Gaseous State

PHYSICAL
CHEMISTRY

1.

 Introduction

y Any matter can be physically classified as solid, liquid or gas which are
most common physical states of matter on earth.

Sublimation

Melting/Fusion Vaporisation
Solid Liquid Gas
Condensation
Freezing

Deposition /crystallization

Characteristics of states of matter

S.No. Property Solid Liquid Gas

Intermolecular
1. Negligible Moderate Very large
distance

Intermolecular
2. Very high Moderate Very low
attraction

3. K.E. of particles Zero Low Very high

4. Shape Definite Indefinite Indefinite

5. Volume Definite Definite Indefinite

6. Density High Moderate Very low

7. Diffusion Negligible Yes/No Always yes

Introduction

2.
 S.No. Property Solid Liquid Gas

Compressible
8. Compressibility Negligible Negligible
always

Always
9. Type of mixture Both Both
homogenous

Gaseous State
To describe a gas, minimum four parameters are required which are as
following:

1. Amount of gas: Moles =

mass gm ( ) =
No. of particles
(
molar mass g / mol ) NA
2. Temperature of gas: T(in Kelvin) = T (°C) + 273
3. Occupied volume of gas: Every gas occupies the entire volume of the
container in which it is kept (ideal gas case).
Hence, Vgas = Volume of container
4. Pressure of gas
y In a gas sample present in a vessel, all particles move with high speeds
and hence collide continuously with each other as well as with walls of
container.
y Hence it is considered that gas particles apply a uniform force on each
point of the wall.
Force
y Since Pressure = so at each point on the wall of container, the
Area
pressure is same which is known as pressure of gas.

Atmospheric Pressure (Patm)

y The force applied by atmospheric gases per unit area of earth’s surface is
known as atmospheric pressure.
Standard Patm = 1.0135 × 105 N/m2 = 1 atm
y Standard Patm is defined at sea-level and as height from sea level increases
Patm decrease.
Introduction

3.
 Note: In an apparatus, from every open end, Patm is applied.

Patm

Patm

Patm
Introduction

4.
 Calculation of pressure

y At any point, the pressure is due to all substances present above that point.
y Since all present at same horizontal level, pressure is same.
Vacuum
i.e. PA = PB = PC = P [Pvaccum = 0]
Force
P = +0  Force = mg 
Area
 
∵= mg ( V × ρ ) ( A × h) ρg  m = Volume × density(ρ) 
P = = g
A A A  Volume
= area × height  h
 
P = ρgh

Note: In above relation, all values must be put in S.I units only
i.e. ρ(density) = kg/m3   
g(gravitational constant) = 9.8 m/s2 A B C
h(height) = meter
P(Pressure) = N/m2 or Pascal

ILLUSTRATION:

Q1 Calculate the pressure at A point in mercury column of given figure.

A1 PA = Pcolumn + Pvacuum
PA = ρgh + 0
= (13.6 × 103 kg/m3) (9.8 m/s2) (76/100 m)
= 1.01325 × 105 N/m2 = 1 atm
= 76 cm of Hg = 760 mm of Hg

Q2 Calculate height of water column which exerts 1 atm pressure at the

bottom.

A2 P = ρgh +0
= (1.01325 × 105 N/m2) = (1 × 103 kg/m3) (9.8 m/s2) h
⇒ h = 10.33 m = 1033 cm
Calculation of pressure

5.
 Note: If same pressure is applied at the bottom of different columns:
Vacuum

Vacuum

Vacuum Vacuum

If P1 = P2 = P3 = P4
⇒ (r1h1) = (r2h2) = (r3h3) = (r4h4)
i.e For previous question
( 1 atm)Hg = ( 1 atm)H O
2

13.6 × 76 cm= 1×h

h = 1033 cm

Q3 Calculate the pressure at A and B in the given figure (1) and figure(2).

A3 Patm

38 cm

76 cm

A
Figure (1)
Calculation of pressure

(i) PA = (ρ.g.h) + Patm = (114 cm of Hg) + (1 atm)

= (1.5 atm) + 1 atm = 2.5 atm
PB = (ρgh) + Patm
= (0.5 atm) + 1 atm
= 1.5 atm

6.
(ii) PA = (ρ1.g.h1) + Patm
and PB = (ρ2gh2) + (ρ1gh1) + Patm
or PB = (ρ2gh2) + PA

Density = 1g/ml h1 cm

Density = 2g/ml h2 cm

B
Figure
gur (2)

Barometer
A device used to measure atmospheric pressure.

Vacuum

B A

Hg

PA = ρ.g.h + 0
Calculation of pressure

PB = Patm
 A and B same level i.e. PA = PB
Patm = ρ.g.h
i.e. at sea level, h = 76 cm

7.
 Pgas

A B


PA = (ρ.g.h) + Pgas
PB = Patm
 PA = PB
ρgh + Pgas = Patm

P=
gas
Patm − ρgh
Calculation of pressure

8.
 Manometer

y It is used to measure pressure of gas sample present in a vessel.

y It is a ‘J’ shaped glass tube filled with Hg(l).
y Smaller tube is called inner tube which will be connected to gas
sample.
y Larger tube is called outer tube which may be open or closed.
y Before connecting to the gas, Hg level in both tubes is same, but after
connecting the liquid moves and then a stable height difference of
Hg levels in both columns is observed. Using that pressure of gas is
calculated.
y Depending upon the outer tube, there are two types of monometer
as following:

1. Closed end manometer

y Outer tube is closed.
y After connecting to the gas sample, liquid always
moves inner to outer tube side.
P1 = Pgas and P2 = (ρ.g.h) + 0
Since 1 and 2 are at same level
P1 = P2
⇒ Pgas = ρ.g.h

2. Open end manometer

y Open tube remains opened hence Patm is applied.
y After connecting to the gas, there can be any of
the following three possibilities.

Case 1
PA = Pgas and PB = (ρ.g.h) + Patm
PA = PB
i.e. Pgas > Patm

Case 2
PA = (ρgh) + Pgas
PA = PB
⇒ Pgas = Patm – (ρgh)
i.e. Pgas < Patm
Manometer

9.
 Case 3 Patm
PA = PGas opened
PB= Patm
PA= PB
Gas
∴ PA = Patm
⇒ Pgas =Patm
h
A B
Manometer

10.
ILLUSTRATION:

Q1 From the following set-up, calculate moles of the gas present in the con-
tainer of volume 24.63 L at 600 K if the level of mercury in the open tube of
the manometer is 38 cm higher.
(Given: Atmospheric pressure = 76 cm of mercury)
...............
. ...............
. ...............
. ...............
. ...............
. ...............
. ...............
. ...............
. . . . . . . . . . . .. . . .
. ...............
. ............... 36 cm
. ...............
. ...............
. ...............
. ...............
. ...............
. ...............
. ............... Hg

V  24.63L
T  600K

A1 Pgas = Patm + ρgh

= (76 cm of Hg) + (38 cm of Hg)
= 114 cm of Hg
PV = nRT
 114 
 ( )
 × 24.63 =n × 2 × 24.63 ⇒ n = 3/4 moles
 76 

Manometer

11.
 Q2 Calculate the number of moles of gas present in the container of volume = 10
litre at 300 K. If the manometer containing glycerine shows 5 m difference in
level as shown in diagram.
(Given: dglycerin = 2.72 gm/ml, dmercury = 13.6 gm/ml)

Patm  1 atm
...............
................
................
................
................
................
................
................
. . . . . . . . . . . .. . . . 5m
................
................
................
................
................
................
................
................
................

