MONICA BEDI

Ph.D Chemistry
12+ Years of Teaching Experience
Trained Million+ students
Author - Top Ranker’s Series (TRS)
INTRODUCTION
Solid State. The matter in solid state possesses a definite volume, a
definite shape and a definite mass.
INTRODUCTION
Liquid State: A definite volume, a definite mass, but no definite shape.
INTRODUCTION

Gaseous State: neither has definite volume nor definite shape but it has definite mass.
LIVE Telecast of a Gas

Gases: Molecules Continuously Dance & that creates Pressure

 MEASURABLE PROPERTIES OF GASES
Mass/Moles
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 = n 
molecular mass of gases  M 
Two other useful formulae to calculate number of moles of gas are -
no. of molecules of given gas  N 
(ii) number of moles = n  
Avogadro's number of molecules  NA 

volume of given gas in litres at NTP*

(iii) no. of moles =
22.4L
MEASURABLE PROPERTIES OF GASES

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 =106 cm3 = 106ml
MEASURABLE PROPERTIES OF GASES

Temperature
Degree of hotness or coldness of a body is measured by temperature
C K  273 F  32
 
100 100 180
C - Celsius 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 = T (in K)
 MEASURABLE PROPERTIES OF GASES

Pressure
F
Force acting per unit area P
A

Pressure Measuring Devices

(1) Barometer: A barometer is an instrument that is
used for the measurement of atmospheric pressure. The
construction of the barometer is as follows.
Units of pressure:
1 atm = 76 cm of Hg
= 760 mm of Hg
= 760 torr
= 1.01325 x 105 N/m2
= 101.325 kPa
= 1.01325 bar
Density
m
Mass per unit volume : d =
v
Units
CGS : g/cm3
MKS : kg/m3
Relation : 1 kg/m3 = 10–3 g/cm3
NTP vs STP

NTP and STP are different

1) NTP means normal temperature and pressure - 1 atm and 273 K
2) STP means standard temperature and pressure - 1 bar and 273 K
In Most numerical solving they can be assumed to be same.
GAS LAWS
BOYLE'S LAW.
This law describes the pressure-volume,
relationship of gases at constant temperature.

The volume of a fixed mass of a gas is inversely

proportional to its pressure at constant
temperature.
 MATHEMATICAL INTERPRETATION OF THE LAW

P1V1 = P2V2
P1 = first pressure
P2 = second pressure
V1 = first volume
V2 = second volume
MATHEMATICAL INTERPRETATION OF THE LAW

For a given amount of the gas, the product of pressure and volume is constant at
constant temperature.
GRAPHICAL REPRESENTATION OF BOYLE'S LAW
GRAPHICAL REPRESENTATION OF BOYLE'S LAW

Plot of p against 1/V at different temperatures.

PRACTICAL IMPORTANCE OF BOYLE'S LAW

The atmospheric pressure at Mount Everest is only about 0.5 atm. The
decrease in pressure at high altitudes causes altitude sickness.
My own Experience
 Crack it !!

1. Representing P, V and T as pressure, volume and temperature, which of the

following is the correct representation of Boyle’s law?
(a) V  1/T (p constant) (b) V  1/P (T constant)
(c) PV = RT (d) PV = nRT
GRAPHICAL REPRESENTATION OF BOYLE'S LAW
GRAPHICAL REPRESENTATION OF BOYLE'S LAW
Boyle’s Law: Another Presentation

since density is  1/V

p  1/V gives p  d

P1 P2
or  = Const.
d1 d 2
Boyle‘s Law Application
Interiors of jet aero planes which fly at very high altitudes (about 10,000 m) are
artificially maintained at normal pressure to have proper oxygen for breathing.
They are also equipped with emergency oxygen supply in case of pressure falls.
 Crack it !!

2. Which of the following graphs represents the correct Boyle's law?

(a) (i), (ii) and (iii) (b) (i) and (iv)

(c) (ii) and (iii) (d) (i), (ii) and (iv)
 Crack it !!
3. Graphs between pressure and volume are plotted at different temperatures. Which
of the following isotherms represents Boyle's law as PV = constant?

(a) Only (ii) is correct representation of Boyle s law.

(b) Only (iv) is correct representation of Boyle's law.
(c) All are correct representations of Boyle s law.
(d) None of these representations is correct for Boyle s law.
Charles' Law
Charles' Law

Charles’s law, a statement that the volume occupied by a fixed amount of gas is directly
proportional to its absolute temperature, if the pressure remains constant.
Charles' Law

V1/T1 = V2/T2
 Charles' Law
Charles's law states that the volume of a gas is directly related to the absolute
temperature when there is no change in the pressure or amount of gas:
V1/T1 = V2/T2

Lower temperature Higher temperature

smaller volume Larger volume
 Charles' Law
Graphical representation:

Graphs between V and T

at constant pressure
are called Isobars.
Charles' Law: Word by Word
1
The volume of a fixed mass of a gas increases or decreases by
273.15
of its volume at 00C for each degree rise or fall of temperature, provided pressure
is kept constant.
 Charles' Law Formula: V1/T1 = V2/T2

■ A balloon inflated in a room at 24°C has a volume of 4.00L. The balloon Is then
heated to a temperature of 58°C. What is the new volume if the pressure remains
constant?

