE-Chemistr y

12. What would be the S.I. unit for the quantity pV 2T 2 / n ?

pV 2 T 2 ( Nm 2 ) (m 3 )2 (K)2
Ans. 
n mol

 Nm 4 K 2 mol 1.
13. What is the value of universal gas constant ? What is its value in SI units ?
Ans. R  8.314 JK 1 mol 1 .
14. Explain the significance of the vander Waal’s parameters ?
Ans. ‘a’ is a measure of the magnitude of the intermolecular forces of attraction while b is a measure of the
effective size of the gas molecules.
15. Give most common application of Dalton’s law.
Ans. The air pressure decreases with increases in altitude. That is why jet aeroplane flying at high altitude need
pressurization of the cabin so that partial pressure of oxygen is sufficient for breathing.
16. N 2O and CO2 have the same rate of diffusion under same conditions of temperature and pressure. Why ?

Ans. Both have same molar mass ( 44 g mol 1 ). According to Graham’s law of diffusion, rates of diffusion of
different gases are inversely proportional to the square root of their molar masses under same conditions of
temperature and pressure.
17. At what temperature will oxygen molecules have the same K.E. as ozone molecules at 30°C ?
Ans. At 30°C, kinetic energy depends only on absolute temperature and not on the identity of a gas.
18. Which two postulates of the kinetic molecular theory are only approximations when applied to real gases ?

Ans. (i) Inter molecular forces between molecules are negligible.

(ii) Molecules of a gas have negligible volumes.
19. Account for the following properties of gases on the basis of kinetic molecular theory,
(i) High compressibility
(ii) Gases occupy whole of the volume available to them.
Ans. (i) High compressibility is due to large empty spaces between the molecules.
(ii) Due to absence of attractive forces between molecules, the molecules of gases can easily separate from
one another.
20. Critical temperature of carbon dioxide and CH 4 are 31.1°C and –81.9°C respectively. Which of these has
stronger intermolecular forces and why ?
Ans. Higher the critical temperature, more easily the gas can be liquefied i.e. greater are the intermolecular forces
of attraction. Therefore, CO2 has stronger intermolecular forces than CH4 .
Short Answer (2 & 3 Mark)
21. (i) What will be the pressure exerted by a mixture of 3.2 g of methane and 4.4 g of carbon dioxide contained
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

in a 9 dm3 flask at 27 °C ?
(ii) Give two example of Covalent solids.
Or
(i) Calculate the total number of electrons present in 1.4 g of nitrogen gas.
(ii) Which of the two gases, ammonia and hydrogen chloride, will diffuse faster and by what factor ?
(iii) Why urea has sharp melting point but glass does not?
nRT 3.2 0.0821 L atm K 1 mol 1  300 K
Ans. (i) pCH4  V  16  9L

0.2  24.63 4.926

pCH 4    0.547 atm
9 9

4.4 0.0821 300 0.1 24.63 2.463

pCO2      0.273 atm
44 9L 9 9
Total pressure = 0.547 atm + 0.273 atm = 0.820 atm

50
 Gaseous State
(ii) Boron and silicon are example of Covalent solids.
Or
(i) 28 g of Nitrogen gas contains 2  7  6.023  10 23 electrons.

2  7  6.023  10 23
1.4 g of Nitrogen gas contains  1.4
28

2  7  6.023  1023 84.32  1023

 
20 20

 4.2161  10 23 electrons.
(ii) NH3 will diffuse faster

rNH 3 36.5
  2.14  1.46 times faster..
rHCl 17
(iii) Urea is a crystalline solid therefore it has sharp melting point whereas glass does not have sharp melting point
because it is amorphous, i.e., does not have regular three dimensional structure.
22. What will be the minimum pressure required to compress 500 dm3 of air at 1 bar to 200 dm3 at 30 °C ?

Ans. V1  500 dm 3 V2  200 dm 3

P1  1 bar P2  ?

P1 V1  P2 V2

3 3 500
1 bar  500 dm  P2  200 dm  P2   2.5 bar..
200
23. A manometer is connected to a gas containing bulb. The open arm reads 43.7 cm whereas the arm connected
to the bulb reads 15.6 cm. If the barometric pressure is 743 mm mercury, what is the pressure of the bulb
reads 15.6 cm. If the barometric pressure is 743 mm mercury, what is the pressure of the gas in bar ?

Ans. Pressure of gas = Atmospheric pressure + Difference between levels of Hg

= 743 mm + (43.7 cm  15.6 cm)
= 74.3 cm+ 28.1cm
102.4
P = 102.4 cm P in bar =  1.347 bar..
76
24. Calculate the number of moles of hydrogen (H2) present in a 500 cm3 sample of hydrogen gas at a pressure
of 760 mm Hg and 27 °C.
Ans. PV  nRT , P  1 atm, V  500 cm 3 , n  ?,
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

R  82.1 atm cm 3 K 1mol 1 , T  300 K

1 atm,  500 cm3

n  0.02 mol.
(82.1 atm cm3 K 1mol 1 )  (300 K )
25. 34.05 ml of phosphorus weight 0.0625 g at 546 °C and 1 bar pressure. What is the molar mass of phosphorus?
Or
In terms of Charle’s law explain why –273 °C is the lowest possible temperature.
Ans. pV  nRT

34.05 0.0625
1 bar  L  0.083  819 K
1000 M

0.0625  0.083  819 K  1000 4248.5625

M 
34.05 34.05

M  124.77 g mol 1

51
JEE-Chemistr y
Or
Charle’s plotted the volume against temperature in °C. These plots when extraplotted intersect the temperature
axis at the same point 273C. He concluded that all gases at this temperature could have zero volume and
below this temperature volume would be negative. It shows 273C is lowest temperature attainable.
26. A vessel of 120 mL capacity contains a certain amount of gas at 35°C and 1.2 bar pressure. The gas is
transferred to another vessel of volume 180 mL at 35°C. What would be its pressure ?
Ans. Since temperature and amount of gas remains constant, therefore, Boyle’s law is applicable.
p1 V1  p 2 V2

p1  1.2 bar p2  ?

V1  120 mL V2  180 mL

 1.2  120  p 2  180

1.2  120
 p2  180
 0.8 bar..

27. A balloon is filled with hydrogen at room temperature. It will burst if pressure exceeds 0.2 bar. If at 1 bar
pressure the gas occupies 2.27 L volume, upto what volume can the balloon be expanded ?

Ans. According to Boyle’s law, at constant temperature,

p1 V1  p 2 V2

If p1  1 bar then V1  2.27 L

If p 2  0.2 bar, then

p1 V1 1 bar  2.27 L
V2    11.35 L
p2 0.2 bar
Since balloon bursts at 0.2 bar pressure, the volume of the balloon should be less than 11.35 L.
28. A student forgot to add the reaction mixture to the round bottomed flask at 27°C but instead, he/she placed
the flask on the flame. After a lapse of time, he realized his mistake, and using a pyrometer, he found the
temperature of the flask was 477°C. What fraction of air would have been expelled out ?
Ans. Suppose volume of vessel  V cm 3
i.e., volume of air in the flask at 27C  Vcm3

V1 V2 V V
 , i.e.,  2 or V2  2.5 V
T1 T2 300 750

 Volume expelled  2.5 V  V  1.5 V

1.5 V 3
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Fraction of air expelled   .

2.5 V 5
29. What is the difference in pressure between the top and bottom of a vessel 76 cm deep at 27°C when filled
with (i)water (ii)mercury? Density of water at 27°C is 0.990 g cm–3 and that of mercury is 13.60 g cm–3.
Ans. Pressure = height  density  g
Case (i). Pressure
 76 cm  0.99 g / cm 3  981 cm / s 2

 7.38  10 4 dynes cm 2

 0.073 atm (1 atm  1.013  10 6 dynes cm 2 )

Case (ii). Pressure
 76 cm  13.6 g / cm 3  981 cm / s 2

 1.013  10 6 dynes cm 2  1 atm.

52
 Gaseous State
30. An iron cylinder contains helium at a pressure of 250 kPa at 300K. The cylinder can withstand a pressure of
1  10 6 pa. The room in which cylinder is placed catches fire. Predict whether the cylinder will blow up before
it melts or not. (M.P. of the cylinder = 1800 K)
Ans. P1  250 K Pa, T1  300 K

P2  ? T2  1800 K
Applying pressure – temperature law
P1 P2 250 P2
  or P2  1500 kPa
T1 T2  300 1800

As the cylinder can withstand a pressure of 10 6 Pa  10 3 kPa  1000 kPa, hence it will blow up.
31. On a ship sailing in a pacific ocean where temperature is 23.4°C, a balloon is filled with 2 L air. What will be
the volume of the balloon when the ship reaches Indian ocean, where temperature is 26.1°C ?

Ans. According to Charles’ law

V1 V2

T1 T2

V1  2 L V2  ?

T1  273  23.4  296.4 K T2  273  26.1  299.1

V1 T2 2L  299.1 K
 V2  T   2.018 L.
1 296.4 K

32. What is the increase in volume when the temperature of 800 mL of air increases from 27 °C to 47°C under
constant pressure of 1 bar ?
Ans. Since the amount of gas and the pressure remains constant, Charles’ law is applicable. i.e.
V1 V2

T1 T2

V1  800 mL V2  ?

T1  273  27  300 K ; T2  273  47  320 K

800 mL V2 (800 mL)

 or V2   (320 K )  853.3 mL.
300 K 320 K (300 K )

 Increase in volume of air  853.3  800  53.3 mL.

33. A cylinder containing cooking gas can withstand a pressure of 14.9 atmospheres. The pressure gauge of the
cylinder indicates 12 atmosphere at 27°C. Due to sudden fire in the building, temperature starts rising. At
what temperature will the cylinder explode ?
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Ans. Since gas is confined in a cylinder, its volume will remain constant
Initial conditions Final conditions
p1  12 atm p 2  14.9 atm

T1  273  27  300 K T2  ?
At constant volume
p1 p 2 p 2 T1
 or T2 
T1 T2 p1

14.9  300
  372.5 K
12.0
or Temperature at which cylinder explodes
 372.5  273  99. 5C.

53
JEE-Chemistr y

34. What will be the pressure exerted by a mixture when 0.5 L of H 2 at 0.8 bar and 2.0 L of oxygen at 0.7 bar
are introduced in 1 L container at 27 °C.
Ans. P1 V1  P2 V2 0.8  0.5 L  1  P2
P2  0.4 bar P1 V1  P2 V2

0.7 bar  2.0  P2  1  P2  1.4 bar

Total pressure  0.4 bar + 1.4 bar = 1.8 bar..
35. Calculate the temperature of 4.0 moles of a gas occupying 5 dm3 at 3.32 bar
(R = 0.083 bar dm3 K–1 mol–1).
Ans. According to ideal gas equation :
pV  nRT

p  3. 32 bar, V  5 dm 3 , n  4. 0 mol.
3 1 1
R  0.083 bar dm K mol

pV 3.32 bar  5 dm3

T   50 K.
nR 4.0 mol  0.083 bar dm3 K 1 mol 1
36. When 2g of gas A is introduced into an evacuated flask kept at 25°C, the pressure is found to be 1 atm. If 3
g of another gas B is then added to the same flask the total pressure becomes 1.5 atm at the same temperature.
Assuming ideal behaviour of gases, calculate the ratio of molecular weights M A : M B .
Ans. According to ideal gas equation,
pV  nRT

mRT
or pV 
M
m m
or M RT n 
pV M

Let the molecular weight of A and B be M A and M B respectively..

RT 3 RT
MA  2 and MB 
1 V 0.5  V

MA 2 1
or   0.5 
MB 3 3

 M A : M B  1 : 3.
37. An evacuated glass vessel weighs 50.0 g when empty, 148.0 g when filled with a liquid of density
0.98 g m–1 and 50.5 g when filled with an ideal gas at 760 mm Hg at 300 K. Determine the molecular weight
of the gas.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

Ans. Weight of liquid  148  50  98 g

Density of liquid  0.98 g ml 1
98
 Volume of liquid  0.98  100 ml .

Weight of gas  50.5  50.0  0.5 g

100
Volume  L, P  1 atm, T  300 K
1000
W
pV  nRT or pV  RT
M
1  100 0.5
  0.082  300
1000 M
1
 M  123.15 g mol .

54
 Gaseous State
38. At 0°C, the density of a gaseous oxide at 2 bar pressure is same as that of nitrogen at 5 bar. What is the
molecular mass of the gaseous oxide ?
Ans. Calculation of density of N 2 at 5 bar and 0°C

PM 5 (bar)  28 (g mol 1)

d 
RT 0.0831 (L bar K 1 mol 1)  273.15 (K )

 6.168 g L1
Calculation of molar mass of gaseous oxide
dRT
M
P

6.168 (g L1 )  0.0831 (L bar K 1 mol 1 )  273.15 (K )


2

 70.0 g mol 1.

39. Density of a gas is found to be 5.46 g/dm3 at 27°C and 2 bar pressure. What will be its density at S.T.P. ?
P1 M P M
Ans. d1  ; d2  2
RT1 RT2
d1 PT d1 T1 P2
or  1 2 or d2 
d 2 T1 P2 P1 T2
Substituting the values, we have
5.46 (g dm 3 )  300 (K)  1 (bar)
d2   5.998 or 6.0 g dm 3 .
1 (bar)  273.15 (K)
40. What will be pressure exerted by a mixture of 3.2 g of methane and 4.4 g of carbon dioxide contained in a
9 dm3 flask at 27°C ?
n w RT
Ans. p RT 
V M V

 3.2  0.0821 dm3 atm K 1 mol 1  300 K

pCH 4   mol 
 16  9 dm 3

 0.55 atm

 4 .4  0.0821 dm 3 atm K 1 mol 1  300 K

pCO 2   mol 
 44  9 dm3

 0.27 atm

pTotal  0.55  0.27  0.82 atm.

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41. Calculate the total pressure in a mixture of 8 g of O2 and 4g of H 2 confined in a vessel of dm3 at 27 °C, R
= 0.083 bar dm3 K–1 mol–1. Atomic mass of O = 16 u, H = 1 u.
Ans. pV  nRT

8 24.9
p 1   0.083  300   6.225 bar
32 4
4
p 1   0.083  300  49.80 bar
2
Total Pressure = 6.225 + 49.80=56.025 bar.
42. For 10 minutes each, at 27 °C, from two identical holes, nitrogen and an unknown gas are leaked into
common vessel of 3 L capacity. The resulting pressure is 4.18 bar and the mixture contains 0.4 mole of
nitrogen. What is the molar mass of the unknown gas ?
Ans. Moles of N 2 diffused = 0.4 mole in 10 min
Moles of unknown gas diffused  n1 moles in 10 min

55
JEE-Chemistr y

PV 4.18  3 12.54
n    0.5036
RT 0.083  300 24.90
Number of moles of unknown gas  0.5036  0.4  0.1036

rN 2 Mg nN 2 t M
   
rg 28 t ng 28

0.4 10 M
    M  417.18 g mol 1 .
10 0.1036 28
43. Pay load is defined as the difference between the mass of displaced air and the mass of the balloon.
Calculate the pay load when a balloon of radius 10 m, mass 100 kg is filled with helium at 1.66 bar at 27°C.
(Density of air = 1.2 kg m–3 and R = 0.083 bar dm3 K–1 mol–1).
Ans. Pay load is the difference between the mass of displaced air and the mass of the balloon.
4
Volume of ballon   r3
3
Radius of balloon, r  10m
4
V  3.14  (10)3  4186.7 m3
3

Mass of displaced air  4186.7 m3  1.2 kg m3

 5024.04 kg

pV
Moles of gas present 
RT

1.66  4186.7  103

  279.11  10 3 mol
0.083  300
Mass of helium present  279.11  103  4

 1116.44  10 3 g  1116.4 kg

Mass of filled balloon  100  1116.4  1216.4 kg

Pay load = mass of displaced air -– Mass of balloon
= 5024.4  1216.44  3807.6 kg.
44. A balloon of diameter 20 m weights 100 kg. Calculate the pay load if it is filled with He at 1.1 atm and 27°C.
Density of air is 1.2 kg m–3 (R = 0.082 dm3 atm K–1 mol–1).
Ans. Volume of balloon,
4
V  r 3 r  10 m
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4 3 3
 V  3  3.14  (10)  4187 m

Mass of displaced air  4187 m3  1.2 kg m3

= 5024.44 kg
PV 1  4187  103
Moles of gas present, n  
RT 0.082  298

 171.3  10 3 mol

Mass of He present  171.3  10 3  4

 685.3  10 3 g

 685.3 kg

Mass of filled balloon  100  685.3  785.3 kg

56
 Gaseous State
Pay load = Mass of displaced air – Mass of balloon
= 5024.4 – 785.3 = 4239.1 kg.
45. Using vander Waal’s equation, calculate the constant ‘a’ when two moles of a gas confined in a 4L flask
exerts a pressure of 11.0 atmospheres at a temperature of 300 K. The value of b is 0.05 L mol–1.
Ans. Vander Waals’ equation is

 2
 p  an  (V  nb)  nRT
 V 2 


n  2 mol , V  4 L, p  11 atm,

T  300 K, b  0.05 L mol 1

Substituting the values

 a4 
 11   (4  2  0.05)  2  0.082  300
 16 

176  4a
 3.9  49.2
16

(176  4 a) 3.9  49.2  16

15.6 a  787.2  686.4

a  6.4616 atm L2 mol 2 .

46. 34.05 mL of phosphorus vapour weigh 0.0625 g at 546°C and 1 bar pressure. What is the molar mass of
phosphorus ?
PV
Ans. Mole of phosphorus vapour (n) 
RT

1 (bar )  34.05  10 3 (L)

  5.0  10  4
0.0831 (bar L K 1 mol 1)  819.15 (K )

Let molar mass of phosphorus be M g mol 1.

0.0625
 Mole of phosphorus vapour 
M

0.0625 0.0625
Now,  5.0  10  4 or M 
M 5.0  10  4

 125 g mol 1 .
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

47. The drain cleaner, Drainex contain small bits of aluminium which react with caustic soda to produce hydrogen.
What volume of hydrogen at 20°C and 1 bar will be released when 0.15 g of aluminium reacts ?
Sol. The chemical reaction taking place is

2 Al  2 NaOH  2H 2O  2 NaAlO2  3H 2

2 mol 3 mol
2  27 g 3 mol

54 g of Al produces hydrogen  3 mol

0.15 g of Al produces hydrogen
3  0.15
 mol  8.33  10  3 mol
54

Calculation of volume of 8.33  10 3 mol of hydrogen at 20°C and 1 bar

nRT
V 
P
57
JEE-Chemistr y

8.33  10 3 (mol )  0.083 (bar L K 1 mol 1 )  293 (K )


1 (bar)

 0.20257 L or 202.57  10 3 mL.

48. For a real gas obeying vander Waal’s equation, a graph is plotted between PVm (y-axis) and P (x-axis) wheree
Vm is the molar volume. Find y-intercept of the graph.

Sol. For a real gas, the plot of PVm vs P can be of the type A or B but at the
point of intercept, P  0 and at any low pressure, vander Waal’s equation
B
reduce to ideal gas equation.
A
PVm
PV  nRT or PVm  RT
RT
Hence, y-intercept of graph will be = RT.

