CHEMISTRY LECTURE NOTES

COURSE - VIKAAS (JA)

(LECTURE No. 1 TO 14)

TOPIC : GASEOUS STATE

 Lecture # 1 & 2
Introduction :
Matter as we know broadly exists in three states.
There are always two opposite tendencies between particles of matter which determine the state of matter
 nter molecular attractive forces.
 The molecular motion / random motion.

In this chapter the properties and behaviours of the gases will be analysed and discussed in detail. These
properties are measured with the help of the gas laws as proposed Boyle,Charles,Gay lussac etc

Boyle’s law and measurement of pressure :

Statement :
For a fixed amount of gas at constant temperature, the volume occupied by the gas is inversely proportional
to the pressure applied on the gas or pressure of the gas.
1
V 
P
hence PV = const
this constant will be dependent on the amount of the gas and temperature of the gas.
P1V1 = P2V2

P
P2 B
P1 A

V2 V1 v

Applications of Boyles Law. For the two parts ‘A’ and ‘B’ P1V1 = K & P2V2 = K
hence it follows that P1V1 = P2V2 .

RESONANCE page # 2
 Units

Volume Pressure : Temperture

Volume of the gas is the Pressure = N/m2 = Pa  S.I. unit Kelvin scale  Boiling point = 373 K
Volume of the container C.G.S unit = dyne-cm2 ice point = 273 K

S.I. unit  m3 Convert 1N/m2 into dyne/cm2 Farenheit scale  B.P. = 212º F
ice point = 32º F
1N 10 5 dyne
3 
C.G.S. unit cm Celcius scale  B.P. = 100ºC
1 m2 10 4 cm 2
1  = 10–3 m3 1N/m2 = 10 dyne/cm2 ice point = 0ºC
1  = 103 cm9
C0 K  273 F  32
1dm3 = 1  = 10–3 m3 1 atm = 1.013 × 105 N/m2  
100  0 373  273 212  32
R  R(0)
1ml = 10–3  = 1 cm3 =
R(100)  R(0)
where R = Temp. on unknown scale.

Atmospheric pressure :
The pressure exerted by atomosphere on earth’s surface at sea level is called 1 atm.
1 atm = 1.013 bar
1 atm = 1.013 × 105 N/m2 = 1.013 bar = 760 torr

Solved Examples
Example A rubber balloon contains some solid marbles each of volume 10 ml. A gas is filled in the balloon at
a pressure of 2 atm and the total volume of the balloon is 1 litre in this condition. If the external
pressure is increased to 4atm the volume of Balloon becomes 625 ml. Find the number of marbles
present in the balloon.
Sol. Let the no. of marbles be = n .
volume of marble = 10 n ml.
volume of balloon earlier = 1000 ml.
later = 625 ml.
Now for the gas inside the balloon temperature and amount of the gas is constant, hence boyles law
can be applied
P1V1 = P2V2
4× (625 – 10n) = 2 × (1000 – 10n)
625 × 4 = 2000 – 20n + 40n
625 × 4 – 2000 = 20n
625  4 – 2000 125
= n. =n n = 25
20 5

MEASUREMENT OF PRESSURE
Barometer :
A barometer is an instrument that is used for the measurement of pressure.The construction of the barometer
is as follows

Perfect Vaccum
Mg
Hg is filled upto brim
P0 P0= Patm
Thin
nairow
glass P0
tube P0

Cross sectional view of the capillary column

RESONANCE page # 3
 A mercury barometer is used to measure atmospheric pressure by determining the height of a mercury
column supported in a selaled glass tube. The downward pressure of the mercury in the column is exactly
balanced by the outside atmospheric pressure that presses down on the mercury in the dish and pushes it
up the column.

A thin narrow callibrated capillary tube is filled to the brim, with a liquid such as mercury, and is inverted into
a trough filled with the same fluid.Now depending on the external atmospheric pressure, the level of the
mercury inside the tube will adjust itself, the reading of which can be monitored. When the mercury column
inside the capillary comes to rest, then the net forces on the column should be balanced.
Applying force balance, we get,
Patm × A= m×g (‘A’ is the cross-sectional area of the capillary tube)
If ‘’ is the density of the fluid, then m = × v
hence, Patm × A = ( × g × h) × A (v = A × h)
(‘h’ is the height to which mercury has risen in the capillary)
or, Patm = gh