A2 Height difference by glycerine = 5 m = 500 cm

Let height of mercury = h cm
5 m of glycerine ⇒ Hg
(ρ.h)glycerine = (ρ.h)Hg
2.72 × 500 cm = 13.6×h
h = 100 cm of Hg
Now, Pgas = Patm + ρgh = 76 cm +100 cm = 176 cm of Hg
PV = nRT
176
⇒ × 10 =n × 24.6
76
176 10
⇒ n= × =
0.94 moles
76 24.6
PA=(Pgh) + Pgas Gas Pgas
Also PA= Patm
⇒ Patm = (Pgh) +Pgas Hg
16 cm
⇒ Pgas = (76 cm of Hg) − (16 cm of Hg)
= 60 cm of Hg A
Manometer

12.
 Ideal Gas Law

Ideal Gas
y The gas which obeys each and every point of
kinetic theory of gases.
Or
y The gas which obeys all gas laws is known as
Ideal gas.
y Various gas laws are as following:

1. Boyle’s Law
It states that volume of a fixed mass of gas is
inversely proportional to its pressure at constant
temperature.
1
V ∝ (At constant n and T)
P
PV = constant

2. Charles Law
Pext  Constant
It states that volume of given mass of gas at
constant pressure is directly proportional to its
temperature on the Kelvin scale.
V ∝ T (Kelvin) (At constant n and P) .. ... ... ... ... .. ... .. ... .. ..
Movable
. . ..
.. .. ..Ideal.. .. .. .. .. .. .. ..
.. .. .. .. . . .. . .. .. ..
V
i.e. = Constant ... ... ... ...Gas
.. . .. .. .. .. ..
. . . . .. .. .. .. .. .. ..
T .. .. .. .. .. . .. .. .. .. ..
. . . . . .. . . . .
. .. . ..
3. Gay Lussac’s law
It states that the pressure of a given mass of gas
is directly proportional to the Kelvin temperature
at constant volume.
P ∝ T (Kelvin) (At constant n and V)
P
⇒ = constant
T
Ideal Gas Law

13.
 4. Avogadro’s law
It states that equal volumes of all gases under similar conditions of
temperature and pressure contain equal number of molecules.
n ∝ V (At constant P and T)
n
= constant
V
Note: W hen all gas laws are combined together then Ideal gas equation is
formed which is as following:
PV = nRT
Where R= Universal gas constant
= 0.0821 atm. lit. / mol. K
= 8.314 J /mol. K
= 2 cal / mol. K

Graphs
(A vs B)
By default, A → y − axis
B → x − axis
Equation between A and B in given condition.
Put A= y and B = x
⇒ Equation in terms of x and y

Straight line
General equation: y = mx + c
Ideal Gas Law

14.
Parabola:

y
General equation
y  x2

y  x2
x
x  y2 o

x  y2

Rectangular hyperbola:

xy = constant x
o

Exponential:

y y  ex

y  e x
y  ex
x
and 0
y  e x
Ideal Gas Law

15.
 Graphs for Boyle’s law (PV = Constant)
i) P vs V

P V  constant

xy  constant V
0
i.e. Rectangular hyperbola
Ideal Gas Law

16.
 Graphs for Boyle’s Law

ii) PV vs V

PV vs V PV nRT
PV  constant
y = constant V
0

iii) PV2 vs V

PV  K  cons tant
PV 2 KV PV 2
y = kx
V

P  1 
iv)   vs  
V V

 PV  K

2
PV2
P  1
 k  
V  V
2  1
y = Kx  
 V Graphs for Boyle’s Law

17.
 y log (P) vs log (V) for Boyle’s law

log P
K>1
PV  K
log(PV)  logK 135 0 135 135
log V
logP + log V = log K
K=1
O < K<1

⇒ y =−x + log K
On comparing with line equation, we get
=
y mx + c

slope = ( −1)
⇒= θ 135°
and Intercept = log k

V vs T(Kelvin) for Charles’s Law :

V  nR 
K K  P 
T(Kelvin)  

V
V = KT

 y  k.x
 nR 
y  mx   tan1  
0  P 
On comparing with equation of straight line T(in Kelvin)
c=0
nR
m  tan 
P
Graphs for Boyle’s Law

18.
V vs T(°C) for Charles’s Law:
V = KT(in Kelvin) V
V = K[T(°C) + 273]
V = K.T(°C) + K(276) (K273)
0 T(°C)
273
 y  (k) x  (k .273) (°C)
m0 C>0

VT vs T2 for Charles’s Law

VT

V = K.T
VT = KT2
 y  k.x T2
0

log (V) vs log T for Charles’s Law

V  KT
K1
∴ log V  logK  log T log V
K1

y  x  logK
K1
y  mx  c 45 45 45 
log T
m  (1)    45
 nR 
c = log  
 P 
Graphs for Boyle’s Law

19.
 P vs T(K) for Gay Lussac’s law
P

 nR 
P  KT K  
 V 


 y  K.X 0 T(K)
 nR 
tan  K   
 V 

(P/T) vs T for Gay Lussac’s law

P 
 
T

P  KT  nR 
P  
K  V 
T
 y  constant 0
T

PT vs T for Gay Lussac’s law

PT 
P  KT

2
PT  K T

y  kx2 0
Graphs for Boyle’s Law

20.
log P vs log T for Gay Lussac’s law
log P
K1

K1

P  KT
K1

 logP  logK  log T

log T
y  x  logK

Equation of State
An ideal gas present in a state, if subjected to another state:

P1 P2
V1 Ideal gas V2 Ideal gas
n1, T1 n2, T2
State  1 State  2
 P1V1  n1RT1  P2V2  n2RT2

P1V1 P2 V2
= Equation of state
n1T1 n 2 T2

Types of container
1. Open Container
Atleast one wall must be open e.g. Drinking glass, Jug, Test Tube, Bucket
etc.
Open
Pgas = Patm (by default constant)
Also
Vcontainer = Constant Gas
∴ PV = nRT
Graphs for Boyle’s Law

K
(n)gas =
T
If T↑ ⇒ (n)gas ⇒ gas escapes out and vice − versa
If temperature increases then number of moles inside decreases.
∴ Gas escapes out

21.
 Dalton’s Law

2. Closed rigid container

It is surrounded by rigid walls.
e.g. gas cylinder, closed room etc.
i.e.,

...................
................... Volume = Constant
Ideal
................... Moles = Constant (by default)
Gas
...................
...................

Note: If the gas takes part in a reaction then moles may be changed.

3. Closed non−rigid container

Atleast one wall must be movable e.g. piston−fitted vessel, balloon, bubble
etc.
y If massless piston, Pgas= Patm (by default constant)
y If piston has mass, Pgas = Patm + Ppiston
i.e. PGas = constant by default
=Pv nRT P ∝ nT
P1 P2
P∝T =
n1T1 n2 T2
P1 T1
⇒ =
P2 T2
• Cas e of open • Case of rigid
container c losed container
Dalton’s Law

22.
ILLUSTRATION:

Q1 An amount of CO2(g) occupies 30 L at 27°C and 1 atm pressure. What would

be the volume of same amount of CO2(g) collected at 227°C and 0.8 atm.

A1 P1 V1 PV
= 2 2
T1 T2
1 × 30 0.8 × V2
=
300 500
⇒ V2 = 62.5 L

Q2 A gas is present at a pressure of Patm. Calculate the % increases in pressure,

which should be done so that the volume of the gas can be decreased to 1/4th
of the initial volume if the temperature is maintained constant.

A2 P1V1 = P1V2
V
P×V = P2 ×
4
⇒ P2 = 4P
increasein P 3P
⇒ % increase in pressure = × 100 = × 100 =300%
Inital P P

Dalton’s Law

23.
 Q3 Pressure of ideal gas contained in a closed rigid vessel is increased by 20%
when it is heated by 60 K. Calculate its final temperature.

A3 Closed rigid vessel ⇒ V = constant, n=constant (by default)

P1 P2
=
T1 T2
P 1.2P
⇒ =
( )
T − 60 T

⇒ T = 1.2 (T−60)
T = 1.2 T − 72
⇒ 72 = 1.2 T − T
72 = 0.2 T
72 72
⇒ T= = × 10 = 360 Kelvin
0.2 2
If T2 = T ⇒ T1= (T−60) = 360 − 60 = 300 K

Q4 At a constant temperature what should be the percentage increase in pres-

sure for 10% decrease in the volume of gas.