V1 = 4.00L V2 = ?
T1 = 24°C ----> 295K T2 = 580C + 273= 331 K
On the Graph
 Crack it !!

1. Absolute zero can be defined as the temperature at which

(a) pressure becomes zero
(b) volume becomes zero
(c) mass becomes zero
(d) density becomes zero
 Crack it !!

2. If the temperature is increased from 0°C to 39°C at a constant pressure of gas

having fixed mass, then the ratio of initial and final volume will be -
(a) 91:101 (b) 91:104
(c) 91:111 (d) 91:121
 Crack it !!

3. Air at sea level is dense. This is a practical application of

(a) Boyle's law (b) Charle’s law
(c) Avogadro's law (d) Dalton's law
Gay Lussac's Law (Pressure - Temperature Relationship)
Gay Lussac's Law (Pressure - Temperature Relationship)

The relationship between pressure and temperature was given by Joseph Gay
Lussac and is known as Gay Lussac's law. It states that
At constant volume, pressure of a fixed amount of gas varies directly with
temperature.
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
P1 P2
or 
T1 T2
 Graphical representation
:

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

On the Graph
 Avogadro’s Law (Volume-Amount Relationship
Equal volume of all gases –under the same conditions of temperature and pressure
contain equal number of molecules.
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
0r 
n1 n2
 Crack the PYQ

1. For 1 mol of an ideal gas at constant temperature T, the plot of (log P) against (log V)
is a____.
(P: Pressure, V : Volume):-
[AIEEE ONLINE - 2012]
(1) Straight line parallel to x-axis
(2) Curve starting at origin
(3) Straight line with a negative slope
(4) Straight line passing through origin
 Crack the PYQ

2. The initial volume of a gas cylinder is 750.0 mL If the pressure of gas inside the cylinder
changes from 840.0 mm Hg to 360.0 mm Hg, the final volume the gas will be
[JEE MAINS - ONLINE - 2014]
(1) 1.750 L (2) 7.50 L
(3) 3.60 L (4) 4.032 L
 Crack the PYQ

3. A car tyre is filled with nitrogen gas at 35 psi at 27°C. It will burst if pressure
exceeds 40 psi. The temperature in oC at which the car tyre will burst is______.
(Rounded-off to the nearest integer)
[JEE MAINS - 2021 - ONLINE]
 Crack the PYQ

4. The combination of plots which does not represent isothermal expansion of an

ideal gas is:
[JEE MAINS - ONLINE - 2019]

(1) (A) and (C) (2) (A) and (D)

(3) (B) and (D) (4) (B) and (C)
Ideal Gas Equation
GAS LAWS
Boyle’s Law
At constant temperature, the volume of a definite mass of a gas is
inversely proportional to its pressure.

P1V1 = P2V2
P1 = first pressure
P2 = second pressure
V1 = first volume
V2 = second volume
My own Experience
Charles' Law

Charles’s law, a statement that the volume occupied by a fixed amount of gas is directly
proportional to its absolute temperature, if the pressure remains constant.

V1/T1 = V2/T2
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
P1 P2
or 
T1 T2
Avogadro’s Law (Volume-Amount Relationship

Equal volume of all gases –under the same conditions of temperature and pressure
contain equal number of molecules.

V1 V2

n1 n2
 Can you crack it
1. An iron tank contains helium at a pressure of 3.0 atm at 27°C. 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 1535°C)
 Can you crack it

2. A plot of P vs T for a given mass of gas at constant volume is a straight line. P vs T

at constant volumes V1 and V2 for an ideal gas are shown below:

Which of the following is correct?

(a) V1 > V2 (b) V1 < V2
(c) V1 = V2 (d) V1 = 2V2
Crack the PYQ
 Can you crack it !!

4. On a ship sailing in 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 ?
Ideal Gas Equation
One Equation for all ideal gases
THE IDEAL GAS EQUATIONS
Units of R
1 atm  22.4 lit
(i) In lit atm R = = 0.0821 lit-atm mol–1 K–1
273K
1  76  13.6  980 dyne cm -2  22400 cm 3
(ii) In C.G.S system R =
273K
= 8.314 x 107 erg mol–1 K–1

(iii) In M.K.S. system R = 8.314 Joule mol–1 K–1 [107 erg = 1 joule]
8.314  107 erg mol-1K ?1
(iv) In calories R =
4.184  107 erg
= 1.987 ≈ 2 calorie mol–1 K–1
 Lets understand the Parameters & Units

Units R value

V P
L atm 0.0821 L atm K– mol – 1
mL atm 82.1 mL atm K– mol – 1
L bar 0.08314 L bar K– mol – 1
dm3 bar 0.08314 dm3 bar K– mol – 1
m3 Pa* 8.314 Pa m3 K– mol – 1
or N m–2 or 8.314 Nm K– mol – 1
or 8.314 J K– mol – 1

*Pa = N m–2 and Pa m3 = 1 J = 1 kg m2 s–2

 Can you crack it !!