49. (i) State Graham’s law of diffusion. Arrange the gases CO2 , SO2 , NO2 in order of increasing rates of
diffusion.
(ii) What is the volume of 0.300 mol of ideal gas at 60°C and 0.821 atm pressure ?
Ans. (i) For statement of the Graham’s law. Molar mass of :
CO 2  44 u; SO 2  64 u and NO 2  46 u.

1
As rdiff .  , therefore, larger the molar mass lesser will be the rate of diffusion under similar condition.
M

Thus, increasing order of rates of diffusion is rSO2  rNO2  rCO2

nRT 0.30 (mol)  0.0821(L atmK 1 mol1 )  333(K)

(ii) V  P  0.821(atm)

 9.99 L  10.8 L.
50. Through two ends of a glass tube of length 200 cm HCl and NH3 gases are allowed to enter. At what distance
ammonium chloride will first appear ?
rNH 3 l1 M HCl 36.5
Ans.   
rHCl 200  l 1 M NH 3 17

l1
 2.147  1.465
200  l 1
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

l 1  293  1.465 l 1 ; 2.465 l 1  293

293
l1   118.88 cm
2.465
200  l 1  200  118.88  81.12 cm from HCl end.
51. Equal volumes of two gases A and B diffuse through a porous pot in 20 and 10 seconds respectively. If the
molar mass of A be 80, find the molar mass of B.

rA MB tB MB
Ans.  or 
rB MA tA MA

t A  20 sec, t B  10 sec, M A  80, M B  ?

10 MB

20 80

80
MB   20 g mol 1 .
4
58
 Gaseous State
52. A mixture of hydrogen and oxygen at one bar pressure contains 20% by weight of hydrogen. Calculate the
partial pressure of hydrogen.
Ans. As the mixture H 2 and O 2 contains 20% by weight of hydrogen, therefore, if H 2  20 g, then O 2  80 g
20 80
n H2   10 moles, nO 2   2.5 moles
2 32

n H2 10
pH2   Ptotal   1 bar  0.8 bar..
n H 2  n O2 10  2.5

53. Calculate the total pressure in a mixture of 8 g of oxygen and 4 g of hydrogen confined in a vessel of 1
dm3 at 27 °C (R = 0.083 bar dm3 K–1 mol–1).
Ans. Partial pressure of oxygen gas,

nRT
p
V

8
n mol, V  1 dm 3 , T  300 K
32

8  0.083  300
p (O 2 )   6.225 bar
32  1
Partial pressure of hydrogen gas
nRT
p
V

4
n  2 mol
2

2  0.083  300
p(H 2 )   49.8 bar
1

Total pressure  p(O2 )  p( H 2 )

 6.225  49.8  56.025 bar..

54. A vessel of 1.00 dm3 capacity contains 8.00 g of oxygen and 4.00 g of hydrogen at 27°C. Calculate the
partial pressure of each gas and also the total pressure in the container (R = 0.083 bar dm3 K–1mol–1).
Ans. Let the partial pressure of hydrogen be p H 2 and the partial pressure of oxygen be pO2 .

4
The number of mole of hydrogen (n1 )   2 mole
2
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8
The number of mole of oxygen (n2 )   0.25 mole
32
Now, applying ideal gas equation for each gas
p H 2  V  n1 RT

n1 RT 2  0.083  300
p H2    49.8 bar
V 1

Similarly, p O2 V  n 2 RT

n 2 RT 0.25  0.083  300

p O2    6.225 bar
V 1
Total pressure of gaseous mixture
 p H 2  p O2  49.8  6.225  56.025 bar.

59
JEE-Chemistr y
55. Calculate
(i) Average kinetic energy of 32 g of methane molecules at 27°C R =8.314 JK–1 mol–1.
(ii) Root mean square speed and (ii) Most probable speed of methane molecule at 27°C.
3n RT
Ans. (i) Average kinetic energy is given as E k 
2

32
Here, n   2; R  8.314 JK 1 mol 1 ; T  300 K
16

3  2  8.314  300
 Ek   7482.6 J
2
(ii) Root mean square speed is given as

3 RT
urms 
M

Here use R  8.314  10 7 ergs K 1 mol 1 to get speed in cm s 1

3  8.314  107  300

urms   68385.85 cm s 1  68.38 ms1
16
(iii) Most probable speed
urms 683.8
( )    558.7 ms 1.
1.224 1.224
56. Calculate root mean square speed (rms) of ozone which is kept in a closed vessel at 20°C and a pressure of
82 mm of Hg.
Ans. Volume occupied by 1 mol of O 3 at 20°C and 82 mm pressure is calculated by applying general gas
equation,

P1V1 P2V2

T1 T2
P1V1T2 76  22400  293
 V2    22281.92 cm3
T1 P2 273  82

3 PV
Now, u 
M
Here,
we use P in dyne / cm2 , P  82  13.6  981 dyne / cm2

3  82  13.6  981  22281.92

 u  3.90  10 4 cm s 1 .
48
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57. (i) Explain Boyle’s law with the help of Kinetic theory of gases.
(ii) An open beaker at 27 °C is heated to 477 °C. What fraction of air would have been expelled out ?
Ans. (i) The kinetic theory of gases assumes that pressure of gas is due to collision of gas molecules with the walls
of the container. The more will be frequency of collision, more will be pressure. The reduction in volume of
gas increases no. of molecules per unit volume to which pressure is directly proportional. Therefore, the
volume of the gas is reduced if pressure is increased or pressure is inversely proportional to volume.
1 3
mu 2  kT
2 2

1 N 2 N 1 2 N 3
p mu 2 or p   mu 2   kT
3 V 3 V 2 3 V 2

1
 pV  N kT  P .
V
It can be seen that at a constant temperature for a fixed number of gas molecules, the pressure is inversely
proportional to volume.
60
 Gaseous State

1T 1 n T1  27C  273  300 K

(ii) T  n T2  477  273  750 K
2 2

300 K n1 n1 2
 
750 K n2 , n2 5 bv

2 3
fraction of air escaped  1   .
5 5
58. At which temperature average velocity of oxygen molecules is equal to the rms velocity at 27°C ?

8 RT
Ans. Average velocity   M

Root mean square velocity

3 RT 3 R  300 K
 
M M

8 RT 3 R  300
For equal values, 
 M M

8 RT 3 R  300 8T
or  or  900
M M 

or T  353.57 K  80.57C.
59. At a constant temperature, a gas occupies a volume of 200 mL at a pressure of 0.720 bar. It is subjected
to an external pressure of 0.900 bar. What is the resulting volume of the gas ?
Ans. Boyle’s law is applicable as the amount and temperature are unaltered
p1 V1  p 2 V2

or p1 / p 2  V 2 / V1 ‘Substituting the values’

0.720 bar/0.900 bar  V2 / 200 mL

720
V2   200 mL  160 mL
900
Boyle’s law is manifested in the working of many devices used in daily life such as cycle pump, aneroid
barometer and tyre pressure gauge etc.
60. Calculate the number of nitrogen molecules present in 2.8 g of nitrogen gas.
Ans. Number of moles of nitrogen  2.8 g / 28 g mol 1  0.1 mol.
Number of nitrogen
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

molecules  0.1 mol  6.022  10 23

mol 1  6.022  10 22.

61. If the density of a gas at the sea level at 0°C is 1.29kg m 3 , what is its molar mass ? (Assume that pressure
is equal to 1 bar)
Ans. pVm  RT or p M / d  RT or M  dRT / p

1.29kg m 3  8.314 NmK 1 mol 1  273.15 K


1.0  10 5 Nm  2 (or Pa)

1.29  8.314  273.15kg mol 1


1  10 5

 0. 0293kg mol 1 or molar mass is 29.3 g mol 1 .

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JEE-Chemistr y
62. Which of the two gases, ammonia and hydrogen chloride, will diffuse faster and by what factor ?
Ans. r NH 3 / rHC1  (M HC1 / M NH 3 )1 / 2

 (36.5 / 17)1 / 2  1.46 or rNH 3  1.46 rHC1

Thus ammonia will diffuse 1.46 times faster than hydrogen chloride gas.
63. A 2.5 flask contains 0.25 mol each of sulphur dioxide, and nitrogen gas at 27°C. Calculate the partial
pressure exerted by each gas and also the total pressure.
Ans. Partial pressure of sulphur dioxide,
p SO2  nRT / V

0.25 mol  8.314 JK 1 mol 1  300 K


2.5  10  3 m 3

 2. 49  10 5 Nm 2  2.49  10 5 Pa

Similarly p N 2  2.49  10 5 Pa

Following Dalton’s law p Total  p N 2  p SO2

 2.49  10 5 Pa  2.49  10 5 Pa  4.98  10 5 Pa.

Long Answer (5 Mark)
3
64. An open vessel at 27°C is heated until parts of the air in it has been expelled. Assuming that the volume
5
of the vessel remains constant, find the temperature to which the vessel has been heated.
Ans. As the vessel is open, pressure and volume remain constant. Thus, if n1 moles are present at T1 and n2
moles are present at T2 , we can write
PV  n1 RT1 ; PV  n 2 RT2
Hence, n1 RT1  n 2 RT2 or n1 T1  n 2 T2
n1 T2
or, 
n2 T1
Suppose the no. of moles of air originally present = n
3
After heating, no. of moles of air expelled  n
5
3 2
 No. of moles left after heating  n  5 n  5 n

2
Thus, n1  n, T1  300 K ; n 2  n, T2  ?
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n T 5 T
 2 or  2
2 300 2 300 or , T2  750 K
n
5
Alternatively, suppose the volume of the vessel = V
i.e. Volume of air initially at 27°C = V
3
Volume of air expelled  V
5
2
 Volume of air left at 27C  5 V

However, on heating to T°K, it would become = V

As pressure remains constant, (vessel being open),
V1 V2 2/5 V V
 i.e.  or T2  750 K .
T1 T2 300 K T2

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 Gaseous State
65. A glass bulb contains 2.24 L of H 2 and 1.12 L of D2 at S.T.P.. It is connected to fully evacuated bulb by a
stopcock with a small opening. The stopcock is opened for sometime and then closed. The first bulb now
contains 0.10 g of D2 . Calculate the percentage composition by weight of the gases in the second bulb.
Ans. Weight of 2.24 L of H 2 at S.T.P.. = 0.2 g
(Mol. mass of H 2  2)  0.1 mol
Weight of 1.12 L of D2 at S.T.P.. = 0.2 g
(Mol. mass of D 2  4)  0.05 mol
As number of moles of two gases are different but V and T are same, therefore, their partial pressures will be
different, i.e., in the ratio of their number of moles. Thus,
PH 2 n H2 0.1
  2
PD2 n D2 0.5

Now, D2 present in the first bulb = 0.1 g (Given)

 D2 diffused into the second bulb
 0.2  0.1  0.1 g  0.56 L at S.T.P.

2 2
rH
2
PH MD
Now, r  P  M
D2 D2 H2

 H2 t PH 2 M D2
Or,   
t  D2 PD 2 M H2

 H2 t 4
  2
t 0.56 L 2

or  H 2  1.584 L  0.14 g of H 2

 Weight of the gases in 2nd bulb

 0.10 g (D 2 )  0.14 g (H 2 )  0.24 g
Hence, in the 2nd bulb,
0.10
% of D2 by weight   100  41.67%
0.24

% of H 2 by weight  100  41.67  58.33%.

66. An LPG (Liquefied Petroleum Gas) cylinder weights 14.8 kg when empty. When full, it weighs 29.0 kg and
shows a pressure of 2.5 atm. In the course of use at 27 °C, the mass of the full cylinder is reduced to 23.2 kg.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

Find out the volume of the conditions, and the final pressure inside the cylinder. Assume LPG to be n-butane
with normal boiling point of 0 °C.
Ans. Weight of LPG originally present = 29.0 – 14.8
= 14.2 kg
Pressure = 2.5 atm
Weight of LPG present after use = 23.2 – 14.8
= 8.4 kg
Since volume of the cylinder is constant, applying
pV  nRT

p1 n1 W1 / M W1 2.5 14.2
   
p 2 n 2 W2 / M W2 p2 8.4

2.5  8.4
p2   1.48 atm
14.2
or Weight of used gas = 14.2 – 8.4 = 5.8 kg

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JEE-Chemistr y

5.8  10 3
Moles of gas =  100 moles
58

Normal conditions
p  1 atm; T  273  27  300 K

Volume of 100 moles of LPG at 1 atm and 300 K

nRT 100  0.082  300

V   2460 litre
p 1

V  2.460 m3 .

67. The compressibility factor for one mole of a vander Waals gas at 0 °C and 100 atm pressure is found to be
0.5. Assume that the volume of gas molecule is negligible, calculate vander Waals constant ‘a’.

pV
Ans. Compressibility factor Z 
RT

100  V
0.5 
0.082  273

0.5  0.082  273

V 100
 0.1119 L

If volume of molecules is negligible i.e. b is negligible vander Waals’ equation :

 a 
 p  2  (V )  RT
 V 

or pV  RT  a / V or a  RTV  PV 2

 (0.082  273  0.1119)  (100  0.1119  0.1119)

 1.253 atm L2 mol 2 .

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 Gaseous State

ANSWERS
BEGINNER'S BOX-1
1.(A) 2.(D) 3.(B) 4.(C) 5.(A) 6.(B)

BEGINNER'S BOX-2
1.(D) 2.(B) 3.(B) 4.(B) 5.(C) 6.(B) 7.(C) 8.(D) 9.(C)
10.(C) 11.(C) 12.(C) 13.(D) 14.(D) 15.(D) 16.(B)

BEGINNER'S BOX-3
1.(B) 2.(A) 3.(B) 4.(C) 5.(C) 6.(C) 7.(C) 8.(A) 9.(B)
10. (B)

BEGINNER'S BOX-4
1. (D) 2. (C) 3. (A) 4. (C) 5. (B) 6. (A) 7. (D) 8. (B) 9. (D)
10. (C) 11. (B) 12. (B) 13. (B) 14. (D) 15. (B)

BEGINNER'S BOX-5
1. (C) 2. (D) 3. (D) 4. (A) 5. (B) 6. (A) 7. (A) 8. (A) 9. (D)
10. (B) 11. (B) 12. (D) 13. (C) 14. (A) 15. (A) 16. (D)

BEGINNER'S BOX-6
1. (B) 2. (C) 3. (D) 4. (D) 5. (C) 6. (B) 7. (A) 8. (D) 9. (A)
10. (A) 11.(D) 12. (B) 13. (B) 14. (C) 15. (D) 16. (B) 17. (A) 18.(C)

19. (D) 20. (A) 21. (B) 22. (C) 23. (D)

EXERCISE-1
SINGLE & MORE THAN ONE OPTION CORRECT
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C B A A C C C B A D D A B A D
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical\Eng\NPC-2 \1.Gaseous State\Exe.

Ans. A A D C B A A C A,C A,D B,C B,D A,B,C A,D B,C

Que. 31 32 33 34 35 36
Ans. A,C A,C,D A,B B,D A,B A,B,C
EXERCISE-2
Comprehension Based Questions
Comprehension-1: 1. (A) 2. (C) Comprehension-2: 3. (B) 4. (D) 5. (A)
Comprehension-3: 6. (A) 7. (A,C) Comprehension-4: 8. (A) 9. (A)
Comprehension-5: 10. (A) 11. (D) 12. (D) Comprehension-6: 13.(D) 14. (A) 15. (C)
Comprehension-7: 16. (B) 17. (C) 18. (B) Comprehension-8: 19. (A) 20. (B) 21. (A)
Comprehension-9: 22. (B) 23. (C)
Match the column
24. (A) - P ; (B) - Q ; (C) - S ; (D) - R 25. (A) - R ; (B) - Q ; (C) - P ; (D) - S
*26. (A) - PS ; (B) - R ; (C) - PQ ; (D) - R
*****
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JEE-Chemistr y

REDOX REACTION
1.0 OXIDATION & REDUCTION
Let us do a comparative study of oxidation and Reduction ;
Oxidation Reduction
(1) Addition of oxygen (i) Removal of oxygen
e.g. 2Mg + O2  2MgO e.g. CuO + C  Cu + CO
(2) Removal of Hydrogen (ii) Addition of Hydrogen
e.g. H2S + Cl2  2HCl + S e.g. S + H2  H2S
(3) Increase in positive charge (iii) Decrease in positive charge
e.g. Fe2+  Fe3+ + e– e.g. Fe3+ + e  Fe2+
(4) Increase in oxidation number (iv) Decrease in oxidation number
(+2) (+4) (+7) (+2)
SnCl2  SnCl4 MnO4–  Mn2+
(5) Removal of electron (v) Addition of electron
2+ 4+ –
e.g. Sn  Sn + 2e e.g. Fe3+ + e–  Fe2+
1.1 Oxidation Number
It is an imaginary or apparent charge gained by an element when it goes from its elemental free state to
combined state in molecules.
It is calculated on basis of a arbitrary set of rules.
It is a relative charge in a particular bonded state.
 Rules governing oxidation number
The following rules are helpful in calculating oxidation number of the elements in their different compounds. It
is remember that the basis of these rule is the electronegativity of the element.
 Fluorine atom
Fluorine is most electronegativity atom (known). It always has oxidation no. equal to –1 in all its compounds.
 Oxygen atom
In general and as well as in its oxides, oxygen atom has oxidation number equal to –2.
In case of : (i) peroxide (e.g. H2O2, Na2O2) is –1
(ii) super oxide (e.g. KO2) is – ½
(iii) ozonide (KO3) is – 1 3
(iv) oxygen fluoride OF2 is +2 & in O2F2 is +1
 Hydrogen atom
In general, H atom has oxidation number equal to +1. But in metallic hydrides (e.g. NaH, KH) it is –1.
 Halogen atom
In general, all halogen atom (Cl, Br, I) has oxidation number equal to –1.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

But if halogen atom is attached with an more electronegative atom than halogen atom then it will show
positive oxidation numbers.
5 5 7 5
e.g. KClO HIO HClO KBrO
3 3 4 3

 Metals
(a) Alkali metal (Li, Na, K, Rb, ..........) always have oxidation number +1.
(b) Alkaline earth metal (Be, Mg, Ca ........) always have oxidation number +2.
Note : Metal may have negative or zero oxidation number.
(c) Aluminium always have +3 oxidation number
Oxidation number of an element in free state or in allotropic forms is always zero.
0 0 0 0
e.g. O , S ,P ,O
2 8 4 3
Sum of the charges of elements in a molecule is zero.
Sum of the charges of all elements in an ions is equal to the charge on the ion.
If the group no. of an element in periodic table is n then its oxidation number may vary from n to
n – 8 (but it is mainly applicable in p-block elements)
e.g. N-atom belongs to v group in the periodic table therefore as per rule its oxidation number may vary from
3 2 3 4 5
–3 to +5 (NH 3 ,NO,N 2 O3 ,NO2 , N2 O5 )
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 REDOX REACTION
1.2 Calculation of average oxidation number
Ex.1 Calculate oxidation number of underlined element Na2S2O3 :
Sol. Let oxidation number of S-atom is x. Now work accordingly with the rules given before.
(+1) × 2 + (x) × 2 + (–2) × 3 = 0
x=+2
Ex.2 Na2 S 4O6 :
Sol. Let oxidation number of S-atom is x
(+1) × 2 + (x) × 2 + (–2) × 6 = 0
x = + 2.5
It's important to note here that Na2S2O3 have two S-atom and there are four S-atom in Na2S4O6 but
none sulphur atom in both the compound have +2 or +2.5 oxidation number, it is the average charge
(O. No.) Which reside on each sulphur atom therefore we should work to calculate the individual
oxidation number of each sulphur atom in these compound.
Ex.3. Calculate the O.S. of all the atoms in the following species :
(i) ClO–, (ii) NO2–, (iii) NO3– (iv) CCl4 (v) K2CrO4 and (vi) KMnO4
–
Sol. (i) In ClO , the net charge on the species is –1 and therefore the sum of the oxidation states of
Cl and O must be equal to –1. Oxygen will have an O.S. of –2 and if the O.S. of Cl is
assumed to be 'x' then
x – 2 should be equal to –1.
x is + 1
(ii) NO–2 : (2 × –2) + x = –1 (where 'x' is O.S. of N)
 x = +3
(iii) NO–3 : x + (3 × –2) = –1 (where 'x' is O.S. of N)
x = +5
(iv) In CCl4, Cl has an O.S. of –1
x + 4 × –1 = 0
   x = +4 (where 'x' is O.S. of C)
(v) K 2CrO 4 : K has O.S. of +1 and O has O.S. of –2 and let Cr has O.S. 'x' then,
2 × (+1) + x + 4 × (–2) = 0
   x = +6
(vi) KMnO4 : +1 + x + (4 × –2) = 0
   x = +7 (where x is O.S. of Mn).