A4 Given 10% decrease in volume of gas

P1V1=P2V2
P×V = P2×(0.9V) (P1 = P)
PV × 10
P2 =
9V

10P
P2 =
9
 10P 
 − P
9 100
% increase in pressure=   × 100 = %
P 9
Dalton’s Law

24.
Q5 A certain amount of H2 gas occupies a volume of 5 L at 2 atm pressure and
27°C. Now the temperature is changed to 327°C at constant pressure where
all H2 molecules are dissociated into H(g). Calculate the final volume of con-
tainer

A5 H2(g) → 2H(g)

If x mole
 2x
 mole

1:2

V1 V
= 2 [∴ Pressure is constant, R = constant]
n1T1 n2T2

5 V2
=
’ x ’× 300 2 ’ x ’× 600
5 × ’2x ’× 600
V2 = = 20 L
’ x ’× 300
H2(g) → 2H(g)
If x mole dissociates then 2x mole formed (1 : 2)

Dalton’s Law

25.
 Dalton’s Law
In a gaseous mixture containing two or more gases, the total pressure of
the mixture is equal to the algebraic sum of partial pressure of all gases
present. (Gases should be inert to each other).
PTotal = Pmix
A(g) B(g) C(g)
PA 
 always homogeneous
PB  Partial
 pressure of gas mixture
PC 

So, PTotal = PA + PB + PC

Proof :
PA.V= nART …(1)
PBV = nBRT …(2)
PCV = nCRT …(3)
Also
PTotal V = nTotalRT …(4)
On dividing (1) by (4), we get
PA  n 
= A 
PTotal n
 Total 
i.e. PA = χA.PTotal
Similarly
PB=χBPTotal

PC=χCPTotal
Now,
⇒ PA + PB + PC = PTotal (χA+χB + χC)
⇒ = PA + PB + PC = PTotal as χA + χB + χC = 1
Hence proved
So,
In a gaseous mixture

(Partial pressure )
Gas
= (Mole Fraction )
Gas
.PTotal
Dalton’s Law

26.
ILLUSTRATIONS:

Q1 A non−reacting mixture of gases A,B and C is kept into 8.21 litre container
at 27°C. If mixture consists 12.5 gm A, 0.5 moles of B and 88 gm of C, then
calculate total pressure and partial pressure of each gas in the container.
(Molar mass A and C be 25 and 88 g/mol respectively).

A1 Given:
Mass of gas A = 12.5 gm
Molar Mass of A = 25
12.5 g
Moles of gas A = = 0.5 mole
25 g / mol
Moles of gas B = 0.5 mole
Mass of gas C = 88 gm
Molar mass of gas C = 44 g/mol
88 g
= 2mole
Moles of gas C = 44g / mol

Total moles = (0.5 + 0.5 + 2) mole

= 3 mole
nTotal .RT 3 × 0.0821 × 300
Using Ptotal = = = 9 atm
V 8.21

0.5
i.e. PA = = × 9 1.5 =
atm PB
3
= PB
2
PC= ×9 =6 atm
3
Dalton’s Law

27.
 Vapour pressure of volatile
liquid

Vapour pressure of volatile liquid:

At a constant temperature, the pressure exerted by vapour of the substance
when an equilibrium is present between liquid and gaseous phases of the
substance is known as vapour pressure of that liquid at that temperature.
At T Kelvin

y For a particular volatile liquid, the vapour pressure depends upon

temperature.
As. T↑ ⇒ V.P increases
T ↓ ⇒ V.P decreases
y Vapour pressure of water is also known as aqueous Tension
Examples
(i) At T Kelvin

PInside  Px  PH O
2
 (P)x  (V.P)H O
2

X(g) H2+O(g)

H2O(l)

X(g)
PX = ?
Vapour pressure of volatile liquid

PA =ρ( gh − PGas + V.P 

 Same level
(ii) PB = ρatm 
PGas = ρatm − ρgh − ( V.P )H O h
2

A
B
H2O

28.
ILLUSTRATION:

Q1 To an evacuated vessel with movable piston under external pressure of 1

atm, 0.1 mol of He and 1.0 mol of an unknown compound (vapour pressure
0.68 atm, at 0°C) are introduced. Considering the ideal gas behavior, the to-
tal volume (in litre) of the gases at 0°C is close to:

A1 For piston − fitted vessel

Pin = Pext Pext = 1 atm
(PHe + Px ) =
1atm ............
............ Massless
............
⇒ PHe =
0.32 atm ............
He X (g)
For He B
PV = nRT
0.32×V = 0.1×22.4
X(l)
V=7L

Vapour pressure of volatile liquid

29.
 Relative Humidity (R.H)
y It is a measure of moisture present in the atmosphere.
 PH O(g)in atmosphere 
=R.H  2  × 100 at same temperature
 V.P of H2O(l) 

ILLUSTRATION:

Q1 Calculate the weight of water in grams per lite of air at 27°C and 50% rela-
tive humidity. Vapour pressure of water at 27°C is 19 mm of Hg.
(Given R = 0.08 atm − litre / mole − K)

A1 Given Relative humidity = 50%

Vapour pressure of water at 27°C = 19 mm of Hg
 PH O(g)in atmosphere 
= R.H  2  × 100 at same temprature
 V.P of H2O 
PH2O
=
50 × 100
19
19 × 50
PH2O =
100
19
= mm of Hg
2
For H2O(g)
PV = nRT
19/2 w
× 1= × 0.08 × 300
760 18
19 × 18
=
2 × 760 × 0.8 × 300
Vapour pressure of volatile liquid

3
= g
320

30.
 Effusion: .............
. .............
The process in which a gas comes out of the . .............
vessel through a small opening or hole. . . . . . . X(g)
........
. .............
. .............
. . . . 0.2
. . . .atm
......
. .............
. .............
. .............

Diffusion:
The natural tendency of gases to be intermixed with each other thoroughly.

X(g) Y(g) Partition Homogeneous

removed
 X(g) Y(g)
5 atm 10 atm mixture of X & Y

y Both effusion and diffusion of gas involve travelling of the gas.

y A gas travels due to pressure difference of that gas only.

Rate of diffusion / effusion (r)

It can be defined as the following:

Moles of gas effused

 Time taken


 Volume of gas effused

 Time taken

r=
Decrease in pressure

 Time taken


Distance travelled in narrow tube
 Time taken

Vapour pressure of volatile liquid

31.
 Graham’s Law

Note: Rate of effusion of a gas is directly proportional to the pressure

difference of that gas only.
(r) ∝ (∆P)x only
i.e.
(r)x ∝ (Pin − Pout )x

Graham’s Law
For different gases, in same conditions of T and P, the rate of effusion of a
gas into vacuum is inversely proportional to the square root of the density
of the gas.

1
rgas ∝
dgas

Case − I : For different gases in similar conditions

.............
.V .............
..............
. T. . . A
..........
. . . . . .(g)
........ 1
..............
. P. . . d
. . . . . .M.... rA Vacuum ∵r 
. . . . . A. . . . . . A. . . d
. n. . . . . . . . . . . . .
..............
.............
.V. . . . . . . . . . . . .
.............. rA dB
.T. . . . . . . . . . . . .  
. . . . .B.(g)
........ rB Vacuum
.............. rB dA
.P. . . . . . . . . . . . .
. . . . .d.B. . . . M....
. . . . . . . . . . . .B. .
.n. . . . . . . . . . . . .
For a gas,
PM = dRT
PM
⇒ d =
RT
d ∝ M [For same P and T]
1 rA MB
So, r ∝ ⇒ =
M rB MA
Graham’s Law

32.
Case − II: For different gases in different conditions
 gases are different
.............
.V. . . . . . . . . . . . .
..............
.T. . . .A. (g)
........
..............
.P. . . . . . . . . . . . . Vacuum
. .A. . . . . . . . . . . .
.n. . . . .M. A. . . . . . .
. .A. . . . . . . . . . . . 1
..............
.............
.V. . . . . . . . . . . . .
rgas 
..............
.T. . . .B. . . . . . . . . Mgas
. . . . . .(g)
........
.P. . . . . . . . . . . . . Vacuum
. .B . . . . . . . . . . . .
.n. . . . .M. . . . . . . .
. .B. . . . . . . . . . . .
. . . . . . .B. . . . . . .
Also,
(
rgas ∝ Pin − Pout )Gas
But Pout = 0
Pin
rGas ∝
M

rA PA MB
⇒ =
rB PB MA
Also,
 Pinside ∝ ninside
ninside
So, r ∝
M

rA nA MB
⇒ =
rB nB MA
Note: Until given specifically, consider conditions to be identical. Graham’s Law

33.
 ILLUSTRATION:

Q1 The ratio of the rate of diffusion of helium and methane under identical con-
dition of pressure and temperature will be
(A) 4 (B) 2 (C) 1 (D) 0.5

A1 (B)
Given: Identical condition of P and T
1
We know that r ∝ Only
M

rHe MCH
= 4

rCH MHe
4

16
=
4
2
=
1
=2
Or
moles effused
 r=
time
 nHe effused 
rHe  time 
So, =  
rCH4  CH4
n effused 
 
 time 
If time is same
rHe n  2
= = He 
rCH  nCH  1
4  4 effused

i.e. In a given time if one mole CH4 is effused then in same time 2 mole
He will be effused
Note: Effused molar ratio = Ratio of rates of effusion (In same time)
Graham’s Law

34.
Q2 32 ml of He effuses through a fine orifice in 1 minute then what volume of
(CH4 will effuse in 30 seconds under the similar condition.