1. A sample of oxygen occupies a volume of 2.0 L at a pressure of 0.5 bar at

40°C. Calculate the pressure if the gas is compressed to 0.225 mL at – 60C.
Can you crack it !!
2. At 25°C and 760 mm of Hg pressure, a gas occupies 500 mL volume. What
will be its pressure at a height where temperature is 10°C and volume of the
gas is 640 mL.
 Can you crack it !!
3. Calculate the mass of hydrogen (H2) present in a 500 mL sample of hydrogen
gas at a pressure of 1 bar and 27°C.
 Can you crack it !!
4. Calculate the volume occupied by 2.045 x 1023 molecules of oxygen at 270C and
having a pressure of 0.935 bar.
 Can you crack it
5. At what temperature 28 g of N2 will occupy a volume of 20 litres at 2 atm?
(a) 300.0 K (b) 487.2 K
(c) 289.6 K (d) 283.8 K
 Can you crack it

6. What is the density of CO2 at 27 °C and 2.5 atm pressure?

(a) 5.2 gL-1 (b) 6.2 g L-1
(c) 7.3 gL-1 (d) 4.46 gL-1
 Can you crack it

7. How many number of moles of nitrogen will be present in 2.24 L of nitrogen gas at
STP?

(a) 9.9 (b) 0.099

(c) 0.001 (d) 1.00
 Can you crack it

8. The drain cleaner, Drainex contains small bits of aluminium which react with
caustic soda to produce dihydrogen. What volume of dihydrogen at 20 °C and one
bar will be released when 0.15 g of aluminium reacts?

(a) 204 mL (b) 200 mL

(c) 203 mL (d) 400 mL
 Can you crack it
9. N2 + 3H2 —> 2NH3
1 mole N2 and 4 moles H2 are taken in 15L flask at 27°C. After complete conversion
of N2 into NH3, 5L of H2O is added. Pressure set up in the flask is (assume water
dissolves NH3)
3  0.0821  300 2  0.0821  300
(A) atm (B) atm
15 10

1  0.0821  300 1  0.0821  300

(C) atm (D) atm
15 10
 Can you crack it
10. An open manometer attached to a flask containing ammonia gas have no
difference in mercury level initially as shown in diagram. After sparking into the
flask, ammonia is partially dissociated as 2NH3 (g) —> N2 (g) + 3H2 (g). Now it have
difference of 18 cm in mercury level in two columns, what is partial pressure of H2
(g) at equilibrium ?

(A) 9 cm of Hg
(B) 18 cm of Hg
(C) 27 cm of Hg
(D) None of these
 Can you crack it
11. An air column closed in a tube sealed at one end by a Hg column having height h .
When the tube is placed with open end down, the height of the air column is I1. If
the tube is turned so that its open end is at the top, the height of the air column is
I2. What is the atmospheric pressure (P0)-
h  l1  l2 
(A) P0  cm of Hg
 l2  l1 
h  l1  l2 
(B) P0  cm of Hg
 l2  l1 

(C) 76 cm of Hg

h  l1  l2 
(D) P0  cm of Hg
 l1  l2 
DALTON'S LAW OF PARTIAL PRESSURES
At constant temperature, the pressure exerted by a mixture of two or more non-
reacting gases enclosed in a definite volume, is equal to the sum of the individual
pressures which each gas would exert if present alone in the same volume at the
same temperature.
DALTON'S LAW OF PARTIAL PRESSURES
If pTotal is the pressure of the mixture of non-reacting gases at temperature T and
volume V, and P1, P2, P3......represent the partial pressures of the gases, then,

PTotal = P1 + P2 +P3 + •••••• (T, V are constant)

Utility of Dalton's law
This law is useful in calculating the pressure of the gas collected by the
displacement of water.
The gas being collected over water also contains water vapors.
Utility of Dalton's law.
The observed pressure of the moist gas is equal to the sum of the pressure of the
dry gas and the pressure of the water vapors.
The pressure of the water vapors is constant at a given temperature and is known
as aqueous tension at that temperature.

pobserved = Pgas + aqueous tension

\
pgas = pobserved - aqueous tension
Illustration of Dalton's law of partial pressures.
Partial Pressure in Terms of Mole Fraction

Mole fraction is the ratio of the number of moles of the component to the total
number of moles.

pA = nART/V ; pB = nBRT/V
 Can you Crack it!!