 MISCELLANEOUS EXAMPLES
In order to determine the exact or individual oxidation number we need to take help from the structures of the
molecules. Some special cases are discussed as follows :
O O

 The structure of CrO5 is Cr

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

O O O
From the structure it is evident that in CrO5 there are two peroxide linkages and one double bond.
The contribution of each peroxide linkage is –2. Let the O.N. of Cr is x.
 x + (–2)2 + (–2) = 0 or x = 6
 O.N. of Cr = +6 Ans.
O
 The strcuture of H2SO5 is H O O S
O
H O
From the structure, it is evident that in H2SO5. there are one peroxide linkage, two sulphur - oxygen
double bond and one OH group. Let the O.N. of S = x.
+1 – 2 + x + (–2) 2 + (–2) + 1 = 0
or x + 2 – 8 = 0
or x – 6 = 0
or x = 6
 O.N. of S in H2SO5 is +6 Ans

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JEE-Chemistr y
 Paradox of fractional oxidation number
Fractional oxidation state is the average oxidation state of the element under examination and the
structural parameters reveal that the element for whom fractional oxidation state is realised is actually
present in different oxidation states. Structure of the species C3O2, Br3O8 and S4O62– reveal the
following bonding situations.
 The element marked with asterisk in each species is exhibiting the different oxidation state (oxidation
number) from rest of the atoms of the same element in each of the species. This reveals that in C3O2, two
carbon atoms are present in +2 oxidation state each whereas the third one is present in zero oxidation
state and the average is 4/3. However the realistic picture is +2 for two terminal carbons and zero for the
middle carbon.
2 0 2
O  C  C*  C  O
Structure of C3O2
(Carbon suboxide)
 Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and the
middle bromine is present in +4 oxidation state. Once again the average, that is different from reality is
16/3.

Structure of Br3O8 (tribromooctaoxide)

 In the same fashion, in the species S4O62–, is 2.5, whereas the reality being +5,0,0 and +5 oxidation
number respectively for each sulphur.
O O
+5 0
0 +5 –
O S S* *
S S O
O O

Structure of S4O62– (tetrathionate ion)

1.3 Oxidising and Reducing Agent
 Oxidising agent or Oxidant
Oxidising agents are those compound which can oxidise others and reduced itself during the chemical reaction.
Those reagents whose O.N. decrease or which gain electrons in a redox reaction are termed as oxidants
e.g. KMnO4, K2Cr2O7, HNO3, conc. H2SO4 etc, are powerful oxidising agents.

 Reducing agent or Reductant

Reducing agents are those compound which can reduce others and oxidise itself during the chemical reaction.
Those reagents whose O.N. increase or which loses electrons in a redox reaction are termed as reductants.
e.g. KI, Na2S2O3 are powerful reducing agents.
Note : There are some compounds also which can work as both oxidising agent and reducing agent.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

e.g. H2O2, NO–2

 HOW TO IDENTIFY WHETHER A PARTICULAR SUBSTANCE IS AN OXIDISING OR

REDUCING AGENT :

Find the O.State of the central atom

If O.S. is=Max. O.S. or (valence electron) If O.S. =Minimum O.S. If O.S. is intermediate b/ w max & minimum

Its Oxidizing It's a reducing It can act both as reducing

agent agent agent & oxidising agent

It can disproportionate
as well

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 REDOX REACTION
2.0 REDOX REACTION
A reaction in which oxidation and reduction simultaneously take place.
In all redox reactions the total increase in oxidation number must equal the total decrease in oxidation
number.
2 7 3 2
e.g. 10 FeSO4 + 2K MnO4 + 8H2SO4  5 Fe2 (SO4 )3 + 2 Mn SO 4 + K2SO4 + 8H2O

2. 1 Dispropor tionations reactions

A redox reaction in which a same element present in a particular compound in a definite oxidation state is
oxidized as well as reduced simultaneously is a disproportionation reaction.
Disproportionation reactions are a special type of redox reactions. One of the reactants in a disproportionation
reaction always contains an element that can exist in at least three oxidation states. The element in the
form of reacting substance is in the intermediate oxidation state and both higher and lower oxidation states of
that element are formed in the reaction.
 1 1  1 2 0
2 H 2 O2 (aq)  2 H 2 O () + O2 (g)
0 2 2
S8 (s) + 12OH–(aq)  4 S2  (aq) + 2 S 2O 23  (aq) + 6H2O ()
0 1 1
Cl2 (g) + 2OH– (aq)  ClO (aq) + Cl (aq) + H2O ()
Consider following reactions :
(a)2KClO3 = 2KCl + 3O2
KClO3 plays a role of oxidant and reductant both. Because same element is not oxidised and reduced.
Here, Cl present in KClO3 is reduced and O present in KClO3 is oxidized. So its not a disproportion
reaction
although it looks like one.
(b) NH4NO2  N2 + 2H2O
Nitrogen in this compound has –3 and +3 oxidation number so it is not a definite value, so its not a
disproportion reaction. Its a example of comproportionation reaction which is a class of redox reaction in
which a element from two different oxidation state gets converted into a single oxidation state.
(c) 4KClO3 3KClO4 + KCl
Its a case of disproportionation reaction in which Cl is the atom disproportionating.
List of some important disproportionation reaction :
1. H2O2  H2O + O2
2. X2 + OH– (dil.) X– + XO–
3. X2 + OH– (conc.)  X– + XO3–
F2 does not (can not) undergo disproportionation as it is the most electronegative element.
F2 + NaOH (dil)  F – + OF2
F2 + NaOH (conc.) F – + O2
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Reverse of disproportionation is called Comproportionation. In some of the disproportionation reactions by

changing the medium (from acidic to basic or reverse) the reaction goes in backward direction and can be
taken as an example of Comproportionation.
I – + IO3– + H+ I2 + H2O (acidic)

Some examples of redox reactions are

 R
O

 O
R

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JEE-Chemistr y

 If one of the half reactions does not take place, other half will also not take place. We can say oxidation
and reduction go side by side.

In the above reaction, we can see that Cl2 has been oxidized as well as reduced. Such type of redox reaction
is called disproportionation reaction.
Some More examples

2. 2 Balancing of Redox Reactions

All balanced equations must satisfy two criteria
1.Atom balance (mass balance)
That is there should be the same number of atoms of each kind in reactant and products side.
2. Charge balance :
That is the sum of actual charges on both side of the equation must be equal
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

There are two methods for balancing the redox equations

(a) Oxidation - number change method
(b) Ion electron method or half cell method

(a) Oxidation number change method

This method was given by Jonson. In a balanced redox reaction, total increase in oxidation number must be
equal to total decreases in oxidation number. This equivalence provides the basis for balancing redox reac-
tions.
The general procedure involves the following steps :
(i) Select the atom in oxidising agent whose oxidation number decreases and indicate the gain of electrons.
(ii) Select the atom in reducing agent whose oxidation number increases and write the loss of electrons.
(iii) Now cross multiply i.e. multiply oxidising agent by the number of loss of electrons and reducing agent by
number of gain of electrons.
(iv) Balance the number of atoms on both sides whose oxidation numbers change in the reaction.
(v) In order to balance oxygen atoms, add H2O molecules to the side deficient in oxygen. Then balance the
number of H atoms by adding H+ ions in the hydrogen.

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 REDOX REACTION

Illustration 1. Balance the following chemical reaction by oxidation number method and write their skeleton
equation :
(i) Chloride ions reduce maganese dioxide to manganese (II) ions in acidic medium and get itself
oxidized to chlorine gas.
(ii) The nitrate ions in acidic medium oxidize magnesium to Mg2+ ions but itself gets reduced
to nitrous oxide.
Solution (i) The skeleton equation for the given process is
MnO2 + Cl–  Mn2+ + Cl2 + H2O
4 2 4 1 2
– 2+
Step (1) : MnO 2 + Cl  Mn + Cl2  H 2O

O.N. decreases by 2 per Mn

+4

Step (2) :
O.N. increases by 1 per Cl
Step (3) : Equalize the increase/decrease in O.N. by multiplying
MnO2 by 1 and Cl – by 2
MnO2 + 2Cl –  Mn2+ + Cl2 + H2O
Step (4) : Balance other atoms except H and O. Here they are all balanced.
Step (5) : Balance O atoms by adding H2O molecules to the side falling short of O atoms.
MnO2 + 2Cl –  Mn2+ + Cl2 + H2O + H2O
Step (6) : Balance H atoms by adding H+ ions to the side falling short of H atoms.
MnO2 + 2Cl – + 4H+ Mn2+ + Cl2 + 2H2O
(ii) The skeleton equation for the given process is
Mg + NO3– Mg2+ + N2O + H2O
0 5 2 1 2 1 2
Step (1) : Mg  (N O 3 )– Mg2+ + N 2O  H 2 O
Multiply NO3– by 2 to equalize N atoms

Step (2) :
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Step (3) : Equalize increase/decrease in O.N. by multiplying Mg by 4 and 2NO3– by 1.

4Mg + 2NO3– Mg2+ + N2O + H2O
Step (4) : Balance atoms other than O and H
4Mg + 2NO3– 4Mg2+ + N2O + H2O
Step (5) : Balance O atoms
4Mg + 2NO3– 4Mg2+ + N2O + H2O + 4H2O
Step (6) : Balance H atoms as is done in acidic medium.
4Mg + 2NO3– + 10H+ 4Mg2+ + N2O + 5H2O

(b) Ion electron method or half reaction method :

By this method redox equation are balanced in two different medium
(a) Acidic medium (b) Basic medium

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JEE-Chemistr y
Balancing in acidic medium
Students are advised to follow the following steps to balance the redox reactions by ion electron
method in acidic medium.

Illustration 2. Balance the following redox reaction.

FeSO4 + KMnO4 + H2SO4  Fe2(SO4)3 + MnSO4 + H2O
Solution Step-I assign the oxidation No. to each elements present in the reaction.
2 6 2 1 7 2 1 6 2 3 62 2 6 2 1 2
Fe S O 4 + KMnO 4 + H 2 SO 4  Fe2 (SO 4 )3 + MnSO 4 + H 2 O
Step-II Now convert the reaction in ionic form by eliminating the elements or species which are not
going either oxidation or reduction
7
Fe2+ + MnO4 Fee3+ + Mn2+

Step-III Now identify the oxidation / reduction occurring into the reaction.

Step-IV Split the ionic reaction in two half one for oxidation and other for reduction
oxidation
Fe2+  e3+
 Fe MnO4– 
Reduction
 Mn2+

Step-V Balance the atom other than oxygen and hydrogen atom in both half reactions

Fe2+ Fe3+ MnO4–  Mn2+

Fe & Mn atom are balanced in both side.
Step-VI Now balance O & H atom by H2O & H+ respectively by the following way for one excess
oxygen atom add one H2O on the other side and two H+ on the same side.
Fe2+ Fe3+ (no oxygen atom) ..........(i)
8H+ + MnO–4 Mn2+ + 4H2O .........(ii)
Step VII Now see equation (i) & (ii) is balanced atomwise. Now balance both equations chargewise
to balance the charge add electrons to the electrically positive side.
Fe2+ 
oxidation
e3+ + e–
 Fe ..........(1)

5e– + 8H+ + MnO4– 

Reduction 2+
 Mn + 4H2O ..........(2)
Step VIII The number of electrons gained and lost in each half-reaction are equalised by multiply
suitable factor in both the half reaction and finally the half reactions are added to give the over all
balanced reaction.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Here we multiply equation (i) by 5 and (ii) by one

Fe2+ Fe3+ + e– .............(1) × 5
5e– + 8H+ + MnO4–  Mn2+ + 4H2O .............(2) × 1

5Fe2+ + 8H+ + MnO–4  5Fe3+ + Mn2+ + 4H2O

(Here at this stage you will get balanced redox reaction in ionic form)
Step IX Now convert the ionic reaction in to molecular form by adding the elements or species
which are removed instep (II).
Now by some manipulation you will get
5
5 FeSO4 + KMnO4 + 4H2SO4  Fee2(SO4)3 + MnSO4 + 4H2Oor
2
10 FeSO4 + 2KMnO4 + 8H2SO4  5Fe2(SO4)3 + 2MnSO4 + 8H2O + K2SO4
Balancing in basic medium
In this case except step VI all the steps are same. We can understand it by following example balance
the redox reaction in basic medium
72
 REDOX REACTION
Illustration 3. ClO– + CrO2– + OH– Cl– + CrO42– + H2O
Solution By using up to step V we will get
1 3 6
Oxidation
 CrO 24
 
–
ClO  Reduction
 Cl – CrO2 

Now student are advised to follow step VI to balance 'O' and 'H' atom

2H+ + ClO– Cl– + H2O 2H2O + CrO–2 CrO42– + 4H+

Now since we are doing balancing in basic medium therefore add as many as OH– on both side of
equation as there are H+ ions in the equation.
2OH– + 2H+ + ClO–  Cl– + H2O+2OH– 4OH– + 2H2O + CrO2–  CrO42– + 4H+ +
4OH–
Finally you will get Finally you will get
– – –
H2O + ClO  Cl + 2OH ........(i)
4OH– + CrO2–  CrO42– + 2H2O .........(ii)
Now see equation (i) and (ii) in which O and H atoms are balanced by OH– and H2O
Now from step VIII
2e– + H2O + ClO–  Cl– + 2OH– .............(i) × 3
– – –2 –
4OH + CrO2  CrO4 + 2H2O + 3e .............(ii) × 2
Adding : 3ClO– + 2CrO2– + 2OH–  3Cl– + 2CrO42– + H2O

3.0 EQUIVALENT WEIGHT (E)

Molecular weight Mol. wt.
Eq. wt (E) = =
valency factor (v.f) n  factor

mass of a sample
no of Equivalents =
eq. wt.of that species
Equivalent mass is a pure number when expressed in gram, it is called gram equivalent mass.
The equivalent mass of substance may have different values under different conditions.

3.1 Valency factor calculation For Acids

valence factor = number of replaceable H+ ions
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Illustration 4. HCl, H2SO4 H3PO4 H3PO3

{see there are only two replaceable H+ ions}

Solution valence  1 2 3 2
factor (assume 100%
dissociation)
M M M M
Eq.wt.
1 2 3 2

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JEE-Chemistr y
3.2 Valency factor calculation For Base
v.f. = number of replaceable OH– ions

Illustration 5. NaOH, KOH

Solution v.f. 1 1
M M
E.
1 1

3.3 Valency factor calculation For Acid - base reaction

In case of acid base reaction, the valence factor is the actual number of H+ or OH– replaced in the reaction.
The acid or base may contain more number of replaceable H+ or OH– than actually replaced in reaction.
v.f. for base is the number of H+ ion form the acid replaced by per molecule of the base.

Illustration 6. 2NaOH + H2SO4  Na2SO4 + 2H2O

Base acid
Solution valency factor of base = 1
valency factor of acid = 2
Here two molecule of NaOH replaced 2H+ ion from the H2SO4 therefore per molecule of NaOH
replaced only one H+ ion of acid so v.f. = 1
v.f. for acid is number of OH– replaced from the base by per molecule of acid

Illustration 7. NaOH + H2SO4  NaHSO4 + H2O

Base acid
Solution valence factor of acid = 1
here one of molecule of H2SO4 replaced one OH– from NaOH therefore v.f. for H2SO4 is = 1
mol. wt.of H 2 SO 4
E=
1

3. 4 Valency factor calculation For Salts

(a) In non reacting condition
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

v.f. = Total number of positive charge or negative charge present into the compound.
Ex.1. Na2CO3 Fe2(SO4)3(2Fe3+ + 3SO42–) FeSO4.7H2O
Sol. V.f. 2 2×3=6 2
M M M
E.
2 6 2
(b) Salt in reacting condition :

Ex.2. Na2CO3 + HCl  NaHCO3 + NaCl

Base Acid
Sol. It is a acid base reaction therefore v.f. for Na2CO3 is one while in non reaction condition it will be two.
3. 5 Eq. wt. of oxidising / reducing agents in redox reaction
The equivalent weight of an oxidising agent is that weight which accepts one mole electron in a chemical
reaction.
(a)Equivalent wt. of an oxidant (get reduced)
Mol.wt.
=
No. of electrons gained by one mole

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 REDOX REACTION

Illustration 8. In acidic medium

6e– + Cr2O72– + 14H+ 2Cr3+ + 7H2O
Mol. wt of K 2 Cr2 O7 Mol. wt.
Eq. wt. of K2Cr2O7 = 
6 6
Note : [6 in denominator indicates that 6 electrons were gained by Cr2O72– as it is clear from the
given balanced equation]
(b) Similarly equivalent wt. of a reductant (gets oxidised)
Mol. wt.
=
No. of electrons lost by one mole
Illustration 9. In acidic medium, C2O42– 2CO2 + 2e–

Mol. wt.
Here, Total electrons lost = 2 So, eq. wt. =
2
(c) In different condition a compound may have different equivalent weights. Because, it depends
upon the number of electrons gained or lost by that compound in that reaction.
Illustration 10. (i) MnO4–  Mn2+ (acidic medium)
(+7) (+2)

Mol.wt.of KMnO 4 158

Here 5 electrons are taken so eq. wt. = = = 31.6
5 5
(ii) MnO4–  Mn+4 (neutral medium)
(+7) (+4)
Mol.wt.of KMnO 4 158
Here, only 3 electrons are gained, so eq. wt. = = = 52.7
3 3
(iii) MnO4–  MnO4–2 (alkaline medium)
(+7) (+6)

Mol.wt.of KMnO 4
Here, only one electron is gained, so eq. wt. = = 158
1
Note : It is important to note that KMnO4 acts as an oxidant in every medium although with
different strength which follows the order.
acidic medium > neutral medium > alkaline medium
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Illustration 11. 2S2O3– –  S4O6– – + 2e–

(Reducing agent)
M
equivalent weight of S2O3– – = =M
1

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JEE-Chemistr y
 SOME OXIDIZING AGENTS/REDUCING AGENTS WITH EQ. WT.
Species Changed to Reaction exchanged Electrons Eq. wt.
or change in O.N.
Mn2 M
MnO4–(O.A.) in acidic medium
MnO4– + 8H+ + 5e–Mn2+ + 4H2O 5 E=
5
MnO 2 M
MnO4–(O.A.) in neutral medium MnO4– + 3e– + 2H2O MnO2 + 4OH– 3 E=
3
MnO42 M
MnO4–(O.A.) MnO4– + e–  MnO42– 1 E=
in basic medium 1
Cr 3 M
Cr2O72–(O.A.) in acidic medium
CrO72– + 14H+ + 6e–  2Cr3+ + 7H2O 6 E=
6
Mn 2  M
MnO2(O.A.) in acidic medium
MnO2 + 4H+ + 2e–  Mn2+ + 2H2O 2 E=
2
Cl 2 (O.A.) M
in bleaching powder Cl – Cl2 + 2e–  2Cl – 2 E=
2
CuSO4 (O.A.) M
in iodometric titration Cu+ Cu2+ + e–  Cu+ 1 E=
1
2M
S2O32– (R.A.) S4O62– 2S2O32–  S4O62– + 2e– 2 E= =M
2
(for two molecules)
M
H2O2(O.A.) H2O H2O2 + 2H+ + 2e–  2H2O 2 E=
2
M
H2O2(R.A.) O2 H2O2  O2 + 2H+ + 2e– (O.N. of 2 E=
2
oxygen in H2O2 is –1 per atom)
M
Fe2+(R.A.) Fe3+ Fe2+  Fe3+ + e– 1 E=
1

Illustration 12. To find the n-factor in the following chemical changes.