A2 Given 32 ml of He effuses through a fine orifice in 1 minute.

1 r MCH4  Veffused 
=
r∝ ⇒ He =∴ r
M rCH4 MHe  time 
32 / 60 16
⇒ =
V / 30 4
32 30 4
⇒ × =
60 V 2
16 4
⇒ =
V 2
16 × 2
⇒ V=
4
= 8 ml

Q3 A mixture of H2 and O2 in 2:1 molar ratio is allowed to effuse through an ori-

fice. Calculate the composition of gases coming out initially.

A3 We know that
.
. . . . . . . . . . . . .
. . . . . . . . . . . . .
nin . . . . . . . . . . . . . .
rgas ∝ . . .H . . . . . .O . . . . .
. . . . 2. .and. . . . . . . .
M . . . . . . . . . . .2 . . .
. . . 2. .: .1 . . . . . . . . Effused
rH  nH  MO .
.
. . . . . . . . . . . . .
. . . . . . . . . . . . .
2
= 2  2
. . .Molar
. . . . . ratio
. . . . . . mix = ?
rO  nO  MH
2  2 in 2

2 32
= ×
1 2
2
= × 16
1
= 2×4
8
=
1
Graham’s Law

35.
 Q4 Compare the rate of diffusion for CO and a mixture of He and CH4 in 3:1 mole
ratio under similar condition

A4 Given:
3(4) + 1(16) .............
=Mmix = 7 g / mol ..............
3+1 .V. . . . . . . . . . . . .
.............. CO
We know that .T. . . . . . . . . . . . .
.P. . . CO(g)
..........
.............. r1
1 .n. . . . . . . . . . . . .
r∝ ..............
..............
M
.............
rCO Mmix ..............
.V. . He
. . . . . CH......
= ......& . . . . .4 . . . Mixture
rmix MCO .T. . . . . . . . . . . . .
.P. . . . .3. :. 1. . . . . .
.............. r2
7 .n. .Molar
...........
= . . . . . . . . ratio
......
28 ..............
1
=
4
1
=
2
Graham’s Law

36.
Q5 Two different bottles containing NH3(M.M=18) gas and HCl (M.M=36) gas are
connected to two ends of a 100 cm long narrow tube. Determine the position
of first white ring of NH4Cl formed. if both bottles are opened simultaneous-
ly.

100cm

18 36
NH3 (g) HCl(g)

(100 − x)cm (x cm)

A5 When both gases meet first time, first ring of NH4Cl will be formed.
Similar conditions (by default)
1
So, r∝ only
M
rNH MHCl
3
=
rHCl MNH
3

( 100 − x ) / t 36
= (same time)
x/t 18
100 − x
= 1.4
x
⇒ 100 − x = 1.4x
= 1.4x + x
100
100 = 2.4x
100
⇒ x= cm
2.4
x = 41.66 cm Graham’s Law

37.
 Q6 A classroom consist 13 equidistant rows of benches. From first bench the
teacher releases, laughing gas (N2O) and simultaneously the student from
last bench releases weeping gas (C3H5OBr). Calculate at which bench
students will laugh and weep simultaneously?

A6 N2O →
12m ← C3H5OBr
1 2 3 4 5 6 7 8 9 10 11 12 13
x (12 − x)

x/t 137
= ≈ 1.7
( 12 − x ) / t 44
⇒ x =1.7(12 − x)
x = 20.4 − 1.7x
⇒ x + 1.7x =20.4
2.7x = 20.4
20.4
⇒ x =
2.7
⇒ x =
7.55
⇒ x =
8m i.e., 9th bench from first
Graham’s Law

38.
 Kinetic Theory of Gases

Note: Successive effusion

nA n'A
nB nB'

A(g) ,B(g) n'A n''A nnA

1st step nd th
2 step n step
nA 
 nB' 
 nB'' 
 nBn
nB

 Effused molar ratio =ratio of rates

(n)int ial
Also r ∝
M
In any step,

(nA ) n 
= A
MB
(nB ) effused  nB Inside MA

n’A nA  MB 
1st step =  
nB’ nB  MA 
 

n’’A n’A MB
2nd step = ’
nB’’ nB MA
2
n’’A nA  MB 
=  
nB’’ nB  MA 
So, nth step :
n
nnA nA  MB 
=  
nBn nB  MA 
n
Effused ratio  n ''  n A  MB  No of steps
 A =  
after 'n' steps  n ''  nB  M  Initial ratio
Kinetic Theory of Gases

 B A 

39.
 ILLUSTRATION:

Q1 A mixture of H2 and N2 gases in 1:14 molar ratio is being separated by succes-

sive effusion. Calculate after how many steps the molar ratio becomes 14:1?

A1 Given :
Mixture of H2 and N2 gases in 1:14 molar ratio.
 nH   nH   MN 
 2  = 2   2

 nN     MH 
 2 Effusion  nN2 Initial  2 
n
14 1  28 
=  
1 14  2 

( 14) = ( 14 )
2 n/2

⇒ n=
4
Kinetic Theory of Gases

40.
 Kinetic Theory of Gases:
y Applicable only and only for ideal gases.
y Main postulates of Kinetic theory of gases are as following:
i) A gas is the collection of very large number of particles (Bulk amount).
ii) Volume of particle is negligible as compared to volume of container.
iii) There is no force of attraction between the particles of a gas at
ordinary temperature and pressure.
iv) All particles travel in straight line with high speeds and continuously
stroke with walls of container
v) All collisions are perfectly elastic. Hence no change in total kinetic
energy of gas particles.
vi) The average kinetic energy per molecule depends upon temperature
only.
vii) The pressure of gas is due to collisions by particles with walls of
container.

As per kinetic theory of gases, the pressure exerted by one particle of mass
‘m’ in a container of volume ‘V’ is given as following: (u− speed of particle)
1 mu2
P=
3 V
y For a gas sample containing ‘N’ particles in a container of volume ‘V’ and
having speeds u1, u2, u3 ……….. un,
1m 2
=P u + u22 + u23 + ...........un2 
3 V  1 
1m 2 
P= N. urms
3 V  
y For one mole gas
i.e. N = NA
1m
So, P =
2
.NA urms
3V
Where ‘m’ is mass of one particle.
(mNA) is mass of NA particles or molar mass of gas (M).
1M 2
Kinetic Theory of Gases

So, P = urms
3V
Calculation of K.E:
For one particle,
1
K.E = m.u2
2

41.
 For gas sample containing ‘N’ particles:
1
( )
K.E = m. u21 + u22 + ....................un2
2

1
= m Nurms
2
( 2
)
For 1 mole gas
1 2
K.E = mNAurms
2
1 2
K.E = Murms
2
1
K.E = ( 3PV )
2
3
= (K.E)1mole = PV [ n 1]
2
3
(K.E)1mole = RT
2
For ‘n’ mole gas
3
( )
K.E
Total
= nR T
2
( )
K.E ∝ (n)gas
Total

( )Total
K.E ∝ T(Kelvin)

Average K.E per molecule:

Total K.E
(K.E)avg. =
No. of molecule
3
n.R.T
(K.E)avg. = 2
n.NA
3
(K.E)avg = k.T
2
(K.E )avg ∝ T(Kelvin) only