1. To which of the following gaseous mixtures is Dalton's law not applicable?

(a) Ne + He + SO2 (b) NH3 + HCl + HBr
(c) O2 + N2 + CO2 (d) N2 + H2 + O2
 Crack the PYQ

2. Equal weights of methane and oxygen are mixed in an empty container at 25°C.
The fraction of the total pressure exerted by oxygen is
[IIT-JEE 1981 ]
1 1
(a) (b)
3 2

2 1 273
(c) (d) 
3 3 298
 Crack the PYQ
3. 0.5 moles of gas A and x moles of gas B exert a pressure of 200 Pa in a container of
volume 10 m3 at 1000 K. Given R is the gas constant in JK–1 mol–1 , x is :
[JEE Main 2019 (l)]

(a) 2R (b) 2R
4 R 4R

(c) 4 R (d) 4R

2R 2R
Crack the PYQ
Can you Crack it!!

In a container of capacity 1 liter, air and some liquid water is present in

equilibrium at total pressure of 200 mm of Hg. This container is connected to
another one liter evacuated container. Find total pressure inside the container
when equilibrium is again stabilized (aqueous tension or vapor pressure at this
temp, is 96 mm Hg).
Graham's Law of Diffusion
Graham's Law of Diffusion
GRAHAM'S LAW OF DIFFUSION AND EFFUSION
Diffusion
The process of mixing of gases by random motion of the molecules is called
diffusion.
GRAHAM'S LAW OF DIFFUSION AND EFFUSION
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 equalized. 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

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 r M2 d2
Mathematically , r  or or, 1 = 
Where M d r2 M1 d1
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.
Effusion
It is a particular case of diffusion in which the gases contained in a vessel are
allowed to escape through a small aperture (hole).
The Graham's law of diffusion is also valid for effusion.
Effusion Vs Diffusion
Rate of diffusion in terms of volume diffused

Volume of gas diffused

Rate of diffusion = ------------------------------
Time taken for diffusion V
V
or r=
t
Let V1 be the volume of gas 1 and V2 be the volume of gas 2, then
V1 V2
r1 = r2 =
t1 t2
r1 M 2 V1t2
\  
r2 M 1 V2t2
 Comparison of Rates
(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
V
r1 t1 d2 M2 r t d2 M2
   or 1  2  
r2 V d1 M1 r2 t1 d1 M1
t2
 Comparison of Rates

(ii) Comparison 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,
V1
r1 d2 M2 r V d2 M2
 t   or 1  1  
r2 V2 d1 M1 r2 V2 d1 M1
t
..the formula

When a gas at pressure P and temperature T is separated from vacuum by a small

hole of cross sectional area A0, the rate of effusion of the gas is given by
kPA0 N A
Rate of effusion =
 2 
1/ 2
Can you crack it

Rate of Effusion depends upon (More than one correct)

(A) Size of pin hole (B) pressure
(C) temperature (D) molecular mass
Can you crack it
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.
Can you crack it
At 1200°C, mixture of Cl2 and Cl atoms (both in gaseous state) effuses 1.16 times
as fast as krypton (mm =83.8) effuses under identical conditions. Calculate the avg
molecular mass of Mixture
 Can you crack it

A closed container contains equal number of moles of hydrogen and oxygen gas.
Find the composition (ratio) of oxygen gas in the mixture coming out of a pin hole.
(A) 1:5 (B) 1:16 (C) 1:32 (D) 1:4
 KINETIC THEORY OF GASES

The theoretical model for all the experimental gas laws can be analyzed 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 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)
 KINETIC THEORY OF GASES

(d) Due to the continuous motion, collision between gaseous molecules with the wall
of container 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 occurring are considered to be perfectly elastic which implies that
there is no loss of energy.

(g) The average kinetic energy of gas will depends on absolute temperature only.
Important Derivation
Important Formula from KINETIC THEORY OF GASES

1 3 3
Translational kinetic energy of n moles Mu  PV 
2
nRT
2 2 2
Average translational kinetic energy per molecule = 3 RT 3
 KT
2 N0 2
R
Where k =
NA , k is called Boltzmann's constant.
(1) Its numerical value is 1.38 x 10–16 erg K–1 molecule–1
(2) Average K.E. is proportional to absolute temperature.
(3) If T = 0 K (i.e. – 273.15°C)P then average KE = 0
(4) At Absolute zero (0 K) is the temperature at which molecular motion ceases.
Different types of molecular velocities
(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 n2
Urms (root mean square velocity) = U rms 
N
Different types of molecular velocities
(ii) Average speed (Uav) : It is given by the arithmetic mean of the different speeds
possessed by the molecules of the gases at a particular temperature.

uav = U1  U 2  ....U n
n

uav (average speed) = 8RT

M
 Different types of molecular velocities

(iii) Most probable speed (ump) : It is defined as the velocity possessed by the
maximum number of molecules of a gas at a given temperature.

ump (most probable velocity) = 2RT

M
 MAXWELL'S DISTRIBUTION OF SPEEDS

Distribution of speeds remains constant at given temperature although individual

speeds of molecules may change.
Different types of molecular velocities
..ratta maar