(i) KMnO4  H
 Mn2+ (ii) KMnO4  H2 O
 Mn
4+

6+
(iii) KMnO4   Mn (iv) K2Cr2O7  H
 Cr3+

OH –
2–
(v) C2O4  CO2 (vi) FeSO4  Fe2O3
(vii) Fe2O3  FeSO4
Solution (i) In this reaction, KMnO4 which is an oxidizing agent, itself gets reduced to Mn2+ under acidic
conditions.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

n=|1 × (+7) – 1 × (+2)| = 5

(ii) In this reaction, KMnO4 gets reduced to Mn4+ under neutral or slightly (weakly) basic
conditions.
n=|1 × (+7) – 1 × (+4)| = 3
(iii) In this reaction, KMnO4 gets reduced to Mn6+ under basic conditions.
n=|1 × (+7) – 1 × (+6)| = 1
(iv) In this reaction, K2Cr2O7 which acts as an oxidizing agent reduced to Cr3+ under acidic
conditions. (It does not react under basic conditions.)
n=|2 × (+6) – 2 × (+3)| = 6
(v) In this reaction, C2O42– (oxalate ion) gets oxidized to CO2 when it is reacted with an oxidizing
agent.
n=|2 × (+3) – 2 × (+4)| = 2
(vi) In this reaction, ferrous ions get oxidized to ferric ions.
n=|1 × (+2) – 1 × (+3)| = 1
(vi) In this reaction, ferric ions are getting reduced to ferrous ions.
n = |2 × (+3) – 2 × (+2)| = 2

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 REDOX REACTION
Illustration 13. Calculate the molar ratio in which the following two substances would react ?
Ba3(PO4)2 and AlCl3
Solution n-factor of Ba3(PO4)2 = 3 × (+2) = 6 = n1
While n-factor of AlCl3 = 1 × (+3) = 3 = n2
n1 6 n1 x
 If 
n2 3 n2 y
y
Molar ratio = (inverse of equivalent ratio)
x
 Molar ratio in which Ba3(PO4)2 and AlCl3 will react = 3 : 6 = 1 : 2

Calculation of equivalent weight in Acid - base reactions or neutralisation reactions

1. Find out the oxidation state of element underlined :

(1) NH 4 BF4 (2) SiH 4 (3) Mg 3 (OH)4 [SiO5 ] (4) (Si 2O 5 )n2n

(5) Na 2 B 4 O7 .10H 2O (6) K[B 5O 6 .(OH)4 ] (7) NH 4 NO 3 (8) K 4 [Fe(CN)6 ]

(9) Cr 2 O72 (10) MnO 4 (11) MnO4 2 (12) Na 2[B 4 O 5 (OH)4 ].8H

(13) NH 4  (14) H 2 S2O6 (15) H 2 S2O7 (16) H 2 S2O8

(17) H 2 SO5 (18) Na 2 S 2 O 3 (19) Na 2 S 4 O 6 (20) CrO5

(21) [Fe(CO)5 ] (22) XeO64  (23) K 3 CrO 8 (24) OsO 4

(25) PO 43  (26) SO 4 2 (27) IO 3  (28) ClO 4

(31) Mg 2 P2O7
2
(29) H 3 BO3 (30) NOBF4 (32) C 2O 4

(33) Na 4 P4 O12 .4H 2O (34) [Fe(HPO 4 )3 ]3 (35) NaH 2 PO 2 (36) Ba(MnO 4 )2

(37) BaO 2 (38) KO2 (39) xeo2F2 (40) [Fe(H 2O)6 ]SO 4

2. Determine ‘n’ in the following processes :

 MnO 42
(1) MnO4  ne  (2) X 2  XO n  6e
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

n
(3) A 4 
 AO 4   20e  (4) AO n4   2e  HAO n2 

(5) Cr2O72  6e 

 2Cr  n (6) AO n4   2e 
 HAO2n

(7) Cu 2 S  2Cu 2  SO 2  ne  (8) Cu 3 P  3Cu2  PO 43   ne 

(9) AS 2 S 3  2AsO43   3SO 42  ne  (10) NO 3  ne   NH 3

3. Balance the following Redox Reactions.

1. C2H 5 OH  Cr2O72  H  Cr 3  C 2H 4 O  H 2O


 2
2. 
Sn(OH)3  Bi(OH)3  OH  Sn(OH)6  Bi

3. Zn + NO3 + H+  Zn2+ + NO2 + H2O

4.   
I 2  NO 3  H  IO 3  NO 2  H 2 O
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JEE-Chemistr y

MnO4  SO 32  H 2O  MnO2  SO42  OH


5.

6. I 2  Cl 2  H 2O  HIO3  HCl

7. H 2S  HNO3  NO  S  H 2O

8. NO3  Cl  H   NO  Cl2  H 2O

9.

H 2O 2  I  H  I 2  H 2 O


10. Cr2O72  NO2  H   Cr3  NO3  H 2O

11. N2O4  BrO3  H 2O  NO3  Br   H

12. Zn  NO 3  H  Zn2   NH 4  H 2 O
  

13. ClO 3  SO 2  H   ClO 2  HSO 4



14. Mn 2  S 2O 82   H 2 O  MnO 4  HSO 4  H

  


15. 
Cl 2  IO 3  OH  Cl  IO 4  H 2O


16. H 2 SO 3  Cr2 O72 +H+  HSO 4  Cr 3  H 2O

17. S + OH–  S2– + S2O32–

18. IO 4  I +H+  I 2  H 2 O


19. Zn  NO 3 +H+  Zn 2  NO 2  H 2 O

20. H 2 S  Cr2O72 + H+  Cr 3  S8  H 2O

21. C2H5OH + MnO4  OH   C2H3O  MnO2  H2O

22. MnO 4  SO 32 + H 2O  MnO 2  SO 42  OH 



23. Cr2O72  SO 32 + H  Cr 3  SO 42  H 2O

 
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

24. I 2  SO 2 + H 2 O  SO 42  I  H
 

25. Sn  NO 3  H  SnO 2  NO 2  H 2 O


2
26. MnO4  SO 2  H 2O  Mn2  SO 4  H+

27. MnO4  SO32  OH  MnO24  SO24  H 2O

28.

ClO   Br   BrO 3  Cl

29. MnO4  C 2O 42  H  Mn 2  CO 2  H 2O



30. Fe2  Cr2O72  H  Fe 3  Cr 3  H 2O



31. AsO 33  I 2  H 2O  AsO 43  H   I



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 REDOX REACTION

32. Cl 2  SeO 32  H 2O  SeO42  Cl  H

 

33. Cu 3 P  H  Cr2 O72  Cu 2  H 3 PO 4  Cr 3  H 2



4. In the reaction : 3Br2  6CO 32  3H 2O  5Br   BrO3  6HCO 3

(A) Bromine is oxidised and carbonate is reduced (B) Bromine is oxidised and water is reduced
(C) Bromine is both oxidised and reduced (D) Bromine is neighter oxidised nor reduced.
5. Equivalent wt. of H 2SO 4 in given reaction is:

H 2 SO 4  NaOH  NaHSO 4  H 2O

(A) 49 gm/eq. (B) 98 gm/eq (C) 98/3 gm/eq. (D) none of these
6. Equivalent wt. of H3PO4 in given reactions is respectively:

(i) H 3PO 4  NaOH  NaH 2PO 4  H 2O (ii) H 3PO 4  Ca(OH)2  CaHPO 4  2H 2O

(iii) 2H 3PO 4  3Ca(OH)2  Ca 3 (PO4 )2  6H 2O

(A) 49, 98, 98/3 (B) 98, 49, 98/3 (C) 98, 98, 98/3 (D) 49, 98, 49
7. Equivalent wt. of Na2CO3 in given reaction is Na2CO3 + H2SO4  H2CO3 + Na2SO4

106
(A) 106 gm/eq. (B) 53 gm/eq. (C) gm/eq. (D) 26.5 gm/eq.
3
8. Equivalent wt of aniline in given reaction is
C6H5NH2 + H2SO4  C6H5NH3+ HSO4– (M = molar mass of aniline)

M M M 2M
(A) (B) (C) (D)
1 2 3 3

9. Oxidation number of C in HNC (H — N  C) is :

(A) + 2 (B) – 3 (C) + 3 (D) zero
10. A compound contains atoms X, Y, Z. The oxidation number of X is + 2, Y is +5, and Z is – 2. The
possible formula of the compound is :
(A) XYZ 2 (B) Y2 (XZ 3)2 (C) X3 (YZ 4)2 (D) X3 (YZ 2)2
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

11. Given reation HCHO  CH 3OH + HCOO is an example of

–

(A) intermolecular redox change (B) intramolecular redox change

(C) disproportionation or auto redox change (D) None
12. The decomposition of KClO 3 to KCl and O 2 on heating is an example of
(A) intermolecular redox change (B) intramolecular redox change
(C) disproportionation or auto redox change (D) None
13. When this oxidation–reduction equation is correctly balanced, what is the mole ratio of reducing agent to
oxidizing agent ?
MnO 4– + Sn 2+ + H + Mn 2+ + Sn 4+ + H 2O
(A) 1 : 1 (B) 2 : 1 (C) 4 : 1 (D) 5 : 2

14. In the reaction, Cl2 + OH – 

 Cl– + ClO3 + H 2O :

(A) Chlorine is oxidised (B) Chlorine is reduced

(C) Chlorine is oxidised as well as reduced (D) Chlorine is neither oxidised nor reduced

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15. In the following oxidation–reduction reaction

8H+ (aq) + 4NO 3– + 6Cl– + Sn(s)  SnCl62 + 4 NO 2  + 4H 2O the reducing agent is :

(A) Sn(s) (B) Cl– (C) NO3 (D) H + (aq)

16. Consider the reaction H + + IO 4– + I– 

 I2 + H 2O. The ratio of coefficients of IO 4–, I– and I2 is :
(A) 1 : 7 : 4 (B) 1 : 7 : 8 (C) 7 : 1 : 4 (D) 7 : 1 : 8
17. The ratio of coefficients of CrO 4 2–
and CrO after balancing the reaction
2
–

HSnO 2 + CrO 4 + H 2O  HSnO 3– + CrO 2– + OH – will be :

– 2–

(A) 1 : 1 (B) 1 : 3 (C) 3 : 1 (D) none of these

Calculation of equivalent weight in redox reactions
18. When potassium permanganate is titrated against ferrous ammonium sulphate in acidic medium, the equivalent
weight of potassium permanganate is:

molecular weight molecular weight molecular weight molecular weight

(A) (B) (C) (D)
3 5 2 10

19. Equivalent weight of FeS2 in the half reaction, FeS2  Fee2O3 +SO2 is :
(A) M/10 (B) M/11 (C) M/6 (D) M/l
20. Equivalent weight of H3PO2 when it disproportionate into PH3 and H3PO3 is:
(A) M (B) M/2 (C) M/4 (D) 3M/4

21. Hydrazine reacts with KIO3 in presence of HC1 as N2H4+ IO3 +2H+ +Cl–  ICl + N2 +3H2O

The equivalent masses of N2H4 and KIO3 respectively are:

(A) 8 and 53.5 (B) 16 and 53.5 (C) 8 and 35.6 (D) 8 and 87
22. In the following reaction 28NO3– + 3As2S3 + 4H2O  6AsO43– + 28NO + 9 SO42– + 8H+ equivalent
weight of As2S3 (with molecular weight M) is :
(A) M/2 (B) M/4 (C) M/24 (D) M/28
23. ClF3 (molecular weight, M1) can oxidize UF4 (g) (molecular weight, M2) to UF6(g) and get reduced to Cl2 itself.
Equivalent weights of ClF3 and UF4 respectively in this reaction are :
(A) M2/2, M1/6 (B) M1/3, M2/2 (C) M1/6, M2/2 (D) M1/6, M2/6
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

24. Br2+ can be prepared by treating Br2 with S2O6F2 followed by treatment with SbF5 to form bright red [Br2][Sb3F16].
Equivalent weight of Br2 in this redox reaction is (Br = 80)
(A) 20 (B) 40 (C) 80 (D) 160
25. Equivalent wt. of KMnO4 in acidic, weakly alkaline and neutral medium as an oxidant are respectively:
(M = molar mass of KMnO4).

M M M M M M M M M M M M
(A) , , (B) , , (C) , , (D) , ,
5 1 3 5 2 3 5 3 3 5 4 3
26. Equivalent wt. of FeC2O4 in given reaction is FeC2O4 + MnO4– + H+  Fe3+ + CO2 + Mn2+ is
(A) 144 gm/eq. (B) 72 gm/eq. (C) 48 gm/eq. (D) 96 gm/eq.
27. Equivalent wt. of Cu2S in given reaction Cu2S + Cr2O72– + H+  Cu2+ + SO42– + Cr+3
is (M = Molar mass of Cu2S)

M M M M
(A) (B) (C) (D)
8 2 10 5

80
 REDOX REACTION
28. Equivalent wt. of Br2 in reaction Br2 + OH–  Br– + BrO3– is (Atomic mass : Br = 80)
(A) 80 gm/eq. (B) 96 gm/eq. (C) 160 gm/eq. (D) 40 gm/eq.
29. -Equivalent wt. of H2O in reaction H2O  H2 + 1/2 O2 is
(A) 18 gm/eq. (B) 9 gm/eq. (C) 4.5 gm/eq. (D) none of these
30. Equivalent wt. of KClO3 in reaction KClO3  KCl + 3/2O2 is (M = molar mass of KClO3)
(A) M/2 (B) M/3 (C) M/6 (D) M/4
31. n–factor of IO3– and I– in the reaction IO3– + 5I–  3I2 are respectively
(A) 10, 1 (B) 10, 2 (C) 5, 1 (D) none of thes
32. N2 + 3H2  2NH3 , Molecular weights of NH3 and N2 are x1 and x2 their equivalent weights are y1 and y2.
Then (y1 – y2) is :

 2x1  x 2 
(A)   (B) (x1 – x2) (C) (3x1 – x2) (D) (x1 – 3x2)
 6 

4.0 NORMALITY
Normality of solution is defined as the number of equivalent of solute present in one litre (1000 mL) solutions.
Let a solution is prepared by dissolving W g of solute of eq. wt. E in V mL water.
W
No. of equivalent of solute =
E
W
V mL of solution have equivalent of solute
E
W  1000
1000 mL solution have
E  VmL
W  1000
Normality (N) =
E  VmL

Normality (N) = molarity × Valence factor (n)

or N × V (in mL) = M × V (in mL) × n
or milli equivalents = millimoles × n

Illustration 14. Calculate the normality of a solution containing 15.8 g of KMnO4 in 50 mL acidic solution.
W  1000
Solution Normality (N) =
E  VmL
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

molar mass of KMnO4

where W = 15.8 g, V = 50 mL E= = 158/5 = 31.6
Valencefactor
So, N = 10

Illustration 15. Calculate the normality of a solution containing 50 mL of 5 M solution K2Cr2O7 in acidic medium.
Solution Normality (N) = Molarity × Valence factor
= 5 × 6 = 30 N

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 MOLARITY V/S NORMALITY

Molarity (M) Normality (N)
1. No. of moles of solute present in 1. No. of equivalents of solute present in one litre
one litre of solution. of solution.
W W
2. No. of moles = 2. No. of equivalents =
M E
W W
3. × 1000 = No. of millimoles 3. × 1000 = No. of milliequivalance
M E

4. Molarity × V(in mL)=No. of millimoles 4. Normality × V(in mL) = No. of milliequivalance

milli moles milli equivalents
5. Molarity = 5. Normality =
Volumeof solution in mL Volumeof solution in mL

5.0 LAW OF EQUIVALENCE

The law states that one equivalent of an element combine with one equivalent of the other, and in a chemical
reaction equivalent and mill equivalent of reactants react in equal amount to give same no. of equivalent or
milli equivalents of products separately.
According :
(i) aA + bB  mM + nN
m.eq of A = m.eq of B = m.eq of M = m.eq of N
(ii) In a compound MxNy
m.eq of MxNy = m.eq of M = m.eq of N

Illustration 16. Find the number of moles of KMnO4 needed to oxidise one mole Cu2S in acidic medium.
The reaction is KMnO4 + Cu2S  Mn2+ + Cu2+ + SO2
Solution From law of equivalence
equivalents of Cu2S = equivalents of KMnO4
moles of Cu2S × v.f = moles of KMnO4 × v.f.
moles of Cu2S × 8 = 1 × 5  moles of Cu2S = 5/8
Illustration 17. The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium.
5 2 3 5
(A) (B) (C) (D)
2 5 5 3
Solution Equivalents of C2O42– = equivalents of MnO4–
x (mole) × 2 = 1 × 5
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

5
x=
2
Illustration 18. What volume of 6 M HCl and 2 M HCl should be mixed to get two litre of 3 M HCl ?
Solution Let, the volume of 6 M HCl required to obtain 2 L of 3M HCl = x L
 Volume of 2 M HCl required = (2 – x) L
M1V1 + M2V2 = M3V3
6M HCl 2M HCl 3M HCl
6 × (x) + 2 × (2 – x) = 3 × 2
 6x + 4 – 6x = 6  4x = 2
 x = 0.5 L
Hence, volume of 6 M HCl required = 0.5 L
Volume of 2M HCl required = 1.5 L
Illustration 19. In a reaction vessel, 1.184 g of NaOH is required to be added for completing the reaction. How
many millilitre of 0.15 M NaOH should be added for this requirement ?
Solution Amount of NaOH present in 1000 mL of 0.15 M NaOH = 0.15 × 40 = 6 g
6
 1 mL of this solution contain NaOH = × 10–3 g
1000
1
 1.184 g of NaOH will be present in = × 1.184 = 197.33 mL
6  10 3
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 REDOX REACTION
Illustration 20. What weight of Na2CO3 of 85% purity would be required to prepare 45.6 mL of 0.235N H2SO4?
Solution Meq. of Na2CO3 = Meq. of H2SO4
= 45.6 × 0.235
WNa2 CO3
 × 1000 = 45.6 × 0.235
ENa2 CO3
WNa2 CO3
 × 1000 = 45.6 × 0.235
106 / 2
 WNa2 CO3 = 0.5679 g
For 85 g of pure Na2CO3, weighed sample = 100 g
100
 For 0.5679 g of pure Na2CO3, weighed sample =  0.5679 = 0.6681 g
85

6.0 APPLICATIONS OF THE LAW OF EQUIVALENCE

6.1 Simple Titration
In this, we can find the concentration of unknown solution by reacting it with solution of known concentration
(standard solution).
For example, let there be a solution of substance A of unknown concentration. We are given solution of
another substance B whose concentration is known (N1). We take a certain known volume of A in a flask (V2)
and then we add B to A slowly till all the A is consumed by B (this can be known with the help of indicators).
Let us, assume that the volume of B consumed is V1. According to the law of equivalence, the number of g
equivalents of B at the end point.
 N1V1 = N2V2, where N2 is the conc. of A.
From this we can calculate the value of N2.