Also:
K is Boltzmann’s constant
Kinetic Theory of Gases

 R 
k= 
 N 
 A
8.314J / mol / K
k=
6.02 × 1023 mol −1
k = 1.38×10−23 J/K

42.
 Different speeds of gas

ILLUSTRATION:

Q1 As the temperature is raised from 20°C to 40°C, the average kinetic energy
of neon atoms changes by a factor:
1 313 313
(A) (B) (C) (D) 2
2 293 293

A1 (C)
Temperature is raised from
20°C to 40°C
We know that
(K.E)avg ∝ T(Kelvin)
K.Ef 313
=
K.Ei 293

Q2 Two flasks A and B have equal volumes, A is maintained at 300 K and B at

600 K, while A contains H2 gas, B has an equal mass of CO2 gas. Find the ratio
of total to translational kinetic energy of gases in flaks A to that of B.
(A) 1:2 (B) 11:1 (C) 33:2 (D) 55:7

A2 A is maintained at 300 K and B is at 600 K. A contains H2 gas and B has mass

equal mass of CO2 gas
We know that (K.E)Total ∝ n.T
(K.E)A nH × 300
= 2

(K.E)B nCO × 600

2

(K.E)A w / 2 1
= ×
(K.E)B w / 44 2
(K.E)A 44 1
= ×
(K.E)B 2 2
(K.E)A 11
=
(K.E)B 1
Different speeds of gas

43.
 Different speeds of a gas
For a gas sample containing N particles having speeds u1, u 2, u 3 ………… uN,
there are following three types of speeds

i) Average / Mean speed (uavg)

u1 + u2 + u3 + ..........un
uavg =
N
N

∑u e
i
u avg = i=1
N

ii) Root mean square speed (urms)

N

∑u 2
i
urms = i=1
N
u21 + u22 + u23 .........uN2
urms =
N

2
urms .N = (u 2
1
+ u22 + ..........un2 )
iii) Most probable speed (ump)
The speed corresponding to maximum number of particles.
Let 6 × 103 particles have 10 m/s
1 × 105 particles have 2 m/s
4 × 102 partciles =
12 m/s
So,
ump = 2m/s

For ‘n’ mole gas

3RT 3PV 3P
=
urms = =
M n.M d
8RT 8PV 8P
=
uavg = =
Different speeds of gas

πM πnM πd

2RT 2PV 2P
=
ump = =
M nM d

44.
Note: In above relations put all values in SI units only.
R = 8.314 J/mol.K
T in Kelvin
P in N/m2 or Pascal
V = Volume of container (in m3)
d = density of gas (in kg/m3)
n = moles of gas
M = Molar mass of gas (kg/mol)
For a particular gas at constant temperature:
8
urms : uavg : ump = 3: : 2
π
= 1.73 : 1.62 : 1.41
i.e., U rms > u avg > ump

Different speeds of gas

45.
 ILLUSTRATION:

Q1 The ratio between the root mean square velocity of H2 at 50 K and that of O2
at 800 K is:
1
(A) 4 (B) 2 (C) 1 (D)
4

A1 (C)
T T
We know that :urms ∝ = urms ∝
M M
uH2 50 / 2 × 10−3
=
uO2 800 / 32 × 10−3
uH2 50 × 32
=
uO2 800 × 2
uH2
=1
uO2

Q2 At 400 K, the root mean square (rms) speed of a gas ‘x’ (molecular weight
= 40) is equal to the most probable speed of gas y at 60 K. The molecular
weight of gas y is:

A2 At 400 K, rms of gas x is equal to most probable speed of gas y at 60K.

(urms )x = (uMP )y
 3RT   2RT 
  =  
 M x  M  y
3 × 400 2 × 60
i.e. =
40 M
1 3 × 400
⇒ =
M 40 × 2 × 60
1 1
⇒ =
Different speeds of gas

M 4
⇒ M= 4
∴ Molar mass of gas y = 4

46.
Q3 Which of the following statements is/are correct regarding the root mean
square speed (urms) and average translational K.E (Eav) of a molecule in a gas
at equilibrium.
(A) Urms is doubled when its temperature is increased four times
(B) Urms is inversely proportional to the square root of its molecular mass
(C) Eav at a given temperature does not depend on its molecular mass
(D) Eav is doubled when its temperature is increased four times

A3 A,B,C
Relation of Urms and Eav

3 3RT
= Eav = RT, Urms
2 M
1
Urms ∝
M
Eav does not depend on its molecular mass.
According to the relation given above Eav get doubled when the temperature
is increased 2 times. Thus option (D) is incorrect.
∴ Statements A , B and C are correct regarding the root mean square speed
(Urms) and average translational kinetic energy (Eav) of a molecule if gas at
equilibrium.

Different speeds of gas

47.
 Maxwell’s distribution of
molecular speeds

y In a gas sample, at a certain temperature all particles do not have same

speed but they posses a wide range of molecular speed.
i.e., At T Kelvin

Range of Speed

u min umax

y According to Maxwell, in a gas sample at a certain temperature, the number

of particles corresponding to a particular speed remains constant which
can be given by following equation:
3
 M  2  − 2RT 
Mu2
dN  u2
= 4 πN   e
du  2RT   


where:
N = Total number of particles in gas sample
M = Molar mass of gas 

R = Gas constant  All in SI units
T = Temperature 

u = Speed 

dN
= No. of particles corresponding to speed ‘u’.
du
 dN 
 
du 
Also  = Fraction of particles corresponding to speed ‘u’
N
For a particular gas at a certain temperature:
Maxwell’s distribution of molecular speeds

N max

 dN 
 
 du 

u
u u
mp
u
avg
u
rms max u
min

48.
y At any speed, the height of the curve represents no. of particles corresponding
to that speed.
y So, the peak represents maximum number of particles and hence the
corresponding speed is ump

2RT
For Nmax , put u = ump in the equation, if=
u u=
mp
M
3
M 2RT
 dN   M  2 − 2RT ×  2RT 
  ⇒ Nmax =4 πN   e M
 
 du   2RT   M 
1
4 πN  M  2
Nmax =  
e  2RT 

y In a gas sample, particles having very low and very high speeds are very less
means most particles have speeds near to ump .

y Total area under the curve =N

 dN 
Note: If   is taken on y-axis, area under the curve=1 (sum of fraction)
 du 

Case 1 : for same gas at different temperatures

On increasing temperature, the curve become broader and vice-versa
with same area under the curve.

ump ∝ T
1

Maxwell’s distribution of molecular speeds

Nmax ∝
T
 dN 
 
 du 

T1 T2

ump1 ump2 u

49.
 Case 2 : for different gases at same temperature
If molar mass is more then curve becomes steeper and vice-versa with
same number of particles.

 dN 
 
 du 
1
Ump 
M
M1 > M2
Nmax  M

M2
M1
u 

Maxwell’s distribution of molecular speeds

50.
ILLUSTRATION:

Q1 According to kinetic theory of gases:

(A) Collisions are always elastic
(B) Heavier molecules transfer more momentum to the wall of the container.
(C) Only a small number of molecules have very high velocity.
(D) Between collisions, the molecules move in straight lines with constant
velocities.

A1 A,C,D
Theory Based

Q2 Which one of the following statements is NOT true about the effect of an
increase in temperature on the distribution of molecular speeds in a gas?
(A) The fraction of the molecules with the most probable speed increases.
(B) The most probable speed increases
(C) The area under the distribution curve remains the same as under the
lower temperature.
(D) The distribution becomes broader.

A2 A
The fraction of the molecules with the most probable speed decreases.

Maxwell’s distribution of molecular speeds

51.
 Q3 If the distribution of molecular speeds of a gas is as per the figure shown
below, then the ratio of the most probable, the average and the root mean
square speed respectively is

u
(A) 1 : 1 : 1 (B) 1 : 1 : 1.224
(C) 1 : 1.128 : 1.224 (D) 1 : 1.128 : 1

A3 (B) 1 : 1 : 1.224
Graph represents symmetrical distribution of speed and hence, the most
probable and the average speed should be same, but the root mean square
speed must be greater than the average speed.
Maxwell’s distribution of molecular speeds

52.
 Collision Parameter

ILLUSTRATION:

Q1 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 on contained the gas, while bulb B
was empty before opening the stopcock. The pressure fell down to 40% at
constant temperature in container A. Calculate volume of the bulb B(in cm3).