Relation between rms velocity, average velocity and most probable velocity.

urms : uav : ump = 3RT 8 RT 2 RT 8 = 1.2248 : 1.1284 : 1

: :  3: : 2
M M M 
 Crack the PYQ
1. The relationship among most probable velocity, average velocity and root mean
square velocity is respectively: -
[AIEEE ONLINE-2012]
8 8
(1) 2: : 3 (2) 2: 3:
 
8 8
(3) 3: : 2 (4) : 3: 2
 
 Crack the PYQ
2. For gaseous state, if most probable speed is denoted by C*, average speed ഥC and
mean square speed by C, then for a large number of molecules the ratio of these
speeds are:
[JEE MAINS-2013]
(1) C* : Cത : C = 1.225 : 1.128 :1
(2) C* : Cത : C = 1.128 : 1.225 :1
(3) C* : Cത : C = 1 : 1.128 : 1.225
(4) C* : Cത : C = 1 : 1.225 : 1.128
 Crack the PYQ
3. Which of the following is not an assumption of the kinetic theory of gases ?
[JEE MAINS 2015]
(1) Gas particles have negligible volume.
(2) A gas consists of many identical particles which are in continual motion.
(3) At high pressure, gas particles are difficult to compress.
(4) Collisions of gas particles are perfectly elastic.
 MAXWELL'S DISTRIBUTION OF SPEEDS

The important features of Maxwell's distribution curve

(i) The fraction of molecules with very low or very high speeds is very small,
(ii) The fraction of molecules possessing higher and higher speeds goes on increasing
till it reaches the peak and thereafter it starts decreasing.
 MAXWELL'S DISTRIBUTION OF SPEEDS

(iii) The area under the curve gives the total number of gas molecules.
(iv) The maximum fraction of molecules possesses a speed corresponding to the peak
in the curve. This speed corresponding to the peak in the curve is referred to as
most probable speed.
MAXWELL'S DISTRIBUTION OF SPEEDS
MAXWELL'S DISTRIBUTION OF SPEEDS
The most probable speed may be defined as the speed possessed by the
maximum fraction of molecules at a given temperature.
As most probable speed is inversely proportional to molar mass 
c*  2 RT / M 

Maxwell Boltzmann distribution curves for gases at 300 K.

 Crack the PYQ
4. Points I, II and III in the following plot respectively correspond to
(Vmp : most probable velocity) [JEE MAINS - ONLINE - 2019]

(1) Vmp of N2 (300K); Vmp of H2 (300K); Vmp of O2 (400K)

(2) Vmp of H2 (300K); Vmp of N2 (300K); Vmp of O2 (400K)
(3) Vmp of O2 (400K); Vmp of N2 (300K); Vmp of H2 (300K)
(4) Vmp of N2 (300K); Vmp of O2 (400K); Vmp of H2 (300K)
Faulty Assumptions in Kinetic Theory of Gases

Causes of Deviations from Ideal Behavior

(i) The volume occupied by the gas molecules is negligibly small in comparison
to the total volume of the gas.
(ii) The forces of attraction between the gas molecules are negligible.

Corrections of Deviations — van der Waals equation for Real Gases

BEHAVIOUR OF REAL GASES : DEVIATIONS IDEAL GAS BEHAVIOUR

A gas which obeys the general gas equation ( PV= nRT) and other gas laws at all
temperatures and pressures is called an ideal gas or perfect gas.

Deviations of Real Gases

The gas which does not obey general gas equation and other gas laws at all
temperatures and pressures is called non-ideal or real gas.
Crack the PYQ
1. By how many folds the temperature of a gas would increase when the root mean
square velocity of the gas molecules in a container of fixed volume is increased
from 5 x 104 cm/s to 10 x 104 cm/s ?
[JEE MAINS 2013]
(1) Four (2) Three
(3) Two (4) Six
BEHAVIOUR OF REAL GASES : DEVIATIONS IDEAL GAS BEHAVIOUR

A gas which obeys the general gas equation ( PV= nRT) and other gas laws at all
temperatures and pressures is called an ideal gas or perfect gas.

Deviations of Real Gases

The gas which does not obey general gas equation and other gas laws at all
temperatures and pressures is called non-ideal or real gas.
KINETIC MOLECULAR THEORY OF GASES ?

Causes of Deviations from Ideal Behavior

Faulty Assumptions in Kinetic Theory of Gases
(i) The volume occupied by the gas molecules is negligibly small in comparison
to the total volume of the gas.
(ii) The forces of attraction between the gas molecules are negligible.