Illustration 21. 0.4 M KMnO4 solution completely reacts with 0.05 M FeSO4 solution under acidic conditions. The
volume of FeSO4 used is 50 mL. What volume of KMnO4 was used ?
Solution 0.4 × 5 × V = 0.05 × 50
V = 1.25 mL
Illustration 22. 1.20 g sample of Na2CO 3 and K 2CO 3 was dissolved in water to form 100 mL of a
Solution. 20 mL of this solution required 40 mL of 0.1 N HCl for complete neutralization.
Calculate the weight of Na2CO3 in the mixture. If another 20 mL of this solution is treated with
excess of BaCl2 what will be the weight of the precipitate ?
Solution Let, weight of Na2CO3 = x g
Weight of K2CO3 = y g
 x + y = 1.20 g ....(i)
For neutralization reaction of 100 mL
Meq. of Na2CO3 + Meq. of K2CO3 = Meq. of HCl
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

x y 40  0.1  100
 × 2 × 1000 + × 2 × 1000 =
106 138 20
 69 x + 53 y = 73.14 .....(ii)
From Eqs. (i) and (ii), we get
x = 0.5962 g
y = 0.604 g
Solution of Na2CO3 and K2CO3 gives ppt. of BaCO3 with BaCl2
(Meq. of Na2CO3 + Meq. of K2CO3) in 20 mL = Meq. of BaCO3
 Meq. of HCl for 20 mL mixture = Meq. of BaCO3
 Meq. of BaCO3 = 40 × 0.1 = 4
WBaCO3
× 1000 = 40 × 0.1 = 4
M BaCO3

WBaCO3
× 2 × 1000 = 4
197
 WBaCO3 = 0.394 g

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6.2 Back titration
Back titration is used to calculate % purity of a sample. Let us assume that we are given an impure solid
substance C weighing w gram and we are asked to calculate the percentage of pure C in the sample. We will
assume that the impurities are inert. We are provided with two solutions A and B, where the concentration of
B is known (N1) and that of A is not known. This type of titration will work only if the following condition is
satisfied, i.e. the nature of compounds A, B and C should be such that A and B can react with each other. A
and C can react with each other but the product of A and C should not react with B.
Now, we take a certain volume of A in a flask ( the g equivalents of A taken should be g equivalents of C
in the sample and this can be done by taking A in excess). Now, we perform a simple titration using B. Let
us assume that the volume of B used is V1. In another beaker, we again take the solution of A in the same
volume as taken earlier. Now, C is added to this and after the reaction is completed, the solution is being
titrated with B. Let us assume that the volume of B used up is V2. Gram equivalents of B used in the first
titration = N1V1.
 gm. equivalents of A initially = N1V1
gm. equivalents of B used in the second titration = N1V2
 gm. equivalents of A left in excess after reacting with C = N1V2
gm. equivalents of A that reacted with C = N1V1 – N1V2
N1 V1  N1 V2
If the n-factor of C is x, then the moles of pure C =
x
N1 V1  N1 V2
 The weight of C = × Molecular weight of C
x
N V  N1 V2 Molecular wt. of C
 Percentage of C = 1 1 ×  100
x w

Illustration 23. 20 g of a sample of Ba(OH)2 is dissolved in 10 mL of 0.5 N HCl solution : The excess of HCl was
titrated with 0.2 N NaOH. The volume of NaOH used was 10 cc. Calculate the percentage of Ba(OH)2
in the sample.
Solution Milli eq. of HCl initially = 10 × 0.5 = 5
Milli eq. of NaOH consumed = Milli eq. of HCl in excess = 10 × 0.2 = 2
 Milli eq. of HCl consumed = Milli eq. of Ba(OH)2 = 5 – 2 = 3
 Eq. of Ba(OH)2 = 3/1000 = 3 × 10–3
Mass of Ba(OH)2 = 3 × 10–3 × (171/2) = 0.2565 g
% Ba(OH)2 = (0.2565 / 20) × 100 = 1.28 %

6.3 Redox titrations

Estimation of By titrating Reactions Relation between
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

with O.A. and R.A.

Fe2+ MnO4– Fe2+  Fe3+ + e– 5Fe2+  MnO4–

MnO4– + 8H+ + 5e– Mn2+ + 4H2O Eq. wt. Fe2+ = M/1
Eq. wt. MnO4– = M/5

Fe2+ Cr2O72– Fe2+  Fe3+ + e– 6Fe2+  Cr2O72–

Cr2O72– + 14H+ + 6e– 2Cr3++7H2O Eq. wt. Cr2O72– = M/6

C2O42– MnO4– C2O42–  2CO2 + 2e– 5C2O42–  2MnO4–

MnO4– + 8H+ + 5e– Mn+2 + 4H2O Eq. wt. C2O42– = M/2
Eq. wt. MnO4– = M/5

H2O2 MnO4– H2O2  2H+ + O2 + 2e– 5H2O2  2MnO4–

MnO4– + 8H+ + 5e– Mn2+ + 4H2O Eq. wt. H2O2 = M/2
Eq. wt. MnO4– = M/5

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 REDOX REACTION

As2O3 MnO4– As2O3 + 5H2O  2AsO43– + 10H+ + 4e– Eq. wt. As2O3= M/4
AsO33– BrO3– AsO33– + H2O  AsO43– + 2H+ + 2e– Eq. wt. AsO33–= M/2
BrO3– + 6H+ + 6e– Br– + 3H2O Eq. wt. BrO3– = M/6

Illustration 24. 3.2 g of pyrolusite was treated with 50 mL of 0.5 M oxalic acid and some sulphuric acid. The oxalic
acid left undecomposed was raised to 250 mL in a flask. 25 mL of this solution when treated with 0.02
M KMnO4 required 32 mL of the solution : Find the % of MnO2 in the sample and also the percentage
of available oxygen.
Solution Redox changes are C2O42–  2CO2 (n-factor = 2)
– 2+
MnO4  Mn (n-factor = 5)
MnO2  Mn2+ (n-factor = 2)
Meq. of MnO2 = Meq. of oxalic acid taken - Meq. of oxalic acid left
= 50 × 0.5 × 2 – 32 × 0.02 × 5 × 10 (in 250 mL) = 18
WMnO2 WMnO2
× 2 × 1000 = 18  × 2 × 1000 = 18,
M MnO2 87
 WMnO2 = 0.7821 g
0.7821
 % of MnO2 =  100 = 24.44 %
3.2
Meq. of MnO2 = Meq. of O2
WO2
× 2 × 1000 = 18,  WO2 = 0.144 g
16
0.144
% of available O2 = × 100 = 4.5
3.2
Illustration 25. A 20 g sample of only CuS and Cu2S was treated with 100 mL of 1.25 M K2Cr2O7. The products
obtained were Cr3+, Cu2+ and SO2. The excess oxidant was reacted with 50 mL of Fe2+ Solution
: 25 mL of the same Fe2+ solution required 0.875 M KMnO4 under acidic condition, the volume of
KMnO4 used was 20 mL. Find the % of CuS and Cu2S in the sample.
1.25  6  100
Solution Equivalents of dichromate initially= = 0.75
1000
0.875  5  5  20
Equivalents of Fe2+ in 25 mL= = 0.0875
1000
2+
Equivalents of Fe in 50 mL= 0.0875 × 2 = 0.175
Equivalents of excess dichromate= 0.175
 Equivalents of dichromate consumed by (CuS and Cu2S) = 0.75 – 0.175 = 0.575
If x g is the mass of CuS, the mass of Cu2S is (10 – x) g
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

x (10  x)
× 6 + × 8 = 0.575
95.5 159
 x = 5.74 g
5.74
% CuS = × 100 = 28.7 %
20
% Cu2S = 71.3 %

Illustration 26. A 2.18 g sample contains a mixture of XO and X2O3. It reacts with 0.015 moles of K2Cr2O7 to oxidize
the sample completely to form XO4– and Cr3+. If 0.0187 mole of XO4– is formed, what is the atomic
mass of X?
Solution XO + K2Cr2O7  Cr3+ + XO4–
X2O3 + K2Cr2O7  Cr3+ + XO4–
Let, wt. of XO in the mixture be x g
Equivalent of K2Cr2O7 consumed by the mixture= 0.015 × 6

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x
Equivalents of XO = 5
x  16
2.18 – x
Equivalents of X2O3 = 8
2x  48
x 2.18  x
 5 +  8 = 0.015 × 6
x  16 2x  148
Since 1 mole of XO gives 1 mole XO4– and 1 mole of X2O3 gives 2 moles of XO4–,
x 2x(2.18  x)
 + = 0.0187
x  16 2x  48
On solving, x = 99

6.4 Iodometric and Iodimetric Titration

The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine occurs in these titrations.
I2 + 2e–  2I– (reduction)
2I–  I2 + 2e– (oxidation)
These are divided into two types :
 Iodometic Titration
In iodometric titrations, an oxidizing agent is allowed to react in neutral medium or in acidic medium with
excess of potassium iodide to liberate free iodine.
KI + oxidizing agent  I2
Free iodine is titrated against a standard reducing agent usually with sodium thiosulphate. Halogen, dichromates,
cupric ion, peroxides etc., can be estimated by this method.
I2 + 2NaS2O3  2NaI + Na2S4O6
2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2
K4Cr2O7 + 6KI + 7H2SO4  Cr2(SO4)3 + 4K2SO4 + 7H2O + 3I2
 Iodimetric Titration
These are the titrations in which free iodine is used as it is difficult to prepare the solution of iodine (volatile and
less soluble in water), it is dissolved in KI solution :
KI + I2  KI3 (Potassium triiodide)
This solution is first standardized before using with the standard solution of substance such as sulphite,
thiosulphate, arsenite etc, are estimated.
In iodimetric and iodometric titration, starch solution is used as an indicator. Starch solution gives blue or
violet colour with free iodine. At the end point, the blue or violet colour disappears when iodine is completely
changed to iodide.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

 SOME IODOMETRIC TITRATIONS (TITRATING SOLUTIONS IS Na2S2O3.5H2O)

Estimation of Reaction Relation between

O.A. and R.A.
I2 I2 + 2Na2S2O3  2Nal + Na2S4O6 I2 = 2I  2Na2S2O3
or Eq. wt. of Na2S2O3 = M/1
I2 + 2S2O32–  2I – + S4O62–

CuSO4 2CuSO4 + 4KI  2Cu2I2 + 2K2SO4 + I2 2CuSO4  I2  2I  2Na2S2O3

2+ –
Cu + 4I  Cu2I2 + I 2 Eq. wt. of CuSO4 = M/1
(White ppt.)
CaOCl2 + H2O Ca(OH)2 + Cl2

CaOCl2 Cl2 + 2KI 2KCl + I2 CaOCl2Cl2I22I2Na2S2O 3

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 REDOX REACTION
Cl2 + 2I – 2Cl – + I2 Eq. wt. of CaOCl2 = M/2

MnO2 + 4HCl (conc) 


 MnCl2 + Cl2 + 2H2O
Cl2 + 2KI 2KCl + I2

MnO2 or MnO2  Cl 2  I 2  2I 
2Na2S2O 3
MnO2 + 4H+ + 2Cl–  Mn2+ + 2H2O + Cl2 Eq. wt. of MnO2 = M/2
– –
Cl2 + 2I  I2 + 2Cl

IO3– IO3– + 5I – + 6H+ 3I2 + 3H2O IO3–  3I2  6I  6Na 2S 2O 3

Eq. wt. of IO3– = M/6

H2O2 H2O2 + 2I – + 2H+ I2 + 2H2O H2O2  I2  2I  2Na 2S 2O 3

Eq. wt. of H2O2 = M/2

Cl2 Cl2 + 2I – 2CI – + I2 Cl2  I2  2I  2Na 2S 2O 3

Eq. wt. of Cl2 = M/2

O3 O3 + 6I – + 6H+3I 2 + 3H2O O3  3I2  6I  6Na 2S 2O 3

Eq. wt. of O3 = M/6

Cr2O72– Cr2O72–+14H+ + 6I – 3I2 + 2Cr3++7H2O Cr2O72–  3I2  6I

Eq. wt. of Cr2O72–

MnO4– 2MnO4–+10I– +16H+  2MnO4– + 5I2 + 8H2O 2MnO4–  5I2  10I

Eq. wt. of MnO4– = M/5

BrO3– BrO3–+6I– +6H+  Br– + 3I2 + 3H2O BrO3–  3I2  I 2

Eq. wt. of BrO3– = M/6
As(V) H3AsO4 + 2I– + 2H+  H3AsO3 + H2O + I2 H3AsO4  I2  2I
Eq. wt. of H3AsO4 = M/2

 SOME IODIMETRIC TITRATION (TITRATING SOLUTIONS IS I2 IN KI)

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Estimation of Reaction Relation between

O.A. and R.A.
H2S H2S + I2  S + 2I – + 2H+ H2S  I2  2I
(in acidic medium) Eq. wt. of H2S = M/2

SO32– SO32– + I2 + H2O  SO32– + 2I – + 2H+ SO32–  I2  2I

(in acidic medium) Eq. wt. of SO32– = M/2

Sn2+ Sn2+ + I2  Sn4+ + 2I – Sn2+  I2  2I

(in acidic medium) Eq. wt. of Sn2+ = M/2
As(III) (at pH = 8) H2AsO3– + I2 + H2O  HAsO42– + 2I – + 2H+ H2AsO3–  I2  2I
Eq. wt. of H2AsO3– = M/2

N2H4 N2H4 + 2I2  N2 + 4H+ + 4I – N2H4  2I2  4I

Eq. wt. of N2H4 = M/4

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JEE-Chemistr y

Illustration 27. One litre of a mixture of O2 and O3 at NTP was allowed to react with an excess of acidified solution
of KI. The iodine liberated required 30 mL of M/10 Na2S2O3 solution for titration. What is the weight
percent of ozone in the mixture ?
Ultraviolet radiation of wavelength 300 mm can decompose ozone. Assuming that one photon can
decompose one ozone molecule, how many photons would have been required for the complete
decomposition of ozone in the original mixture?
Solution O3 + 2 KI + H2O  2KOH + I2 + O2
2Na2S2O3 + I2  Na2S4O6 + 2Nal
Millimoles of O3 = Millimoles of I2 = ½ Millimoles of Na2S2O3
= ½ 30 × 1/10 = 1.5 millimoles = 0.0015 moles
Total moles of O3 and O2 in the mixture
PV = n RT
1 × 1 = n × 0.0821 × 273
 n = 0.044
Moles of O2 = 0.044 – 0.0015 = 0.0425

WO2 = 0.0425 × 32 g = 1.36 g

WO3 = 0.0015 × 48 g = 0.072 g

0.072
 % of O3 = × 100 = 5.028 %
1.432
No. of photons required for decomposition of Ozone molecules
= 0.0015 × 6.023 × 1023 = 0.90 × 1021

Illustration 28. An aqueous solution containing 0.10 g KIO3 (formula wt. = 214.0) was treated with an excess of KI
Solution : The solution was acidified with HCl. The liberated I2 consumed 55 mL of thiosulphate
solution to decolourize the blue starch-iodine complex. Calculate molarity of the sodium thiosulphate
solution :

0.1
Solution Moles of KIO3 = = 0.00047
214
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0.00047
 Moles of I2 liberated from KIO3 = = 0.000235
2
Moles of KI reacting = 0.00047 × 5 = 0.00235( n-factor for KIO3 and KI are 5 and 1 respectively)
0.00235
Moles of I2 produced from KI = = 0.001175
2
Total moles of I2 produced and reacted = 0.000235 + 0.001175 = 0.00141 equivalents of I2
reacted = 0.00141 × 2 = 0.00282 = equivalents of thiosulphate Solution :
0.00282  1000
Molarity = =0.0512 M (For thiosulphate n-factor = 1)
55

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 REDOX REACTION

Normality of a solution
1. 50 mL of 0.1 M polyprotic acid (HnA) required 50 mL of 0.2 M NaOH for complete neutralization, then value
of n is
(A) 1 (B) 3 (C) 2 (D) 4
2. 10 gm sample of H3PO4 is dissolved in water to make 1 L solution. 100 mL of this solution requires 200 mL of
0.1 N NaOH for neutralization of H3PO4, according to given reaction
H3PO4 + 2NaOH  Na2HPO4 + 2H2O. Calculate % purity of H3PO4 smaple
(A) 10% (B) 9.8 % (C) 98 % (D) 49%
3. 1.25 g of a solid dibasic acid is completely neutralised by 25 mL of 0.25 molar Ba(OH)2 solution. Molecular
mass of the acid is :
(A) 100 (B) 150 (C) 120 (D) 200
4. 10 mL of N-HCl, 20 mL of N/2 H2SO4 and 30 mL of N/3 HNO3 are mixed together and volume made to one
litre. The normality of H+ in the resulting solution is :

3N N N N
(A) (B) (C) (D)
100 10 20 40
5. 0.45 g of an acid of mol. wt. 90 was neutralised by 20 mL of 0.54 N caustic potash (KOH). The basicity of
acid is :
(A) 1 (B) 2 (C) 3 (D) 4
6. 25 mL of 2 N HCl, 50 mL of 4 N HNO3 and x mL of 2 M H2SO4 are mixed together and the total volume
is made up to 1 L afterdilution. 50 mL of this acid mixture completely reacted with 25 mL of a 1 N Na2CO3
solution. The value of x is :
(A) 250 mL (B) 62.5 mL (C) 100 mL (D) None of these
7. KMnO4 reacts with oxalic acid according to the equation

2MnO4  5C 2O 42  16H 

 2Mn2  10CO2  8H 2O


Here, 20 mL of 0.1 M KMnO4 is equivalent to :

(A) 120 mL of 0.25 M H2C2O4 (B) 150 mL of 0.10 M H2C2O4
(C) 25 mL of 0.20 M H2C2O4 (D) 50 mL of 0.20 M H2C2O4
8. 1 mol of FeC2O4 is oxidised by x mol of Cr2O72– in acidic medium, x is :
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(A) 3 (B) 1.5 (C) 0.5 (D) 1.0

–
9. 1 mol of MnO4 will oxidise x mol of ferric oxalate in acidic medium, x is :
(A) 5/6 (B) 6/5 (C) 5 (D) 6
10. 3 mol of a mixture of FeSO4 and Fe2(SO4)3 required 100 ml of 2 M KMnO4 solution in acidic medium. Hence
mol fraction of FeSO4 in the mixture is :
(A) 1/3 (B) 2/3 (C) 2/5 (D) 3/5
11. A mixture of Na2C2O4 (A) and KHC2O4. H2C2O4 (B) required equal volumes of 0.1 M KMnO4 and 0.1 M
NaOH separately. Molar ratio of A and B in the mixture is :
(A) 1 : 1 (B) 1 : 5. 5 (C) 5. 5 : 1 (D) 3.1 : 1
12. A2Ox is oxidised to AO3– by MnO4– in acidic medium. If 1.5 × 10-3 mole of A2Ox requires 40 ml of 0.03 M-
KMnO4 solution in acidic medium. Which of the following statement(s) is/are correct?
(A) The value of "x" = 1
(B) The value of "x" = 3
(C) Empirical formula of oxide is AO3.
(D) Empirical formula of oxide is A2O.