A1 A B

X g  X g  X g 
Empty 0 0
n,p 0.4p 0.4p

V1  100 cm3 Vcm3 100 cm3 Vcm3

For X(g), PV = nRT

So, P1V1 = P2 V2

(n,R,T are constant )

100 0.4P ( 100 + V )
P ×=
P × 100 = 40P + 0.4PV
100P − 40P =0.4PV
60P = 0.4PV
60P
⇒ V=
0.4P
60
= × 10
4
⇒ Volume of Bulb B = 150 cm3

Collision Parameter

53.
 Q2 Two closed bulbs of equal volume (V) containing an ideal gas initially at
pressure Pi and temperature T1 are connected through a narrow tube of
negligible volume as shown in the figure below. The temperature of one of
the bulbs is then raised to T2 . The final pressure Pf is:

T1 T1 T1 T2

P,V
i
P,V
i  Pf ,V Pf ,V

' x 'mole ' y 'mole 'n1 'mole 'n2 'mole

 TT   T1T2   T1   T2 
(A) 2Pi  1 2    (B) Pi    (C) 2Pi    (D) 2Pi  
T +T
 1 2   T1 + T2   T1 + T2   T1 + T2 

A2 (D)
Initially
PV
Let ‘x’ moles of gas in first bulbs x = i
RT1
PV
and ‘y’ moles of gas in bulb second, y = i
RT1
After the temperature of second bulb is raised to T2, then the number of
moles of gas in both the bulbs are:
Pf V Pf V

= n1 = and n2
RT1 RT2
Total no. of moles of gas in both bulbs remains same in both the cases.
x + y = n1 + n2
2PV
i Pf V Pf V
= +
RT1 RT1 RT2
2PV
i Pf V  1 1 
=  + 
RT1 R  T1 T2 
2PV P V  T + T1 
i
= f  2 
RT1 R  T1T2 
2PVi R  TT 
⇒ Pf= ×  1 2 
Collision Parameter

RT1 V  T2 + T1 
2PT
i 2
Pf =
T1 + T2
Hence, option (D) is correct.

54.
Q3 A closed tank has two compartments A and B, both filled with oxygen (as-
sumed to be ideal gas). The partition separating the two compartments is
fixed and is a perfect heat insulator (Figure 1). If the old partition is replaced
by a new partition which can slide and conduct heat but does NOT allow the
gas to leak across (Figure 2), the volume (in m3) of the compartment A after
the system attains equilibrium is:

1 m 3, 5 bar, 3 m3 , 1 bar, 300 k

400 k B
A
Figure A

A B

Figure B

A3 For compartment
= A, Vi 1= bar, T1 400 k. Let Vf = y m , Pf = P,
m3 , Pi 5=
3

Tf = T . ‘ n ’ is constant.
PV Pf Vf
So: i i
=
RTi RTf
5× 1 P× y
⇒ =
400 T
P 5
⇒ =
T 400 y
.... 1 ()
For compartment B:
=Pi 1 = =
bar, Vi 3m3
, Ti 300 k
’
( 3 − y ) m3 , Tf’ =
P, Vf’ =
Let Pf = T

ni = Pf
Collision Parameter

Pf’ Vf’ Pf’ Vf’

=
RTf’ Rf Tf’
1 × 3 P × (3 − y )
=
300 T

55.
 3 1 P
× =
300 ( 3 − y ) T

P 3 1
⇒ = × ..... ( 2)
T 300 3 − y
On comparing (1) & (2) we get
3 1 5
⇒ × =
300 ( 3 − y ) 400y
3 400 3−y
⇒ × =
300 5 y

4 3−y
=
5 y
⇒ 4y =5 (3 − y )
4y = 15 − 5y
⇒ 9y =
15
15 3
⇒ y = m
9
⇒ 1.67 m3
y =
Collision Parameter

56.
Collision parameters
In a gas sample, since particle collide continuously with each other so
there are some properties related to these collisions.

i) Z1 (Collision frequency)
The average number of collisions made by one particle per unit time,
per unit volume.
For a gas,
Z=
1 2πσ2uavg .N*

where: σ is collision diameter σ =2r ( )

8RT
uavg =
πM
N
N∗ = no. of particles per unit volume  
V
Since, PV = nRT
N
PV = .R.T
NA
PV = N.k.T
N P
⇒ =N∗ =
V k.T

ii) Z11 [Collision frequency (or ZAA)]

The average number of biomolecular collision (between two particles)
for same gas per unit-time, per unit volume.
For a gas,
1
=
Z 11
πσ2 uavgN∗
2
1
i.e. Z11 = Z N∗
2 1

iii) Z12 or ZAB (collision frequency)

The average no. of bimolecular collisions between particles of different
gases per unit time, per unit volume,

A B
Collision Parameter

     r1  r2 
r1 r2

57.
 Mean free path (λ)
The average distance travelled by particle between two successive collisions.

Average of such distances= λ

For a gas:
1
λ=
2πσ2 .N∗

Note:
(
If collision frequency is more, then distance travelled will be lesser less λ )
and vice versa.

Effect of T and P
P
2 1
P Z ∝ T λ∝
Z1 ∝ T. 11    P
T T  
      T
P P 2
Z1 ∝ Z11 ∝ 3 T
T λ∝
T 2 P
Collision Parameter

58.
 Behaviour of Real Gases

ILLUSTRATION:

Q1 ‘X’ and ‘Y’ are two volatile liquids with molar weights of 10 g mol −1 and
40 g mol −1 respectively. Two cotton plugs, one soaked in ‘X’ and other soaked
in ‘Y’, are simultaneously placed at the ends of a tube of length ‘L’ (24cm), as
shown in the figure. The tube is filled with an inert gas at 1 atm pressure and
a temperature of 300 K. Vapours ‘X’ and ‘Y’ react to form a product which is
first observed at a distance ‘d’ cm from the plug soaked in X. Take X and Y to
have molecular diameters and assume ideal behaviour for the inert gas and
the two vapours.

L = 24 cm

X(g) Y(g)

d Cotton wool soaked in Y

Initial formation of the product

Cotton wool soaked in X

The value of d (in cm) shown in figure, as estimated from Graham’s law, is:
(A) 8 (B) 12 (C) 16 (D) 20

A1 AS:
1
r∝
M

rx My
=
ry Mx

d/ t 40
=
(24 − d)/t 10
Behaviour of Real Gases

d 2 ( 24 − d)
⇒=

⇒d=
16 cm

59.
 Q2 The experimental value of d is found to be smaller than the estimate ob-
tained using Graham’s law. This is due to
(A) Larger mean free path for X as compared to that of Y.
(B) Larger mean free path for Y as compared to that of X.
(C) Increased collision frequency of Y with the inert gas as compared to that
of X with the inert gas.
(D) Increased collision frequency of X with inert gas as compared to that of Y
with the inert gas.

A2 (D)
With increase in collision frequency, the molecular speed decreases than the
expected so the distance covered will be less.

Q3 The diffusion coefficient of an ideal gas is proportional to its mean free path
and mean speed. The absolute temperature of an ideal gas is increased 4
times and its pressure is increased 2 times. As a result, the diffusion coeffi-
cient of this gas increase x times, then value of ‘x’ is:

A3 Given: diffusion coefficient µ ∝ λ

Also, µ ∝ uavg
⇒ µ ∝ λuavg
T
⇒µ∝ 
P
( T)
3
T2
⇒µ∝
P
3
µ  T2  2  P1 
⇒ 2 =
   
µ1  T1   P2 
3
µ2  4  2  1 
∴
=  =   4
µ1  1   2 
Behaviour of Real Gases

60.
 Real Gases:
y No gas is always ideal means all are real gases which just can show ideal
behaviour under certain conditions.