Corrections of Deviations — van der Waals equation for Real Gases

Compressibility of a gas (Z)

Compressibility factor : The extent to which a real gas departs from the ideal
behavior 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
 Compressibility of a gas (Z)
Plots of compressibility factor vs pressure
(i) For an ideal gas Z = 1 and is independent of temperature and pressure.
(ii) Exceptional behavior of H2 and He :
for these gases Z > 1. For such gases repulsive forces are predominant.
 ..the real game
Lets Understand the Quantity “PV” of a gas at a given n and temperature
..the real game
 Compressibility of a gas (Z)

(iii) For the gases which are easily liquefied (e,g, CO2) Z dips sharply below the ideal
line in the low pressure region.
 Compressibility of a gas (Z)

(iv) Effect of temperature : An increase in temperature shows a decrease in deviation

from ideal behaviors i.e. PV approaches unity or Z approaches unity with increase
in temperature.
 ..the reality of gases

(a) Gases like H2 and He follow the gas

equation at extremely low pressures, but
pV increases regularly as the pressure
increases. Such gases are said to show
positive deviation.
 ..the reality of gases

(b) For gases like CO and CH4, pV shows a

negative deviation in the beginning,
reaches a minimum value (which is
different for different gases) and there
after it starts increasing with increase in
pressure. It crosses the line for ideal gas
and then shows a positive deviation
continuously.
 ..the reality of gases
Real gases show ideal behavior when pressure approaches zero but deviations
from ideal behavior is observed at high pressures.
 VAN DER WAAL'S EQUATION OF STATE

(a) Volume correction.

The volume of the molecules is not negligible as compared to the total volume of the gas.
The molecules are not free to move about in the entire volume (V) which we observe.
The free volume available to the gas molecules is smaller than the observed volume.
The ideal volume (Vi) is smaller than the observed volume (V).
VAN DER WAAL'S EQUATION OF STATE
 VAN DER WAAL'S EQUATION OF STATE

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.
The free volume Vi is the total volume V minus the volume occupied by the gas
molecules,

Real vol. of gas = Actual vol. of container – vol. occupied by N molecules in motion.
 VAN DER WAAL'S EQUATION OF STATE

Volume Correction
Vi = V – b for one mole of gas
Vi = V – nb for n mole of gas
Where b is termed the ‘excluded volume’ or ‘co-volume’.
It is constant and characteristic for each gas.
VAN DER WAAL'S EQUATION OF STATE
Pressure Correction: The effect of inter molecular forces of attraction

Consider a molecule A is the midst of the vessel.

This molecule is surrounded by other molecules in a symmetrical manner and is
being attracted uniformly on all sides by the neighboring molecules with the result
that this molecule on the whole experiences no net force of attraction.
VAN DER WAAL'S EQUATION OF STATE
Ideal Vs Real Gases
VAN DER WAAL'S EQUATION OF STATE

The pressure that we observe (P) is relatively smaller than the pressure if there
were no attractive forces. In other words, the observed pressure (P) is smaller
than the ideal pressure (Pi).

Significance of 'a'. The value of constant 'a' gives the idea of the magnitude of
attractive forces between the molecules of the gas. Its units are atm L2 mol–2 or
bar L2 mol –2.
 VAN DER WAAL'S EQUATION OF STATE

The total force of attraction on any molecule about to hit a wall is proportional to
the concentration of neighboring molecules, n/V

The number of molecules about to hit the wall per unit wall area is also
proportional to the concentration n/V

Thus, 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,

P (actual) = P(ideal) – n2a/V2

P (ideal) = P(actual) + n2a/V2

VAN DER WAAL'S EQUATION OF STATE

'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 

 n2a 
For n mole of gas  P  2  (V – nb) = nRT
 V 
VAN DER WAAL'S EQUATION OF STATE
 Characteristics of '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.
 Characteristics of 'a' and 'b'

(vi) At low pressure, volume correction for 1 mole of gas is negligible,

\b=0
The gas equation can be written as

where Vm = molar volume, Z is known as the compressibility factor.

 Characteristics of 'a' and 'b'

(vii) At higher pressures, the pressure correction for 1 mole of gas is negligible
a
\ 2
=0
V
or (P + 0) (V – b) = RT
or P (Vm – b) = RT
or PVm = RT + Pb
PVm Pb
or Z= =1+
RT RT
The vander walls constants for some common Gases
Crack the PYQ
2. When does a gas deviate the most from its ideal behaviour ?
[JEE MAINS 2015]
(1) At high pressure and low temperature
(2) At high pressure and high temperature
(3) At low pressure and low temperature
(4) At low pressure and high temperature
 Crack the PYQ

3. At very high pressure, the compressibility factor of one mole of a gas is given by :
[JEE MAINS 2016]
pb b
(1) 1 (2) 1
RT VRT 
pb pb
(3) 1 (4)
RT RT
 Crack the PYQ
4. Vander Waal's equation for a gas is stated as,

[JEE MAINS 2014]

nRT
This equation reduces to the perfect gas equation, p = when,
V
(1) both temperature and pressure are very low
(2) both temperature and pressure are very high
(3) temperature is sufficiently high and pressure is low
(4) temperature is sufficiently low and pressure is high.
 Crack the PYQ