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13. One litre of a mixture of O2 and O3 (O3 O2 + O2–) at 1 atm and 273 K was allowed to react with an
excess of acidified solution of KI. The iodine liberated required 40 ml of M/10 sodium thiosulphate solution for
titration the percent of ozone in the mixture ? (by weight) :

(A) 6.57 % (B) 3.2 % (C) 4.67% (D) 50%

14. An aqueous solution containing 0.10 KIO3 (formula wt. = 214.0) was treated with an excess of KI solution. The
solution was acidified with HCl. The liberated I2 consumed 45.0 ml of thiosulphate solution to decolourise the
blue starch – iodine complex the molarity of the sodium thiosulphate solution.

(A) 0.02 M (B) 0.623 M (C) 0.05 M (D) 0.0235 M

15. In iodometric estimation of Cu2+ ion, the following reactions took place. :
2Cu2+ + 4I–  Cu2I2 + I2
I2 + 2Na2S2O3  2NaI + Na2S4O6
If 100 mL of CuSO4 solution added to excess KI requires 50 mL of 0.2 M Na2S2O3, the molarity of CuSO4
solution is :
(A) 0.05 M (B) 0.1 M (C) 0.2 M (D) 0.25 M
16. 25 mL of household bleach solution was mixed with 30 mL of 0.50 M KI and 10 mL of 4 N acetic acid.
In the titration of the liberated iodine, 48 mL of 0.25 N Na2S2O3 was used to reach the end point. The
molarity of the household bleach solution is
(A) 0.48 M (B) 0.96 M (C) 0.24 M (D) 0.024 M
17. 20 g of a sample of Ba(OH)2 is dissolved in 10 ml of 0.5 N HCl solution. The excess of HCl was titrated
with 0.2 N NaOH. The volume of NaOH used was 10 ml. The % of Ba(OH)2 in the sample.
(A) 2.4 % (B) 3.08 % (C) 1.28 % (D) 1.67%

7.0 HYDROGEN PEROXIDE (H2O2)

H2O2 can behave both like oxidising and reducing agents in both the medium (acidic and basic).
Oxidising agent : (H2O2) –2
e 2
(a) Acidic medium : duc
Re
3
(R)
–1
2e– + 2H+ + H2O2 
4
2H2O 2 2
Ox
v.f. = 2 idis 0
e
2
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(b) Basic medium :

2e– + H2O2 2OH–
v.f. = 2

Reducing agent : (H2O2) :

(a) Acidic medium :
H2O2 O2 + 2H+ + 2e–
v.f. = 2

(b) Basic medium :

2OH– + H2O2 O2 + 2H2O + 2e–
v.f. = 2

Volume strength of H2O2 : Strength of H2O2 is represented as 10 V, 20 V, 30 V etc.

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 REDOX REACTION
20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20 L of O2 gas at S.T.P.
Volume,strength of H 2 O2
Normality of H2O2 (N)=
5.6
N H 2 O2 N H 2O2
 M H 2 O2  =
v.f 2
Volume,strength of H 2 O 2
Molarity of H2O2 (M)=
11.2
Strength (in g/L) : Denoted by S
Strength= molarity × mol. wt. = molarity × 34
Strength= Normality × Eq. weight. = Normality × 17

N
Illustration 29. 20 mL of H2O2 after acidification with dil H2SO4 required 30 mL of KMnO4 for complete
12
oxidation. The strength of H2O2 solution is [Molar mass of H2O2 = 34]
1
Solution 30 × = 20 × N'
12
30 1
N' = =
12  20 8
1
 strength = N' × equivalent mass = × 17 = 2.12 g/L
8

8.0 HARDNESS OF WATER

Temporary hardness - due to bicarbonates of Ca & Mg
Permanent hardness - due to chloride & sulphates of Ca & Mg. There are some method by which we can
softening the water

(a) by boiling : 2HCO3–  H2O + CO2 + CO32– or

by slaked lime : Ca(HCO3)2 + Ca(OH)2  CaCO3 + 2H2O
Ca2+ + CO32–  CaCO3
(b) By Washing Soda : CaCl2 + Na2CO3  CaCO3+ 2NaCl
(c) By ion exchange resins : Na2R + Ca2+  CaR + 2Na+
Parts per million (ppm):
When the solute is present in very less amount then this concentration term is used. It is defined as the number
of parts of the solute present in every 1 million parts of the solution. ppm can both be in terms of mass or in
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

terms of moles. If nothing has been specified we take ppm to be in terms of mass. hence a 100 ppm solution
means that 100 g of solute are present in every 1000000 g of solution.
massof A
ppmA = × 106 = mass fraction × 106
Total mass

Measurement of Hardness
Hardness is measured in terms of ppm (parts per million) of CaCO3 or equivalent to it.

Illustration 30. 0.00012% MgSO4 and 0.000111% CaCl2 is present in water. What is the measured hardness of
water and millimoles of washing soda requires to purify 1000 litre water.
Solution 0.00012% MgSO4 = 1 mg CaCO3 1 L water
0.000111% CaCl2 = 1 mg CaCO3 1 L water
hardness = 2 ppm and mm of Na2CO3 require is 20

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JEE-Chemistr y
9.0 STRENGTH OF OLEUM
Oleum is SO3 dissolved in 100% H2SO4. Sometimes, oleum is reported as more than 100% by weight, say y%
(where y > 100). This means that (y – 100) grams of water, when added to 100 g of given oleum sample, will
combine with all the free SO3 in the oleum to give 100% sulphuric acid. Hence weight % of free SO3 in oleum
= 80(y – 100)/18

10.0 CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF

BLEACHING POWDER
The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or CO2 is
called available chlorine.
CaOCl2 + H2SO4  CaSO4 + H2O + Cl2 CaOCl2 + 2HCl  CaCl2 + H2O + Cl2
CaOCl2 + 2H3CCOOH  Ca(CH3COO)2 + H2O + Cl2 CaOCl2 + CO2  CaCO3 + Cl2
 Method of determination
or KI3 starch
Bleaching powder + CH3COOH + KI   KI3 end point (Blue  colourless)
Hypo
3.55  x  V(mL )
% of Cl2 =
W(g)
where x = molarity of hypo solution, v = mL of hypo solution used in titration.

Illustration 31. 3.55 g sample of bleaching powder suspended in H2O was treated with enough acetic acid and
KI solution. Iodine thus liberated requires 80 mL of 0.2 M hypo for titration. Calculate the % of
available chlorine.
[Available Chlorine = mass of chlorine liberated / mass of bleaching powder × 100]
80  0.2
Solution moles of iodine = moles of chlorine = × 10–3 = 8 × 10–3
2
8  71  10 –3
so required % = × 100% = 16%
3.55

Hardness of water
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1. The volume of O 2 gas liberated at 0°C and 1 atm, when 25 mL of '30 volumes' H 2O 2 is completely
decomposed
(A) 750 mL (B) 75 mL (C) 480 mL (D) 672 mL
2. 20 mL of '20 vol' H 2O 2 solution is diluted to 40 mL. The new volume strength of the solution becomes.
(A) '40 vol' (B) '10 vol' (C) '25 vol' (D) '8 vol'
3. In 200 g of a sample of oleum labeled as 109.00 %, 12 g water is added. The new labeling of the oleum
sample is :
(A) 106.00 % (B) 103.00 % (C) 102.83 % (D) 105.66 %
4. When 200 g of an oleum sample labeled as 109% is mixed with 300 gof another oleum sample labeled as
118% the new labeling of resulting oleum sample becomes :
(A) 114.4 % (B) 112.6% (C) 113.5% (D) 127%
5. 100 ml of 0.01 M KMnO 4 oxidizes 10 ml of H2O2 sample in acidic medium. The volume strength of H2O2
sample is :
(A) 11.2 vol (B) 5.6 vol (C) 2.80 Vol (D) none of these

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 REDOX REACTION
6. The volume strength of 10% (w/w) aqueous H 2O 2 solution of specific gravity 1.19 is :
(A) 10 vol (B) 39.2 vol (C) 32.9 vol (D) 27.7 vol
7. Which of the following salt do not contribute to hardness of water
(A) MgSO 4 (B) NaCl (C) Ca(HCO3)2 (D) MgNO3
8. Temporary hardness is due to
(A) sulphates of Magnesium and calcium. (B) Nitrates of Magnesium and calcium.
(C) Bicarbonates of Magnesium and calcium. (D) None of these
9. Temporary hardness is removed by
(A) heating the water sample (B) by treatment with CaO(s)
(C) both (A) and (B) (D) none of these
10. 1L water sample contains 146 mg of Mg(HCO 3)2. Calculate hardness in units of ppm of CaCO 3.
(A) 50 ppm (B) 100 ppm (C) 200 ppm (D) 25 ppm
11. 1L water smaple contains 16.2 mg of Ca(HCO3)2. Calculate required no. of millimole of CaO(s) to remove
hardness:
(A) 0.05 m moles (B) 0.1 m moles (C) 0.5 m moles (D) 2 m moles
12. 1 L of pond water contains 20 mg of Ca2+ and 12 mg of Mg 2+ ions. What is the volume of a 2 N Na2CO3
solution required to soften 5000 L of pond water?
(A) 500 L (B) 50 L (C) 5 L (D) None of these
13. RH2 (ion exchange resin) can replace Ca2+ ions in hard water as RH2 + Ca2+  RCa. + 2H+.

If 1 L of hard water after passing through RH2 has pH = 3 then hardness in parts per million of Ca2+ is:
(A) 20 (B) 10 (C) 40 (D) 100

wt. in g
 Number of moles of molecules =
Mol. wt.
wt. in g
Number of moles of atoms =
Atomicmass
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Volumeat STP
Number of moles of gases =
Standardmolar volume
Number of particles
Number of moles of particles, e.g. atoms, molecular ions etc. =
Avogadro No.
Moles of solute in solution = M × V(L)
Atomic wt.
 Equivalent wt. of element =
Valence
Mol. wt.
Equivalent wt. of compound =
Total chargeon cation or anion
Mol wt.
Equivalent wt. of acid =
Basicity
Mol wt.
Equivalent wt. of base =
Acidity
Formula wt.
Equivalent wt. of an ion =
Chargeon ion

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JEE-Chemistr y

Molecular wt.
Equivalent wt. of acid salt =
Replaceable H atom in acidsalt
Mol. wt.
Equivalent wt. of oxidizing or reducing agent =
Changein oxidation number per mole
wt.in g
No. of equivalent = N × V(L) =
Eq.wt.
Ws  1000 x  d  10
 Molarity (M) = =
Ms  V Ms
where
Ws = wt. of solute in g
Ms = Mol. wt. of solute
x = % by mass of solute
d = density of solution in g/ml
V = volume of solution in ml
Ws  1000 x  d  1000
 Normality (N) = E  V = Es
s
Ws = wt. of solute in g.
Es = eqv. wt. of solute
V = volume of solution in ml
x = % by mass of solute
d = density of solution in g/ml
wt.of solute
 Moles = M × V(L) =
Mol.wt.
wt.of solute
Millimoles = M × V(ml) =  1000
Mol.wt.
Equivalents of solute = N × V(L)
wt.
Meq. of solute  1000
Eq.wt.

 Molarity equation :
If a solution having molarity M1 and volume V1 is diluted to volume V2 so that new molarity is
M2 then total number of moles remains the same.
M1V1 = M2V2
For a balanced equation involving n1 moles of reactant 1 and n2 moles of reactant 2.
M1 V1 M V
= 2 2
n1 n2
Normality equation : According to the law of equivalence, the substances combine together in
wt.of A Eq. wt.of A
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the ratio of their equivalent masses =

wt.of B Eq. wt.of B
wt.of A wt.of B
 =
Eq. wt.of A Eq. wt.of B
Number of gram equivalents of A = Number of gram equivalents of B
N  VA
Number of gram equivalents of A = A
1000
N B VB
Number of gram equivalents of B =
1000
N A VA N B VB
 = NA × VB = NB × VB
1000 1000
The above equation is called normality equation.

 Normality (N) = Molarity (M) × n

(where n = n-factor)
For acid-base (neutralization reaction or redox reaction)
N1V1 = N2V2 always true

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 REDOX REACTION
But M1V1 = M2V2 (may or may not be true )
But M1n1V1 = M2n2V2 (always true where n-terms represent n-factor)
Molesof solute
 Molality (m) =
wt.of solvent (in kg)
 Strength of solution (S) = N × Eq.wt.
= M × mol. wt.
PROBL

SOME WORKED OUT ILLUSTRATIONS

Illustration 1.
What volume of 0.40 M H2SO4 is required to produce 34.0 g of H2S by the reaction,
8 KI + 5 H2SO4  4 K2SO4 + 4 I2 + H2S + 4 H2O ?
Solution
1 mole of H2S  5 moles of H2SO4
34 g of H2S  5 moles of H2SO4
0.40 × VH 2 SO4  5
5
 VH 2 SO4 = = 12.5 litre
0.40
Illustration 2.
To 50 L of 0.2 N NaOH, 2.5 L of 2N HCl and 15 L of 0.1 N FeCl3 solutions are added. What weight of Fe2O3
can be obtained from the precipitate? Also report the normality of NaOH left in resultant solution :
Solution
Eq. of NaOH = 50 × 0.2 = 10
Eq. of HCl = 2.5 × 2 = 5
Eq. of NaOH left after reaction with HCl = 10 – 5 = 5
FeCl3 + NaOH  Fe (OH)3   Fee2O3


FeCl3 reacts with NaOH to give Fe(OH)3 which on ignition gives Fe2O3
 Eq. of NaOH used for FeCl3 = Eq. of Fe(OH)3
= Eq. of Fe2O3
= 15 × 0.1 = 1.5
 Eq. of NaOH left finally = 5 – 1.5 = 3.5
3.5
Normality of NaOH in the resultant solution = = 0.051
67.5
WFe2 O3
× 6 = 1.5 (n-factor for Fe2O3 = 6)
M Fe2 O3
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1.5  160
WFe2 O3 =  40g
6
Illustration 3.
One litre of a mixture of O2 and O3 at NTP was allowed to react with an excess of acidified solution of KI. The
iodine liberated required 30 mL of M/10 Na2S2O3 solution for titration. What is the weight percent of ozone in
the mixture ?
Ultraviolet radiation of wavelength 300 mm can decompose ozone. Assuming that one photon can decompose
one ozone molecule, how many photons would have been required for the complete decomposition of ozone
in the original mixture?
Solution
O3 + 2 KI + H2O  2KOH + I2 + O2
2Na2S2O3 + I2  Na2S4O6 + 2Nal
Millimoles of O3 = Millimoles of I2 = ½ × Millimoles of Na2S2O3
= ½ × 30 × 1/10 = 1.5 millimoles
= 0.0015 moles
Total moles of O3 and O2 in the mixture
PV = n RT

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JEE-Chemistr y
1 × 1 = n × 0.0821 × 273
 n = 0.044
Moles of O2 = 0.044 – 0.0015 = 0.0425
WO2 = 0.0425 × 32 g = 1.36 g
WO3 = 0.0015 × 48 g = 0.072 g
0.072
 % of O3 = × 100 = 5.028 %
1.432
No. of photons required for decomposition of Ozone molecules = 0.0015 × 6.023 × 1023 = 0.90 × 1021
Illustration 4.
2.249 g of a sample of pure BaCO3 and impure CaCO3 containing some CaO was treated with dil. HCl and
it evolved 168 mL of CO2 at N.T.P. From this solution, BaCrO4 was precipitated filtered and washed. The
precipitate was dissolved in dil. H2SO4 and diluted to 100 mL. 10 mL of this solution when treated with KI
solution liberated iodine which required exactly 20 mL of 0.05 N Na2S2O3. Calculate the percentage of CaO
in the sample.
Solution
Let, weight of BaCO3, CaCO3 and CaO are x,y and z respectively.
 x + y + z = 2.249
BaCO3  BaCrO4
Redox change Cr6+ + 3e–  Cr3+
2I–  I2 + 2e–
Meq. of BaCO3 = Meq. of BaCrO4 = Meq. of I2
x 100
 × 1000 = 20 × 0.05 ×
197 / 3 10
 x = 0.657 g ....(1)
The equivalent weight of BaCrO4 is M/3, therefore for BaCO3, it should be M/3 also because mole ratio of
BaCO3 and BaCrO4 is 1 : 1.
Applying POAC for C atom,
Moles of C in BaCO3 + Moles of C in CaCO3 = Moles of C in CO2
x y 168
 + =
197 100 22400
 200 x + 294 y = 295.5 ....(2)
From equation (1) and (2)
y = 0.416 g
 0.657 + 0.416 + z = 2.249
z = 1.176
1.176
% of CaO = = 52.29 %
2.249
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Illustration 5.
For estimating ozone in the air, a certain volume of air is passed through an alkaline KI solution when O2 is
evolved and iodide is oxidized to iodine. When such a solution is acidified, free iodine is evolved which can be
titrated with standard Na2S2O3 Solution : In an experiment, 10 L of air at 1 atm and 27°C were passed
through an alkaline KI solution, and at the end, the iodine was entrapped in a solution which on titration as
above required 1.5 mL of 0.02 N Na2S2O3 solution. Calculate volume percentage of ozone in the sample.
Solution
The chemical reaction is, H2O + KI + O3  I2 + O2 + KOH
Milliequivalents of iodine = Milliequivalents of KI = Milliequivalents of O3 reacted
Milliequivalents of Na2S2O3 = 1.5 × 0.02 = 3 × 10–2
3  1 0 2
Millimoles of iodine = = 1.5 × 10–2 [n-factor for iodine = 2]
2
Millimoles of ozone = 1.5 × 10–2
nRT 1.5  10 5  0.0821  300
Volume of ozone = = = 36.945 × 10–5 litree
P 1
36.945  10 5
Volume percent of ozone = × 100 = 3.6945 × 10–3
10

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 REDOX REACTION
Illustration 6.
An aqueous solution containing 0.10 g KIO3 (formula wt. = 214.0) was treated with an excess of KI Solution : The
solution was acidified with HCl. The liberated I2 consumed 55 mL of thiosulphate solution to decolourize the
blue starch-iodine complex. Calculate molarity of the sodium thiosulphate solution :
Solution
0.1
Moles of KIO3 = = 0.00047
214
0.00047
 Moles of I2 liberated from KIO3 = = 0.000235
2
Moles of KI reacting = 0.00047 × 5 = 0.00235 ( n-factor for KIO3 and KI are 5 and 1 respectively)
0.00235
Moles of I2 produced from KI = = 0.001175
2
Total moles of I2 produced and reacted = 0.000235 + 0.001175 = 0.00141 equivalents of I2 reacted =
0.00141 × 2 = 0.00282 = equivalents of thiosulphate Solution :
0.00282  1000
Molarity = =0.0512 M (For thiosulphate n-factor = 1)
55