Real Gas

PV=nRT PV ≠ nRT
⇒ Ideal behaviour ⇒ Non − Ideal behaviour
i.e.Ideal gas i.e. Non Ideal gas

y For real gas: -

(i) Volume of gas particles is not negligible as compared to volume of
container.
(ii) Intermolecular forces are present (Both attractive and repulsive
forces).
y Due to above reasons there are some changes (corrections) in pressure of
gas and free volume of gas, which are as following: -
y Volume Correction (VI)
⚪ Free volume of gas:
The volume available for gas particles to move freely (Vgas).
.........
.........
.........
. . . .. . . . .
. .. . . . . . .
.. . . . . . . ..
.........
.......
Let volume of container is V

For an ideal gas volume of particles Negligible

 
 Vgas ideal  V

but for a real gas

(V )
gas Real
<V

Vgas= V − V ’
Behaviour of Real Gases

Where V ’ is effective volume of gas particles.

For a gas:
b → effective volume of 1 mole particles
So for n-mole gas:
( )
Effective volume V ’ = nb

61.
 Vgas= V − nb
Where Vgas is free volume
nb is effective volume of particles.
V is volume of container
y Since gas particles collide continuously with very high frequency (106 per
sec), they acquire some extra volume around themselves in which no other
particle can enter.

y So the actual volume of particle and this extra acquired volume are
collectively known as effective volume.

Calculation of ‘b’
y Gas particles continuously collide with each other in which bimolecular
(
collisions are maximum  99% . )
y So due to high collision frequency particles appear as pairs.

y If all above collisions are superimposed with common centre of mass, then
a sphere is formed which will contain, all these collisions.
If radius of particle =r
Behaviour of Real Gases

⇒ radius of sphere=2r
In this sphere, since no other particle can enter, so effective volume of
4
( )
3
2 particles= π 2r
3

62.
 4 3
= 8. πr
3

4 3
= 4.
Effective volume of one particle πr
3
So, for b (1 mole = NA Particle)
4 
=b 4  πr3NA 
3 
Note: For a gas
(Effective volume = 4 × actual volume of partlce)

ILLUSTRATION:

Q1 The density of mercury is 13.6 g/cm3. Estimate the ‘b’ value of Hg(g).
(Atomic mass of Hg = 200).

A1 58.82 cm3
Given: density of mercury = 13.6 g/cm3
‘b’ is effective volume of one mole particles.
Mass of 1 mole Hg = 200 grams = 200 grams
200
Volume of 1 mole Hg(l) = cm3
13.6
= actual volume of 1 mole particles.
Effective volume 4 × m = 4 × actual value of particles
200
b = 4× cm3 =58.82 cm3
Behaviour of Real Gases

13.6

63.
 Pressure & Volume Correction,
Vander Waal’s Equation

Pressure correction (P′)

y The pressure of a gas is due to collisions by particles with walls of container.

P P
n Ideal n Real
T gas Pideal gas
T

y There are no forces among particles of an ideal gas, so its particles strike on the wall with
same speed as they possess.
But in a real gas, the particle which is going to strike on the wall is being attracted by other
particles. Hence it will strike on the wall with lesser speed as compared to an ideal gas
under similar conditions.
y Hence the pressure exerted by a real gas in similar conditions of n, V and T is lesser as
compared to an ideal gas.

In Similar Conditions
=
Pgas Pideal − P ’

where Pgas = Pressure of gas, Pideal = Pressure of ideal gas, P′ = Pressure correction

For a real gas,

Pressure & Volume Correction, Vander Waal’s Equation

an2
P′ =
V2

an2
⇒ Pgas = Pideal -
V2
where, n = moles of gas, V = volume container, a = (+) constant for gas

Vander Waal Equation

y To describe behaviour of a real gas, many equations were proposed
out of them, most used equation is Vander Waal equation which is as
following:
For ‘n’ mole,
 an2 
 P +  ( V - nb ) =
nRT
 V2 

For 1 mole,

64.
  a 
 P + 2  ( Vm - b ) =
RT
 Vm 

Where P is pressure of gas

volume of container (Vm = volume for 1 mole gas)
n = moles of gas
R = 0.0821 L atm/mole.K
T = Kelvin temperature
a, b = Vander Waal constant for gas

Note:
For a particular gas, a and b have certain fixed values.

Constant ‘a’
y For a gas ‘a’ is the measure of intermolecular attractive forces (IMAF).
More IMAF ⇒ More value of a ( )
Less IMAF ⇒ Less value of ’a’

e.g.

H2 ⇒H H Non polar molecule

–

Pressure & Volume Correction, Vander Waal’s Equation

+
HCl ⇒ H Cl Polar molecule

N
H H Vector addition
H

H

C
H H Vector addition
H

65.
 Types of molecule IMAF

Polar Dipole-dipole (Strong)

Non Polar London Forces (Weak)

London < dipole −dipole < H -bonding

If type of IMAF is same then,
|IMAF| ∝ Size of molecule → (surface area)
e.g. H2 (non polar) and CO2 (Non polar)
London forces in both but size of CO2 is greater than size of H2.
⇒ IMAF > IMAF
CO2 H2

( )CO
i.e. a
2
> a ( )H
2

Constant ‘b’
For a gas, ‘b’ is the measure of size of molecule.
More molecular size ⇒ More value of ‘b’.
Less molecular size ⇒ Less value of ‘b’
4
Since b = 4. πr3 .NA
3
Pressure & Volume Correction, Vander Waal’s Equation

b ∝ r3

Units of a and b
an2 PV2
=
P ⇒ =
a
V2 n2
i.e. a = atm.L2 .mol −2
V = nb ⇒ b = V/n
i.e. b = L mol–1

66.
 Compressibility Factor (Z)
It gives information about the behaviour of a gas in given conditions.

P P
Ideal Real
n n
gas gas
T T

Vcontainer = Videal Vcontainer ≠ VReal

VR eal
( Z )R eal = VIdeal

y For ideal
P.Videal = nRT
PVreal
(Z)Real = VReal / (nRT/P) = =
nRT
PV PVm PM P
=Z = =
nRT RT
=
dRT CRT

Where
P is pressure of gas (atom);

Pressure & Volume Correction, Vander Waal’s Equation

V, Vm is volume of container (l)
n is mole of gas
R = 0.0821 L atm/mol.K
T = Kelvin Temperature
M = Molar mass (g/mol)
d = density (g/L)
C = Molarity of gas (Mol/L)

67.
 Compressibility factor &
Related Graphs

P P Real
Ideal
n gas n gas
T T

VReal
(Z ) = V
gas
ideal

y The value of Z gives information about the behaviour of gas as following:-

If Z = 1 ⇒ PV = nRT i.e. Ideal behaviour
Also, VReal = VIdeal

i.e. Both attractive and repulsive forces are mutually balanced with each
other (Fnet = 0).
If If Z ≠ 1 then PV ≠ nRT ⇒ Non-Ideal behaviour

Z<1 Z>1

VReal < VIdeal VReal > Videal

i.e. Repulsive force dominant
i.e. Attractive forces dominant.
(+ve deviation from ideal behaviour
(-ve deviation from ideal behaviour)

Behaviour in some standard conditions

For 1 mole gas,
 a 
Compressibility factor & Related Graphs

 P + 2  ( Vm − b ) =
RT … (i)
 Vm 

PVm
Also Z=
RT
1. For H2 and He gas:
These are lightest gases present on earth (Mass of one particle ~
negligible)
Type of IMAF ⇒ London forces (Weakest)
Also |IMAF| ∝ size ~ very very small
i.e. a → 0 put in equation (i)

68.
 (P + 0) (Vm – b) = RT
PVm – Pb = RT

Pb
Z= 1 + i.e Z > 1 (always) ⇒ repulsive forces dominant.
RT

2. For typical real gases: The behaviour of such gases varies with pressure
(i) At very low pressure (P → 0)
 1 
i.e. very high Vm ⇒ Vm2 very very high ⇒  2  very very low
 Vm 

 a  
 P + 2  ~ P 
 Vm   Put in equation (i)
( Vm − b) ~ Vm 
(P )( Vm )  RT
⇒ Z = 1 ⇒ ideal behaviour
(ii) In low pressure range (P ~ 1 atm)
 RT a 
=
As, P  −
 V − b V2 
 m m 