5. If Z is a compressibility factor, van der Waals equation at low pressure can be

written as: [JEE MAIN 2014]
RT a
(1) Z  1 (2) Z  1
Pb VRT
Pb Pb
(3) Z  1 (4) Z  1
RT RT
 Crack the PYQ

6. At a given temperature T, gases Ne, Ar, Xe and Kr are found to deviate

RT
from ideal gas behavior. Their equation of state is given as p = at T.
V b
[JEE MAINS 2019]

Here, b is the van der Waals constant. Which gas will exhibit steepest increase in
the plot of Z (compression factor) vs p?
(1) Ne (2) At
(3) Xe (4) Kr
Crack the PYQ

Consider the following table : [JEE MAINS 2019]

Gas a (k Pa dm6 mol–1) b (dm3 mol–1)
A 64232 0.05196
B 155.21 0.04136
C 431.91 0.05196
D 155.21 0.4382
a and b are vander waals constant. The correct statement about the gases is :

(1) Gas C will occupy lesser volume than gas A; gas B will be lesser compressible than gas D
(2) Gas C will occupy more volume than gas A; gas B will be lesser compressible than gas D
(3)Gas C will occupy more volume than gas A; gas B will be more compressible than gas D
(4) Gas C will occupy lesser volume than gas A; gas B will be more compressible than gas D
Why gas behaves Ideal a low Pressure
 LIQUEFACTION OF GASES
The phenomenon of converting a gas into liquid is known as liquefaction. The
liquefaction of a gas takes place when the inter molecular 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.
Andrew’s 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.

Isotherms for carbon dioxide showing critical region

 Observations from Andrew’s Isotherms
(a) At Low temperatures : For the curve ABCF as the pressure increases, volume of the
curve decreases (curve A to B).
At point B, at constant pressure, liquefaction commences and the volume decreases
rapidly (because gas is converted to liquid with higher density).
 Observations from Andrew’s Isotherms

(a) 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.
AB, represent gaseous state, BC represent liquid and
vapor in equilibrium. CF represent liquid state.
The pressure corresponding to the line BC is there vapor
pressure of the liquid.
Observations from Andrew’s Isotherms

(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 48°C), the isotherms are

like those of ideal gas.

(d) At temperature (31.1°C) : The horizontal portion is

reduced to a point. The isotherm at TC is called critical
isotherm.
Critical Constants
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 temperature TC.
8a
TC =
27 Rb
Critical Constants
Critical pressure (PC) : The minimum pressure required to liquefy the gas at the
temperature TC is called the critical pressure PC.
a
PC =
27b 2
Critical Constants
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
ANDREWS EXPERIMENT & CRITICAL PHENOMENA

The plots of p vs V at different temperatures

(Isotherms of carbon dioxides)
Critical Constants
The point X is called critical point.
The temperature corresponding to
point X is called critical temperature.

The kinetic energy of gas molecules

above this temperature is sufficient
enough to overcome the attractive
forces.
Critical Constants

Critical temperature of the gas may be

defined as the temperature above which it
cannot be liquefied by application of pressure.
Critical temperature is denoted by Tc.
For example, Tc of CO2 = 304.1 K.

Critical Pressure (pc). The pressure required

to liquefy the gas at critical temperature is
called critical pressure.
For example, the value of pc for CO2 = 73.9
bar.
Critical Constants

Critical Volume (Vc). The volume of one mole

of the gas at critical temperature and critical
pressure is called critical volume.
For eg, value of Vc for CO2 = 94.0 cm3 mol–1.

It may be noted that the parameters Tc, Pc and

Vc for a gas are collectively called critical
constants.
Crack the PYQ
 Can you Crack it
2. It is easier to liquefy ammonia than oxygen because
(a) it is easier to compress oxygen than NH3
(b) NH3 has a very low critical temperature as compared to O2
(c) O2 has a higher value of van der Waals constant a and higher critical
temperature than NH3
(d) NH3 has a higher value of van der Waals constant a and higher critical
temperature than oxygen.
Virial Equation of State For 1 Mole of Gas

PV 1 1 1
Z=  1+B +C 2 +D 3 + ….(B, C, D... are temp. dependent constant)
RT V V V
Virial Equation (Derivation)
Virial Equation (Derivation)
Virial Equation (Derivation)
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.

So to use ideal gas equation for real gas, we will use some correction factor for
volume as well as for pressure.
a
TB =
Rb
Critical Constants of Gases
Gas PC (atm) Vm,C (CM3 mol–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
H2 O 218.0 55.6 647.3
NH3 111.5 72.5 405.0
CH4 45.6 98.7 190.6
SURFACE TENSION

The behaving of the surface of any liquid like a stretched membrane is called surface tension.
 SURFACE TENSION

Watch out the behavior at Macro level

Surface Molecule vs Bulk Molecule
There is a tendency of being pulled inwards for a surface molecule.
A Surface molecule adheres to its neighbors with a stronger force of attraction known as
Surface Tension
SURFACE TENSION

For a plane surface, the force acting parallel to the surface and perpendicular to a
line per unit length anywhere in the surface is called surface tension.
SURFACE TENSION