Illustration 7.
Mg can reduce NO3– to NH3 in basic medium.
NO3– + Mg (s) + H2O  Mg (OH)2 (s) + OH– (aq.) + NH3(g)
A 25.0 mL sample of NO3– solution was treated with Mg. The NH3 (g) was passed into 100 mL of 0.15 N HCl.
The excess of HCl required 32.10 mL of 0.10 N NaOH for neutralization. What was the molarity of NO3– ions
in the original sample ?
Solution
Meq. of NH3 formed = Meq. of HCl used
= 100 × 0.15 – 32.10 × 0.10
= 11.79
Here, n-factor of NH3 is 1 (acid - base reaction)
For redox change,
(n - factor = 8)
5 3
8 e
NO  NH 3

3
 Meq. of NH3 for n-factor 8 = 8 × 11.79
94.32
 Normality of NO3– = = 3.77
25
3.77
Molarity of NO3– =  0.47125
8

Illustration 8.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

30 mL of a solution containing 9.15 g/litre of an oxalate KxHy (C2O4)z.nH2O are required for titrating
27 mL of 0.12 N NaOH and 36 mL of 0.12 N KMnO4 separately. Calculate x,y,z and n. Assume all H atoms
(except H2O) are replaceable and x,y,z are in the simple ratio of g atoms.
Solution.
Let molecular weight of oxalate salt is M
(i) n - factor in acid - base reaction = 2
(ii) n - factor in redox titration = 2 × z
(C2O42– 2CO2 + 2e)
 Meq. of acid in 30 mL = Meq. of NaOH used
9.15
30 ×  y = 27 × 0.12 ...(1)
M
9.15
Also, 30 ×  (2z) = 36 × 0.12 ...(2)
M
y 27 y 3
From equations (1) and (2)    ...(3)
2z 36 z 2
Also, total cationic charge = total anionic charge
 x + y = 2z ...(4)

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JEE-Chemistr y
By equations (3) and (4)
x : y : z :: 1 : 3 : 2
These are in simplest ratio and molecular formula is KH3 (C2O4)2.nH2O
Molecular weight of salt = 39 + 3 + 176 + 18n = 218 + 18n
30  9.15  3
From equation (1), M = = 254.16
27  0.12
 218 + 18n = 254.15
n=2
 Oxalate salt is KH3(C2O4)2.2H2O

Illustration 9.
Hydrogen peroxide solution (20 mL) reacts quantitatively with a solution of KMnO4 (20 mL) acidified with
dilute H2SO4. The same volume of the KMnO4 solution is just decolourized by 10 mL of MnSO4 in neutral
medium simultaneously forming a dark brown precipitate of hydrated MnO2. The brown precipitate is dissolved
in 20 mL of 0.2 M sodium oxalate under boiling condition in the presence of dilute H2SO4. Write the balanced
equations involved in the reactions and calculate the volume strength of H2O2.
Solution
Meq. of MnO2 = Meq. of Na2C2O4
= 20 × 0.2 × 2 = 8
(C2O42–  2CO2, n-factor = 2)

8
Millimoles of MnO2 = 4
2

or 2MnO4– + 3Mn2+  5MnO2 (Mole ratio is reciprocal of n-factor ratio)

Millimolesof MnO 2 
4

Millimolesof MnO 2 5
2
Millimoles MnO4– = × Millimoles of MnO2
5
2 8
= × 4=
5 5
2KMnO4 + 5H2O2 + 3H2SO4  2 MnSO4 + K2SO4 + 8H2O + 5O2
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Millimolesof H 2 O 2 5

Millimolesof MnO 4 2
5 8
 Millimoles of H2O2 =  =4
2 5
N H 2 O2 × 20 = 4 × 2 (n-factor for H2O2 = 2)

 N H 2 O2 = 0.4

Volume strength of H2O2 = 5.6 × N H 2 O2

= 5.6 × 0.4 = 2.24
Illustration 10.
1.0 g of moist sample of mixture of potassium chlorate (KClO3) and potassium chloride (KCl) was dissolved in
water and solution made upto 250 mL. This solution was treated with SO2 to reduce all ClO3– to Cl– and
excess of SO2 was removed by boiling. The total chloride was precipitated as silver chloride. The weight of
precipitate was found to be 1.435 g. In another experiment, 25 mL of the original solution was heated with 30
ml 0.2 N FeSO4 and unused FeSO4 required 37.5 mL of 0.08 N KMnO4 solutions.
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 REDOX REACTION
Calculate the molar ratio of the ClO3– to the given mixture.
Given that, ClO3– + 6Fe2+ + 6H+  Cl– + 6Fe3+ + 3H2O
3SO2 + ClO3– + 3H2O  Cl– + 3SO42– + 6H+
Solution
ClO3– is reduced to Cl– by SO2 and ClO3– is also reduced to Cl– by Fe2+, hence AgCl is formed due to total Cl–
Meq. of Fe2+ initially taken = 30 × 0.2 = 6
Meq. of Fe2+ unused = 37.5 × 0.08 = 3
 Meq. of Fe2+ = 6.0 – 3.0 = 3.0
Thus, Meq. of ClO3– in 25 mL = 3.0
3.0
Moles of ClO3– in 25 mL = = 0.0005
1000  6
+5
ClO3–  –1 –
Cl (n-factor = 6)
O.N. 5 –1
Thus, moles of ClO3– in 25 mL solution = 0.0005
ClO3– is also reduced to Cl– by SO2 in first experiment and precipitated as AgCl.
Thus, Cl– formed from ClO3– = AgCl from ClO3– = 1.435 g
Total AgCl formed both from actual and Cl– from ClO3– = 1.435 g
1.435
= = 0.01 mol
143.5
Thus, AgCl formed due to Cl– only = 0.01 – 0.0005 = 0.0095 mol
Thus, ClO3– and Cl– are in molar ratio = 1 : 19

Illustration 11.
Chile salt peter a source of NaNO3 also contains NaIO3. The NaIO3 can be used as a source of iodine
produced in the following reactions :
Step 1 : IO3– + 3HSO3–  I – + 3H+ + 3SO42–
Step 2 : 5I – + IO3– + 6H+  3I 2 + 3H4O
One litre of chile salt peter solution containing 6.80 g NaIO3, is treated with stoichiometric quantity of NaHSO3.
Now additional amount of same solution is added to the reaction mixture to bring about the second reaction.
How many grams of NaHSO3 are required in step 1 and what additional volume of chile salt peter must be
added in step 2 to bring in complete conversion of I – to I2 ?
Solution
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

6.8
Meq. of NaHSO3 = Meq. of NaIO3 = N × V = × 6 × 1000
198
I5+ + 6e–  I – (For KIO3, n-factor = 6)
 Meq. of NaHSO3 = 206.06
WNaHSO3
× 1000 = 206.06
M/ 2
206.06  104
 WNaHSO3 = = 10.715 g
2  1000
Also, Meq. of I – formed using n-factor 6 = 206.06
In step 2, n-factor I – is 1 and n-factor for IO3– is 5
206.06
Meq. of I – formed using n-factor 1 =
6
nd 206.06
Meq. of NaIO3 used in 2 step =
6

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JEE-Chemistr y

6.8 206.06
 × 5×V=
198 6

 VNaIO = 199.99 mL
3

Illustration 12.
1 g sample of AgNO3 is dissolved in 50 mL of water. It is titrated with 50 mL of KI Solution : The AgI
precipitated is filtered off. Excess of KI in filtrate is titrated with M/10 KIO3 in presence of 6 M HCl till all I –
converted into ICI. It requires 50 ml of M/10 KIO3 Solution : 20 mL of the same stock solution of KI require
30 mL of M/10 KIO3 under similar conditions. Calculate % of AgNO3 in the sample. The reaction is :
KIO3 + 2KI + 6HCl 3ICI + 3KCl + 3H2O.
Solution
AgNO3 + KI AgI  + KNO3
As present in AgNO3 is removed as AgI by adding 50 mL of KI solution of which 20 mL requires 30 mL of
M/10 KIO3

1
Meq. of KI in 20 mL = Meq. of KIO3 = 30 × 4 For KIO3, I5+ + 4e–  I+
10
I –  I1+ + 2e–
M
 Eq. wt. of KI =
2

30  4  50
 Meq. of KI in 50 mL added to AgNO3 =  30
10  20

1
Meq. of KI left unused by AgNO3 = 50 ×  4  20
10
 Meq. of KI used for AgNO3 = 30 – 20 = 10
 Meq. of AgNO3 = 10

WAgNO3
× 2 × 1000 = 10
170

WAgNO3 = 0.85 g = 85%

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Mole of AgNO3 1
=
Mole of KI 1

M
 If equivalent weight of KI =
2

M
Equivalent weight of AgNO3 =
2

* * * * *

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 Redox Reaction

SINGLE CORRECT
3 2 1
1. The oxidation numbers of C-1, C-2 and C-3 in propyne (C H3 C  C H) respectively are :

(A) – 1, 0, – 3 (B) – 1, 1, – 4 (C) – 2, 0, – 3 (D) + 1, – 2, – 3

2. One mole of N 2H 4 loses 10 mole of electrons to form a new compound Y. Assuming that all nitrogen
appears in the new compound, what is the oxidation number of nitrogen in Y (There is no change in the
oxidation state of hydrogen) :
(A) – 3 (B) + 3 (C) + 5 (D) + 1
3. The number of electrons lost or gained during the change, Fe + H 2O Fe3O 4 + H 2
(A) 2 (B) 4 (C) 6 (D) 8
4. Equivalent mass of a metal M is 2.5 times that of oxygen. The minimum molecular mass of its oxide is :
(A) 28 (B) 42 (C) 56 (D) 112
5. 10 g of a metal gives 14 g of its oxide. The equivalent mass of its oxide and hydroxide will be respectively
(A) 20 and 37 (B) 28 and 37 (C) 56 and 74 (D) None of these

6. KMnO4 oxidizes Xn+ into XO3 , itself changing to Mn2+ in acid solution. 2.68 × 10–3 mol of Xn+ require

1.61 × 10–3 mol of KMnO4. The value of n is :

(A) 1 (B) 2 (C) 3 (D) 5
7. The values of x, y & z in the reaction are respectively
4KO2 + xH2O + yCO2 + 4KHCO3 + zO2
(A) 3, 6, 6 (B) 2, 4, 3 (C) 3, 2, 5 (D) 4, 3, 6
8. A metal oxide has 40% oxygen. The number of moles of H2 required to reduce 1 mole of metal oxide into its
metal [Atomic weight of M = 24]
(A) 1 (B) 2 (C) 3 (D) 4
9. Ax+ + MnO¯
4
 AO¯3 + Mn2+
If 1 mol MnO¯
4
oxidizes 1.67 mol of AX+ to AO¯3 , then the value of X in the reaction is
Ax+ + MnO¯  AO¯3 + Mn2+
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

(A) 1 (B) 2 (C) 3 (D) 4

10. How many electrons should X2H4 liberate so that in the new compound X shows oxidation number of –1/2 [E.N.
of X > H]
(A) 3.5 (B) 4 (C) 3 (D) 1.5
11. 100 mL of 0.1 M NaAl(OH)2CO3 is neutralized by 0.25 N-HCl to form NaCl, AlCl3 and CO2. Volume of HCl
required is :
(A) 10 mL (B) 40 mL (C) 100 mL (D) 160 mL

MORE THAN ONE OPTION CORRECT

12. Which of the following has been arranged in order of decreasing oxidation number of sulphur ?
(A) H 2S2O 7 > Na2S4O 6 > Na2S2O 3 > S8 (B) SO 2+ > SO 42– > SO 32– > HSO 4–
(C) H 2SO 5 > H 2SO 3 > SCl2 > H 2S (D) H 2SO 4 > SO 2 > H 2S > H 2S2O 8

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JEE-Chemistr y
13. Which of the following are redox reactions ?
(A) NalO 3 + NaHSO 3  NaHSO 4 + Na2SO 4 + I2 + H 2O

(B) FeCl3 + K 4 [Fe(CN)6]  KCl + Fe4 [Fe (CN)6]3

(C) AgCl + Na2S2O 3  Na3 [Ag (S2O 3)2] + NaCl

(D) NaBiO 3 + MnSO 4 + HNO 3  HMnO 4 + Bi(NO 3)3 + NaNO 3 + Na2SO 4 + H 2O

14. 100 mL of a 0.1 M SO 42– solution contains ________________of sulphate ion.
(A) 10 millimoles (B) 5 millimoles (C) 20 milliequivalent (D) 40 milliequivalent
15. 0.01 mol of H 3PO X is completely neutralisedby 0.56 g of KOH hence :
(A) x = 3 and given acid is dibasic (B) x = 2 and given acid is monobasic
(C) x = 4 and given acid forms three series of salt (D) x = 2 and given acid does not form acid salt
16. 0.1 mol of MnO 4– (in acidic medium) can
(A) oxidise 0.5 mol of Fe2+ to Fe3+
(B) oxidise 0.166 mol of FeC 2O 4 to Fe3+ and CO 2
(C) oxidise 0.25 mol of C 2O 42– to CO 2
(D) oxidise 0.6 mol of Cr 2O 72– to Cr 3+

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

102
 Redox Reaction

Comprehension Type Questions

Comprehension : 1
The equivalent mass of a substance is not a constant. It depends up on the reaction in which the substance is
undergoing the reaction. It can be mathematically represented either in terms of oxidation number change or in
terms of electron accepted or released by oxidising and reducing agent. For example in case of KMnO4 acting
as an oxidising agent in acidic medium, the equivalent mass is (M/5). {M = Molecular mass}, because it is
converted to +2 oxidation state. When MnO4– is converted to Mn2+, the balanced equation indicates the
acceptance of 5 electrons. It eq. mass is M/5.
1. CuS  Cu2+ + SO2 . For the above reaction ; the equivalent mass of CuS is -
(A) M/7 (B) M/6 (C) M/8 (D) M/1
(Here M is molecular mass of CuS.)
2. In acidified medium K2Cr2O7 act as an oxidising agent according to the following equation.
K2Cr2O7 + 4H2SO4  K2SO4+ Cr2(SO4)3 + 4H2O + 3(O) The equivalent mass of K2Cr2O7 is (K = 39; Cr
= 52)-
(A) 98 gm (B) 49 gm (C) 294 gm (D) can’t be predicted
3. For the reaction
FeS2+ O2  Fe2O3 + SO2
The equivalent mass of FeS2 is -
(A) E = M/1 (B) E = M/10 (C) E = M/11 (D) E = M/12
4. 3MnO4– + 5 Fe C2O4 + 24 H+  10 CO2 + 5 Fe3+ + 3Mn2+ + 12 H2O
For the above reaction what will be ratio of equivalent mass of MnO4– and FeC2O4 if their molar masses are M1
and M2

3M1 M1 5M1 3M1

(A) (B) (C) (D)
5M 2 M2 3M 2 4M 2

5. For the given half-cell reaction equivalent mass of sodium bromate is

2BrO3– + 12H+ + 10e–  Br2 + 6 H2O
(A) equal to molecular mass (B) 1/3 of its molecular mass
(C) 1/6 of its molecular mass (D) 1/5 of its molecular mass
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Comprehension : 2
n-factor in reduction - oxidation reactions :
(i) In intermolecular redox reaction : (reductant and oxidant are different species) n.f. for oxidant or reductant
= Total change in oxidation no. per mole of oxidant or reductant or no. of moles of electrons involved for 1
mole of oxidant or reductant.
(ii) In intramolecular redox reaction (or Decomposition reactions) : (same species act as reductant as well
oxidant but two different atoms in compound undergoes reduction and oxidation simultaneously) n.f. = Total
increase or decrease in oxidation no. per mole of compound. On the basis of above information, answer the
following questions :

 1
6. Chemical reaction gives as KClO4   KClO3 + O 2 is an example of ?
2
(A) Intermolecular redox reaction (B) Decomposition reaction
(C) Disproportionation reaction (D) None of these

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JEE-Chemistr y
7. In above reaction, if M = Molar mass of KClO4 , the its equivalent weight will be
(A) M/1 (B) M/3 (C) M/2 (D) M/6

8. In given intermolecular redox reaction A 2O 3  MnO 4  H   Mn 2  A n , 2 moles of A2O3 losses 8 moles of

electrons, then value of ‘n’ will be :
(A) 1 (B) 5 (C) 4 (D) 2
Comprehension : 3
Five litre of '16.8 vol' H2O2 solution of density 1.051 g/mL is taken in a 50 L vessel and the vessel is sealed.
9. What is the maximum volume of O2 gas, which may be obtained at 1 atm and 273 K, from this solution ?
(A) 16.8 L (B) 50 L (C) 84 L (D) 3.36 L
10. The molality of solution is :
(A) 1.5 (B) 1.5765 (C) 1.427 (D) 2.873
11. If H2O2 present in the solution get decomposed completely, then the total mass of water finally present in the
vessel should be :
(A) 120 g (B) 1051 g (C) 5255 g (D) 5135 g
Comprehension : 4
Oleum is a sample of H2SO4 containing some dissolved SO3. The composition of oleum is normally represented
as percentage labeling. A sample of oleum labeled as (100 + x) % represents that when x g water is added in
100 g oleum, (100 + x) g of pure H2SO4 is obtained. A sample of oleum contains 30 g H2SO4 and 20 g SO3.
12. The mole percent of SO3 in oleum is about
(A) 55 % (B) 45% (C) 50 % (D) 40 %
13. The percent labeling of oleum is :
(A) 109 % (B) 118 % (C) 104.5 % (D) 122.5%
14. If 20 g water is added to this sample of oleum, then the final composition of sample becomes
(A) 50 g pure H2SO4 (B) 54.5 g pure H2SO4
(C) 54.5 g H2SO4 and 15.5 g water (D) 54.5 g H2SO4 and 4.5 g SO3
Match the column
15. Column-I Column-II

3M
(A) P2H 4  PH 3  P4 H 2 (p) E 
4

3M
(B) I 2  I  IO3 (q) E 
 

5
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

2 3M
(C) MnO4  Mn  H 2O  Mn 3O 4  H (r) E 
 

13

5M
(D) H 3PO 2  PH 3  H 3PO 3 (s) E 
6
16. Column-I Column-II
(Solution needed for complete reaction)
(A) 100 mL of 0.3 M-H2C2O4 solution (p) 100 mL of 0.3 M-KOH solution
(B) 50 mL of 0.6 M-KHC2O4 solution (q) 120 mL of 0.1 M-KMnO4 solution in presence of
H2SO4
(C) 50 mL of 0.6 M-HCl solution (r) 60 mL of 0.1 M-KMnO4 solution in presence of
H2SO4
(D) 100 mL of 0.2 M-H3PO4 solution (s) 100 mL of 0.6 M-KOH solution

104
 Redox Reaction

1. Assign oxidation number to the underlined elements in each of the following species :
(1) NaH2PO4 (2) NaHSO4 (3) H4P2O7 (4) K2MnO4
(5) CaO2 (6) NaBH4 (7) H2S2O7 (8) KAl(SO4)2.12 H2O
Ans.
(1) 1(+1) + 2(+1)+x+4(-2) = 0  x = +5
(2) 1 (+1) +1(+1) + x + 4 (–2) = 0  x = +6
(3) 4 (+1) + 2x + 7 (–2) = 0  2x = +10  x = +5
(4) 2 (+1) + x+4 (–2) = 0  x = +6

O
(5) CaO2  Ca |  O = –1
O
(6) (+1)+x+4(–1) = 0  x = +3

O O

(7) H- O - S - O - S - O - H  S=+6
 
O O

(8) S O42  x+4 (–2) = –2  x = +6

2. What are the oxidation number of the underlined elements in each of the following and how do you rationalise
your results ?
(1) KI3 (2) H2S4O6 (3) Fe3O4 (4) CH3CH2OH
(5) CH3COOH

Ans. (1) KI3  I3  3 (x) = –1  x = –1/3

5
(2) H2S4O6  2 (+1) + 4x +6(–2)=0 4x=+10 x=+
2
(3) Fe3O4  3x + 4 (–2) =0 3x = +8 x=+8/3

H H
| |
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

(4)
H - C1 - C2 - O - H
| |  C1= –3  C2 = –1
H H

H
|
H – C1 – C2 – O – H
(5) | ||  C1= –3  C2 = +3
H O

3. Justify that the following reactions are redox reactions :

(1) CuO(s) + H2(g) Cu(s) + H2O(g)
(2) Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
(3) 4BCl3 (g) + 3LiAlH4(s) 2B2H6(g) +3LiCl(s) + 3 AlCl3
(4) 2K(s) + F2(g) 2K+F– (s)
(5) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

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JEE-Chemistr y

Ans. (1) Redox, CuO Reduction

H2 Oxidation
(2) Redox, Fe2O3 Reduction
CO Oxidation
(3) Not redox.
(4) Redox, K  Oxidation
F2 Reduction
(5) Redox, NH3 Oxidation
O2 Reduction
4. Fluorine reacts with ice and results in the change :
H2O(s) + F2(g)  HF(g) +HOF(g)
Justify that this reaction is a redox reaction.
Ans. H2O + F2 HF + HOF
F Reduction
O Oxidation

5. Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2 O27  and N O3 . Suggest
structure of these compounds. Count for the fallacy.