PVm Vm a

= −
RT  b  VmRT
Vm  1 − 
 Vm 

−1
 b  a
Z=
 1 −  −
 Vm  VmRT

    b  
( ) ( )
Compressibility factor & Related Graphs
−1
  1− x = 1 + x + x2 + .....    < 1 always 
    Vm  
  2 
b   b  − a
So, Z = 1 +  +
   + ....
  Vm   Vm   VmRT
 
 a  1 b2
Z =1 +  b −  + + ....
 RT  Vm Vm2
Low pressure ⇒ High Vm
\ Vm2 , Vm3 , Vm4 ..... very high

69.
  1   1 
⇒  2  ,  3  .... negligible
 Vm   Vm 

 a  1
So, Z =1 +  b −  in low pressure range.
 RT  Vm
a
Always b <
RT
⇒ Z<1
a
If b is negligible then Z= 1 −
VmRT

(iii) In high pressure range

a  a 
P >> ⇒ P + 2  ~ P
Vm2  Vm 

( )(
So, P Vm − b =
RT )
Pb
⇒ Z= 1 +
RT
e.g. H2/He only Other
Pb
Z= 1 + Low pressure
RT
 a  1
Z =1 +  z − 
 RT  Vm

High pressure
Compressibility factor & Related Graphs

Pb
Z= 1 +
RT

70.
GRAPHS
1. P vs V at constant temperature
For ideal gas at constant temperature, PV = constant
For Typical Real Gas

High Real gas

Ideal gas
Pressure

Vi< VR VR < Vi
Volume

In low P, Z < 1
⇒ Vreal < Videal
In high P, Z > 1
⇒ VReal > VIdeal

2. ‘Z’ vs ‘P’ graphs (at constant temperature)

Case-I: for different gases at same temperature
(i) For H2 and He gases
b
Z= 1 + P ...(1)
RT
Z
Comparing equation (1) with line equations H2

Compressibility factor & Related Graphs

we get
y= c + mx He
 b 
slope =  
 RT  Z=1
Intercept = 1
 ( Size)H > ( Size)He P
2 O
⇒ (b)H > (b)He
2

i.e. ( Slope)H > ( Slope)He

2

71.
 (ii) For typical real gas at very low pressure, Z = 1
(iii) At low pressure, Z < 1
  a  1 
 Z =1 +  b −  
  RT  Vm 

Note: For typical real gas, if Z vs P graph is given, then to solve, use high
pressure range.

For same gas at different temperature

At high pressure, Z > 1
Pb
Z= 1 +
RT
(i) For H2 or He gas Z
T1
 b 
=Z  P + 1 m1 T2
 RT 
m2 T3
For a particular gas (b = constant) m3
1
m∝ Z=1
T
i.e. if T ↑⇒ m ↓
 m1 > m2 > m3 O P
T1 < T2 < T3

(ii) For a typical real gas

In high pressure range
 b  Z
= Z  P + 1
 RT 
T1
 b  T2 T
Compressibility factor & Related Graphs

Slope =   3
 RT 
For same gas (b = constant) Z=1
1
m∝
T
 m1 > m2 > m3 O P

⇒ T1 < T2 < T3

Also, in low pressure range, as temperature increases, slope of curve also

increases.
So, at a certain temperature, the slope will become zero. This temperature
is known as Boyle’s temperature.

72.
 Boyle’s Temperature &
Liquefaction of gases

Boyle’s Temperature
y The temperature at which a gas behaves ideally for considerable low
pressure range.
In low pressure,
 a  1
 Z =1 +  b − 
 RT  Vm
At T = TB ⇒ Z = 1
 a  1
1 = 1 + b − 
 RTB  Vm


a
⇒ TB =
R.b

Boyle’s Temperature & Liquefaction of gases

73.
 ILLUSTRATION:

Q1 A gas will deviate most from ideal behaviour at

(A) low temperature and low pressure
(B) low temperature and high pressure
(C) low pressure and high temperature
(D) high temperature and high pressure

A1 B
At high pressure and low temperature, a gas deviates most from its ideal
behaviour.

Q2 For a real gas obeying vander Waal’s equation, a graph is plotted between
PVm (y-axis) and P(x-axis) where vm is molar volume. Find y-intercept of the
graph.

A2  an2 
( )
nRT for n moles, where ‘a’ and ‘b’ are vander Waal’s
 P + 2  V − nb =
 V 

constants. For n = 1
a ab
PVm = Pb − + + RT
Vm Vm2

On comparing above equation with equation of straight line:

=y mx + c
Boyle’s Temperature & Liquefaction of gases

a ab
y-intercept: V − V2 + RT
m m

74.
Q3 For one mole of a vander Waal’s gas when b= 0 and T = 300 K, the PV vs 1/V
plot is shown below. The value of the vander Waal’s constant a (atm. litre2
mol–2) is:

PV(litre atm/mol)
24.6
23.1 (Graph not to scale)

21.6
20.1

O 2.0 3.0
1/V (mol /litre)

(A) 1.0 (B) 4.5 (C) 1.5 (D) 3.0

A3 C
Vander Waal’s equation:
 an2 
(
 P + 2  V − nb =
 V 
)
nRT …(i)

Given b = 0 and n = 1 mole
 a 
⇒ P +
 V 2 
( )
 Vm = RT
 m 
aVm
PVm + = RT

Boyle’s Temperature & Liquefaction of gases

Vm2
a
(PVm=) RT −
( Vm )
( )
y =−a x + RT
y2 − y 1
Slope =
x2 − x 1
20.1 − 21.6
( −a ) = 3−2
−1.5
−a =
1
a = 1.5

75.
 Q4 One way of writing the equation for state for real gases is,
 B 
= RT  1 + + .....  where B is a constant .
PV
 V 
Derive an approximate expression for ‘B’ in terms of vander Waal’s constant
‘a’ and ‘b’.

A4 Vander Waal’s equation:

 an2 
P +
 (
 V − nb =
V 
nRT )

 a 
For 1 mole:  P + (
 V −b =
V2 
RT )

 a  RT
 P + 2 
=
 V  V −b( )
RT a 
P = − 2 ×V
V −b V ( ) 
RTV aV
=PV − 2
( V − b) V
RTV a

= PV −
 b V
V 1 − 
 V
RT a

= PV −
 b V
1 − 
Boyle’s Temperature & Liquefaction of gases

 V
−1
 b a
PV = RT  1 −  −
 V V
 b b2  a
PV= RT  1 + + 2 + ...... −
 V V  V
  a  1 b2 
PV= RT 1 +  b −  + 2 + ......
  RT  V V 
On comparing equation with
 B   a 
PV= RT  1 + + .... ; =
B b − 
 V   RT 

76.
 Liquification of Gas
y To liquify a gas, there must be attraction among particles hence an ideal
gas can never be liquified.
y A gas can be liquified at constant temperature just by applying pressure
on it.
y At a constant temperature, a certain minimum pressure is required for
liquification.
y At higher temperature, the minimum required pressure for liquification will
be higher, which can be explained by Andrew’s Isotherms.

Andrew’s Isotherms
These are P vs V graphs for a gas at different constant temperatures like
T1, T2, T3 and T4 where T1 < T2 < T3 < T4

For 1 mole real gas

Boyle’s Temperature & Liquefaction of gases

y At point A, gas is present at low pressure.

From A to B,
P↑ ⇒ V↓ ⇒ Compression of gas

77.
 y At point B liquification starts means minimum required pressure for
liquification at T = 21.5°C is P2.
y From B to C gas liquifies at constant pressure P2.
y After point C, no change in volume on pressure change means liquification
is completed at C.
y At higher temperature, the minimum required pressure is higher than P2 and
also the horizontal segment becomes shorter due to more compression.
y At temperature TC = 30.98°C, the gas liquifies at high pressure but liquid
and gas phases cannot be distinguished at this pressure and temperature.
y Above temperature TC, the gas cannot be liquified irrespective of any
pressure hence TC is known as critical temperature.

Critical Temperature (TC)

The minimum required pressure for liquification at TC.
y The maximum temperature above which gas cannot be liquified at any
pressure.
y Different gases have different values of their TC.

Critical Pressure (Pc)

y More value of TC means more tendency to be liquified.

Critical Volume (VC)

The molar volume corresponding to TC and PC.
For gas
8a
Tc =
27Rb
Boyle’s Temperature & Liquefaction of gases

a
Pc =
27b2

Vc = 3b

PC VC 3
Note: =
RTC 8

78.