For a plane surface, the force acting parallel to the surface and perpendicular
to a line per unit length anywhere in the surface is called surface tension.
VISCOSITY
 VISCOSITY

Every liquid has some internal resistance to flow which is referred to as viscosity.
The internal resistance to the flow arises due to internal friction between the
layers of the fluid as they move past one another during the flow.
 VISCOSITY

Every liquid has some internal resistance to flow which is referred to as viscosity.
The internal resistance to the flow arises due to internal friction between the
layers of the fluid as they move past one another during the flow.
VISCOSITY Formula
 LIQUEFACTION OF GASES
The phenomenon of converting a gas into liquid is known as liquefaction. The
liquefaction of a gas takes place when the inter molecular 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.
Andrew’s 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.

Isotherms for carbon dioxide showing critical region

 Observations from Andrew’s Isotherms
(a) At Low temperatures : For the curve ABCF as the pressure increases, volume of the
curve decreases (curve A to B).
At point B, at constant pressure, liquefaction commences and the volume decreases
rapidly (because gas is converted to liquid with higher density).
 Observations from Andrew’s Isotherms

(a) 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.
AB, represent gaseous state, BC represent liquid and
vapor in equilibrium. CF represent liquid state.
The pressure corresponding to the line BC is there vapor
pressure of the liquid.
Observations from Andrew’s Isotherms

(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 48°C), the isotherms are

like those of ideal gas.

(d) At temperature (31.1°C) : The horizontal portion is

reduced to a point. The isotherm at TC is called critical
isotherm.
Critical Constants
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 temperature TC.
8a
TC =
27 Rb
Critical Constants
Critical pressure (PC) : The minimum pressure required to liquefy the gas at the
temperature TC is called the critical pressure PC.
a
PC =
27b 2
Critical Constants
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
ANDREWS EXPERIMENT & CRITICAL PHENOMENA

The plots of p vs V at different temperatures

(Isotherms of carbon dioxides)
Critical Constants
The point X is called critical point.
The temperature corresponding to
point X is called critical temperature.

The kinetic energy of gas molecules

above this temperature is sufficient
enough to overcome the attractive
forces.
Critical Constants

Critical temperature of the gas may be

defined as the temperature above which it
cannot be liquefied by application of pressure.
Critical temperature is denoted by Tc.
For example, Tc of CO2 = 304.1 K.

Critical Pressure (pc). The pressure required

to liquefy the gas at critical temperature is
called critical pressure.
For example, the value of pc for CO2 = 73.9
bar.
Critical Constants

Critical Volume (Vc). The volume of one mole

of the gas at critical temperature and critical
pressure is called critical volume.
For eg, value of Vc for CO2 = 94.0 cm3 mol–1.

It may be noted that the parameters Tc, Pc and

Vc for a gas are collectively called critical
constants.
Crack the PYQ
 Can you Crack it
2. It is easier to liquefy ammonia than oxygen because
(a) it is easier to compress oxygen than NH3
(b) NH3 has a very low critical temperature as compared to O2
(c) O2 has a higher value of van der Waals constant a and higher critical
temperature than NH3
(d) NH3 has a higher value of van der Waals constant a and higher critical
temperature than oxygen.
Virial Equation of State For 1 Mole of Gas

PV 1 1 1
Z=  1+B +C 2 +D 3 + ….(B, C, D... are temp. dependent constant)
RT V V V
Virial Equation (Derivation)
Virial Equation (Derivation)
Virial Equation (Derivation)
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.

So to use ideal gas equation for real gas, we will use some correction factor for
volume as well as for pressure.
a
TB =
Rb
Critical Constants of Gases
Gas PC (atm) Vm,C (CM3 mol–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
H2 O 218.0 55.6 647.3
NH3 111.5 72.5 405.0
CH4 45.6 98.7 190.6
SURFACE TENSION

The behaving of the surface of any liquid like a stretched membrane is called surface tension.
 SURFACE TENSION

Watch out the behavior at Macro level

Surface Molecule vs Bulk Molecule
There is a tendency of being pulled inwards for a surface molecule.
A Surface molecule adheres to its neighbors with a stronger force of attraction known as
Surface Tension
SURFACE TENSION

For a plane surface, the force acting parallel to the surface and perpendicular to a
line per unit length anywhere in the surface is called surface tension.
SURFACE TENSION

For a plane surface, the force acting parallel to the surface and perpendicular
to a line per unit length anywhere in the surface is called surface tension.
VISCOSITY
 VISCOSITY

Every liquid has some internal resistance to flow which is referred to as viscosity.
The internal resistance to the flow arises due to internal friction between the
layers of the fluid as they move past one another during the flow.
 VISCOSITY

Every liquid has some internal resistance to flow which is referred to as viscosity.
The internal resistance to the flow arises due to internal friction between the
layers of the fluid as they move past one another during the flow.
VISCOSITY Formula