O O O
  
–
Ans. H– O – S – O – O – H S= +6 O – Cr – O – Cr – O– Cr = +6
  
O O O

O
 N = +5
O = N – O–
6. Write formulas for the following compounds:
(1) Mercury(II) chloride (2) Nickel(II) sulphate
(3) Tin(IV) oxide (4) Thallium(I) sulphate
(5) Iron(III) sulphate (6) Chromium(III) oxide
Ans. (1) HgCl2 (2) NiSO4 (3) SnO2 (4) Tl2SO4
(5) Fe2(SO4)3 (6) Cr2O3
7. Suggest a list of the substances where carbon can exhibit oxidation states from –4 to +4 and nitrogen from –3
to +5.
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Ans. NH3, N2H4, NH2OH, N2, N2O, NO, HNO2, NO2, HNO3
CH4 , CH3Cl, CH2Cl2, CHCl3 CCl4
8. While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing agents in their reactions,
ozone and nitric acid act only as oxidants. Why?
Ans. In SO2 and H2O2 , S and O show intermediate oxidation state. i.e. why they may acts as oxidant as well as
reductant but O3 and HNO3 on dissociation give nascent oxygen i.e. why they act only as oxidants.
9. Identify the substance oxidised, reduced, oxidising agent and reducing agent for each of the following reactions.
(1) 2AgBr (s) + C6H6O2(aq) 2Ag(s) + 2HBr (aq) +C6H4O2(aq)
(2) HCHO(l) + 2[Ag(NH3)2]+ (aq) + 3OH– (aq) 2Ag(s) + HCOO–(aq) + 4NH3(aq) +2H2O(l)
(3) HCHO (l) + 2Cu2+(aq) +5 OH–(aq) Cu2O(s) +HCOO–(aq) + 3H2O(l)
(4) N2H4(l) + 2H2O2(l) N2(g) + 4H2O(l)
(5) Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l)
Ans. (1) AgBr - Reduced - Oxidizing agent
C6H6O2 - Oxidized - Reducing agent

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(2) HCHO - Oxidized - Reducing agent
Ag+ Reduced - Oxidizing agent
(3) HCHO Oxidized Reducing agent
Cu+2 Reduced - Oxidizing agent
(4) N2H4 Oxixized Reducing agent
H2O2 Reduced Oxidizing agent
(5) Pb(s) Oxidized Reducing agent
PbO2(s) Reduced Oxidizing agent
10. Why does the following reaction occur ?
Xe O46  (aq) + 2F– (aq) + 6H+(aq) XeO3(g) +F2(g) +3H2O(l)

What conclusion about the compound Na4XeO6(of which Xe O46  is a part) can be drawn from the reaction.

Ans. Xe O64 Reduced - Oxidizing agent

2F- Oxidized - Reducing agent
11. Balance the following redox reactions by ion – electron method:
(1) Mn O4 (aq) + I– (aq) MnO2 (s) + I2(s) (in basic medium)
(2) Mn O4 (aq) + SO2 (g) Mn2+ (aq) + HS O4 (aq) (in acidic solution)
(3) H2O2 (aq) + Fe2+ (aq) Fe3+ (aq) + H2O (l) (in acidic solution)

(4) Cr2 O27  + SO2(g) Cr+3 (aq) +S O24  (aq) (in acidic solution)

Ans. (1) Mn O4 + I –  MnO2 + I2 (Basic Medium)

Mn O4  MnO2 I-  I2
–
Mn O4  MnO2 2 I I2
–
Mn O4  MnO2 + 2H2O 2 I I2
–
4H+ + Mn O4  MnO2 + 2H2O 2 I I2
–
3e- + 4H+ + Mn O4  MnO2 + 2H2O ..(a) 2 I I2+2e- ..(b)
Multiply equation (a) by 2 and equation (b) by 3 and add both the equation.
6e- + 8H+ + 2Mn O4 2MnO2 + 4H2O
–
6 I 3I2 + 6e-
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

–
8H+ + 2Mn O4 + 6I 2MnO2 + 4H2O + 3I2
for basic medium add 8 OH- on both side
–
8OH- + 8H+ + 2Mn O4 +6I- 2MnO2 + 4H2O + 3I2 + 8O H
–
8H2O + 2Mn O4 + 6I- 2MnO2 +4H2O + 3I2 +8O H
–
4H2O + 2Mn O4 + 6I- 2MnO2 + 3I2 + 8O H

(2) Mn O4 + SO2 Mn+2 + HS O4

Mn O4 Mn+2 SO2 HS O4

Mn O4 Mn+2 + 4H2O 2H2O +SO2 HS O4

8H++ Mn O4 + 5e– Mn+2 +4H2O ..(a) 2H2O + SO2 HS O4 + 3H++ 2e- ..(b)

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Multiply equation (a) with 2 and equation (b) with 5 and add both the equation.

10e- + 16H+ + 2Mn O4 2Mn+2 + 8H2O

10H2O + 5SO2 5HS O4 +15H+ + 10e-

2H2O +5SO2 + 2Mn O4 + H+ 2Mn+2 + 5HS O4

(3) H2O2 + Fe+2 Fe+3 + H2O
H2O2 H2O Fe+2 Fe+3
H2O2 H2O +H2O Fe+2 Fe+3
2H + H2O2 2H2O
+
Fe+2 Fe+3
2e– + 2H+ + H2O2 2H2O ..(a) Fe+2 Fe+3 + e- ..(b)
Multiply equation (b) with 2 and add with equation (a)
2e-+ 2H+ + H2O2 2H2O
2Fe+2 2Fe+3 +2e-

2Fe+2+ 2H+ H2O2 2Fe+3 +2H2O

(4) Cr2 O72 +SO2 Cr+3 +S O42
2
Cr2 O72 Cr+3 SO2  SO4

Cr2 O72 2Cr+3 SO2  SO42

Cr2 O72 2Cr+3+7H2O 2H2O +SO2  SO42

14H+ + Cr2 O72 2Cr+3+7H2O 2H2O +SO2  SO42 +4H+

6e- + 14H+ + Cr2 O72 2Cr+3+7H2O ..(a)

2H2O +SO2  SO42 + 4H+ + 2e- ..(b)

Multiply equation (b) with 3 and add with equation (a)
6e- + 14H+ + Cr2 O72 2Cr+3+7H2O

6H2O +3SO2  3SO 42 + 12H+ +6e-

Cr2 O72 + 3SO2 +2H+ 2Cr+3 + 3SO 42 +H2O

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

12. Balance the following equations in basic medium by ion-electron method and oxidation number methods and
identify the oxidising agent and the reducing agent.

(1) P4(s) + OH–(aq) PH3(g) +HP O2 (aq)

(2) N2H4(l) + Cl O3 (aq) NO(g) +Cl– (g)

(3) Cl2O7(g) + H2O2(aq) Cl O2 (aq) + O2(g) + H+

Ans. P4 + OH– PH3 + HPO2–

(1) Indicate the increase and decrease in O.N. per mole

Increase in O. N. = 2 × 4 = 8
0 0 –3 +2
–
P4 + P4  PH 3 + HPO2
Decrease in O. N. = 3 × 4 = 12

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(2) Now, balance the increase and decrease in O.N. by multiplying the reactant by suitable coefficient.

Increase in O. N. = 8 × 3
0 0 –3 +2
–
2P4 + 3P4  PH 3 + HPO2
Decrease in O. N. = 12 × 2

(3) Now balance all other atoms except O and H.

0 0 –3 +2
–
2P4 + 3P4  8PH 3 + 12HPO2

(4) Now balance O by adding H2O and after that H by adding H+

24H2O + 2P4 + 3P4 8PH3 + 12HPO2– + 12H+
(5) Add OH– ions on both sides equal to the number of ions and cancel out H2O molecules.
24H2O + 5P4 + 12OH– 8PH3 + 12HPO2– + 12H+ + 12OH–
24H2O + 5P4 + 12OH– 8PH3 + 12HPO2– + 12H2O
12H2O + 5P4 + 12OH– 8PH3 + 12HPO2– [Balanced)
Oxidizing agent = P4 and reducing agent = P4

(2) Increase in O. N. = 4 × 2 = 4
–2 +5 +2
– –
N2 H 4 + ClO 3  NO + Cl
Decrease in O. N. = 6 × 1 = 6

Increase in O. N. = 8 × 3
–2 +5 +2
– –
3N2 H 4 + 4ClO 3  NO + Cl
Decrease in O. N. = 6 × 4
3N2H4 + 4ClO3– 6NO + 4Cl–
3N2H4 + 4ClO3– 6NO + 4Cl– + 6H2O (Balanced)
Oxidizing agent = ClO3–
Reducing agent = N2H4

Decrease in O. N. = 4 × 2 = 8
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

+7 –1 +3 0
–
(3) Cl2 O7 + H 2 O2  ClO2 + O2
Increase in O. N. = 1 × 2 = 2

Decrease in O. N. = 8 × 1
+7 –1 +3 0
–
Cl2 O7 + 4H 2 O2  ClO2 + O2
Increase in O. N. = 2 × 4

Cl2O7 + 4H2O2 2ClO2– + 4O2

Cl2O7 + 4H2O2 2ClO2– + 4O2 + 3H2O + 2H+
Cl2O7 + 4H2O2 + 2OH– 2ClO2– + 4O2 + 3H2O + 2H+ + 2OH–
Cl2O7 + 4H2O2 + 2OH– 2ClO2– + 4O2 + 5H2O (Balanced)
Oxidizing agent = Cl2O7
Reducing agent = H2O2

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13. What sorts of informations can you draw from the following reaction ?
(CN)2(g) + 2OH–(aq) CN–(aq) + CNO–(aq) + H2O(l)
Ans. CN - Reduced and oxidized both
14. The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+, MnO2, and H+ ion. Write
a balanced ionic equation for the reaction.

Ans. Mn+3 MnO2 + Mn+2 +3

Mn Mn
+2
Mn+ 3MnO 2
Total decrease = Total increase. +3 +2 +3 +4
now add these equation : –1 +1
2Mn+3 MnO2 +Mn+2
balance O by H2O and H by H+
2H2O + 2Mn+3 MnO2 + Mn+2 +4H+
15. Consider the elements :
Cs, Ne, I and F
(1) Identify the element that exhibits only negative oxidation state.
(2) Identify the element that exhibits only postive oxidation state.
(3) Identify the element that exhibits both positive and negative oxidation states.
(4) Identify the element which exhibits neither the negative nor does the positive oxidation state.
Ans. (1) F (2) Cs (3) I (4) Ne
16. Using the standard electrode potentials given in the table predict if the reaction between the following is
feasible:
(1) Fe3+(aq) and I–(aq) (2) Ag+(aq) and Cu(s)
(3) Fe3+ (aq) and Cu(s) (4) Ag(s) and Fe3+(aq)
(5) Br2(aq) and Fe2+(aq).
Ans. (1) Possible (2) Possible (3) Not Possible
(4) Not possible (5) Possible
17. Arrange the following metals in the order in which they displace each other from the solution of their salts.
Al, Cu, Fe, Mg and Zn.
Ans. Mg, Al, Zn, Fe, Cu
18. Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V,
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

Hg2+ /Hg = 0.79V

Mg2+/ Mg = –2.37V. Cr3+/Cr = –0.74V
arrange these metals in the increasing order of their reducing powers.
Ans. Ag+/Ag, Hg+2/Hg, Cr+3/Cr, Mg+2 /Mg, K+/ K
19. Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) Zn2+(aq) +2Ag(s) takes place, Further
show:
(1) Which of the electrode is negatively charged.
(2) The carriers of the current in the cell, and
(3) Individual reaction at each electrode.
Ans. (1) Anode
(2) Electron will flow from anode to cathode while current will flow from cathode to anode
(3) Anode Zn Zn+2 +2e-
Cathode Ag+ + e- Ag

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ANSWERS
BEGINNER'S BOX-1
Q.1. (1) – 3, + 3 (2) + 4 (3) + 4 (4) + 4 (5) + 3
(6) + 3 (7) – 3, + 5 (8) + 2 (9) + 6 (10) + 7
(11) + 6 (12) + 3 (13) – 3 (14) + 5 (15) + 6
(16) + 6 (17) + 6 (18) + 2 (19) 2.5 (20) + 6
(21) Zero (22) + 8 (23) + 5 (24) + 8 (25) + 5
(26) + 6 (27) + 5 (28) + 7 (29) + 3 (30) +3, + 3
(31) + 5 (32) + 3 (33) + 5 (34) + 3 (35) + 1
(36) + 7 (37) – 1 (38) –1/2 (39) + 6 (40) + 2
Q.2. (1) Ans. (1) 2. Ans. (2) 3. Ans. (3) (4) Ans. (3) 5. Ans. (3) 6. Ans. (3)
(7) Ans. (8) (8) Ans. (11) 9. Ans. (28) 10. Ans. (8)
Q.3.

3C2H5OH  Cr2O72  H  2Cr3  3C2H4O  7H2O


1.

2
2.
 
Sn(OH)3  2Bi(OH)3  3OH  3Sn(OH)6  2Bi

3. 4Zn + NO3 + 10H+  4Zn2+ + NO2 + 3H2O

4.

I 2  10NO 3  8H  2IO 3  10NO 2  4H 2 O

2MnO 4  3SO32  H 2O  2MnO 2  3SO 42  2OH


5.

6. I 2  5Cl 2  6H 2O  2HIO 3  10HCl

7. 3H 2 S  2HNO 3  2NO  3S  4H 2 O

8. 2NO 3  6Cl   8H   2NO  3Cl 2  4H 2O

9.

H 2 O 2  2I  2H   I 2  2H 2 O

10. Cr2O72  3NO 2  8H   2Cr 3   3NO 3  4H 2O

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

11. 3N 2 O 4  BrO 3  3H 2O  6NO 3  Br   6H 

12. 4Zn  NO3  10H  4Zn2  NH4  3H2O

  

13. 
2ClO 3  SO 2  H  2ClO 2  HSO 4
 

2Mn 2  5S 2 O 82  8H 2 O  2MnO 4  10HSO 4  6H

  
14.


15. Cl 2  IO3  2OH  2Cl  IO4  H2O
 

16. 2H 2 SO 3  Cr2 O72 +5H+  2HSO 4  2Cr 3   4H 2 O



17. 4S + 6OH–  2S2– + S2O32– + 3H2O

18. IO 4  7I + 8H+  4I 2  4H 2 O


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19. Zn  2NO 3 +2H+  Zn 2  2NO 2  2H 2O



20. 24H 2S  8Cr2O72 +64 H+  16Cr 3  3S8  56H2O

21. 3C2H5OH + 2 MnO4  OH  3C2H3O  2MnO2  5H2O

2
22. 2MnO 4  3SO3 + H 2O  2MnO2  3SO 42  4OH
 

Cr2O72  3SO3 + 8H  2Cr 3  3SO 42  4H 2O

2
23.  

24. I2  SO2 + 2H2O  SO42  2I  4H

 

25. 
Sn  4NO3  8H  SnO2  4NO2  4H2O


2 +
26. 2MnO4  5SO 2  2H 2O  2Mn2  5SO4  4H


27. 2MnO 4  SO 32  2OH   2MnO 42  SO42  H 2O

28.

3ClO   Br   BrO 3  3Cl

2
29. 2MnO4  5C 2O 4  16H  2Mn 2  10CO 2  8H 2O


2
30. 6Fe2  Cr2O7  14H  6Fe3  2Cr 3  7H 2O


31. AsO33  I 2  H 2O  AsO43  2H   2I



32. Cl 2  SeO32  H2O  SeO42  2Cl  2H

 

33. 6Cu 3 P  124H  11Cr2 O72  18Cu 2  6H 3 PO 4  22Cr 3  53H 2 O



4. (C) 5. (B) 6. (B) 7. (B) 8. (A) 9. (A) 10. (C) 11. (C)
12. (B) 13. (D) 14. (C) 15. (A) 16. (A) 17. (A) 18. (B) 19. (B)
20. (D) 21. (A) 22. (D) 23. (B) 24. (D) 25. (C) 26. (C) 27. (C)
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

28. (B) 29. (B) 30. (C) 31. (C) 32. (A)

BEGINNER'S BOX-2
1. (C) 2. (C) 3. (B) 4. (A) 5. (B) 6. (B) 7. (C) 8. (C)
9. (A) 10. (A) 11. (C) 12. (B) 13. (A) 14. (B) 15. (B) 16. (C)
17. (C)
BEGINNER'S BOX-3
1. (A) 2. (B) 3. (C) 4. (A) 5. (C) 6. (B) 7. (B) 8. (C)
9. (C) 10. (B) 11. (B) 12. (C) 13. (A)

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EXERCISE-1
SINGLE & MORE THAN ONE CORRECT
Que. 1 2 3 4 5 6 7
Ans A B D C B B B
Que. 8 9 10 11 12 13 14
Ans A B C D A,C A,D A,C
Que. 15 16
Ans B,D A,B,C

EXERCISE-2
Comprehension Based Questions
Comprehension-1 1. (B) 2. (B) 3. (C) 4. (A) 5. (D)

Comprehension-2 6. (B) 7. (C) 8. (B)

Comprehension-3 9. (C) 10. (A) 11. (D)

Comprehension-4 12. (B) 13. (A) 14. (C)

Match the column

15. A  (S); B  (Q); C  (R); D  (P)

16. A–(Q, S); B–(P, Q); C–(P, R); D–(S)

*****
Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.

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IMPORTANT NOTES

Node-6\Target-2020-21\1.JEE(M+A)\M odule\Nurture\Chemistry\Physical chem.\Eng\NPC-2 \2.Redox Reaction\Th.