 Normal atmospheric pressure which we call 1 atmosphere or 1 atm, is defined as the pressure
exerted by the atmosphere at mean sea level. It comes out to be 760 mm of Hg = 76 cm of Hg. (at mean sea
level the reading shown by the barometer is 76 cm of Hg)
1 atm = (13.6 × 103) 9.8 × 0.76 = 1.013 × 105 Pas.
1 torr = 1 mm of Hg.
1 barr = 105 N/m2 (Pa)
Faulty Barometer : An ideal barometer will show a correct reading only if the space above the mercury
column is vacuum, but in case if some gas column is trapped in the space above the mercury column, then
the barometer is classified as a faulty barometer. The reading of such a barometer will be less than the true
pressure.
For such a faulty barometer
Pgas × A

Patm × A
mg
P0A = Mg + Pgas A
P0 = gh + Pgas or gh = P0 – Pgas

Solved Examples
Example The reading of a faulty barometer is 700 mm of Hg. When actual pressure is 750 mm of Hg. The
length of the air column trapped in this case is 10 cm .Find the actual value of the atmospheric
pressure when reading of this barometer is 750 mm of Hg. Assume that the length of the Barometer
tube above mercury surface in the container remains constant.

RESONANCE page # 4
Sol. P0 = Pgas + 700 g
 Pgas = 750 g – 700 g = 50 g

Now for the gas column in the capillary, amount and temp are constant hence P1V2 = P2 V2
(50 g) (100 A) = Pgas
 × (50 A)

 Pgas
 = 100 g
Now, applying force balance in the new scenario.

 = Pgas
Patm  + 750 g = 100 g + 750 g = 850 g
Hence, the atmospheric pressure is now, 850 cm of Hg.
Example In each of the following examples, find the pressure of the trapped gas.

P0 = 75 cm of Hg

Hg 10 cm

gas column

Sol. Total pressure of gas column

= 75 + 10 = 85 cm of Hg.

Example

Sol. Pgas = 65 cm of Hg.

Example

Pg = 75 + 10 sin .

RESONANCE page # 5
Sol. From the above problem, it can be generalised that, applying force balance every single time is not
necessary. If we are moving up in a fluid, then substract the vertical length, and while moving down
add the vertical length.

Example The diameter of a bubble at the surface of a lake is 4 mm and at the bottom of the lake is 1 mm. If
atmospheric pressure is 1 atm and the temperature of the lake water and the atmosphere are equal.
what is the depth of the lake ?
(The density of the lake water and mercury are 1 g/ml and 13.6 g/ml respectively. Also neglect the
contribution of the pressure due to surface tension)
Sol. P1V1 = P2V2
4 4
 (760 mm × 13.6 × g)  (4 mm/2)3 = (760 mm × 13.6 × g + h × 1 × g)  (1 mm/2)3
3 3
760 × 13.6 × 64 = (760 × 13.6 + h)
h = 64 × 760 × 13.6 – 760 × 13.6
h = 63 × 760 × 13.6 mm
63  760  13.6
h= km = 0.6511 km = 651.1 m Ans.
1000  1000

Example A gas is initially at 1 atm pressure. To compress it to 1/4 th of initial volume, what will be the
pressure required ?
Sol. P1 = 1 atm V1 = V
V
P2 = ? V2 =
4
P1V1 = P1V2 at const. T & n
P1V1 1 atm  V
P2 = V = V = 4 atm Ans.
2
4

Example A gas column is trapped between closed end of a tube and a mercury column of length (h) when this
tube is placed with its open end upwards the length of gas column is (1) the length of gas column
becomes (2) when open end of tube is held downwards. Find atmospheric pressure in terms of
height of Hg column.
case  case 
P0
2 P2

Hg h Hg h

1

P1 P0

Sol. For gas P1 = (PO + h) P2 = (PO – h)

V1 = r21 V2 = r22
at const T. and moles.
P1V1 = P2V2 ; (PO + h) r21 = (PO – h) r22
PO2 + h1 = PO2 – h2
PO2 – Po1 = h, + h2
h(1   2 )
P0 = (    ) cm of Hg column Ans.
2 1

Example If water is used in place of mercury than what should be minimum length of Barometer tube to
measure normal atmospheric pressure.
Sol. PHg = PH2 O = Patm.

0.76 m × 13.6 × g = h H2O × 1 × g

hH2O = 0.76 × 13.6 = 10.336 m Ans.
RESONANCE page # 6
Example A tube of length 50 cm is initially in open atmosphere at a pressure 75 cm of Hg. This tube is dipped
in a Hg container upto half of its length. Find level of mercury column in side the tube.
Sol. If after dipping the tube, the
length of air column be x cm situation shown in the adjoining figure.
Then by using, Pi Vi = Pf Vf
We have.
75 cm Hg × A = Pf × x × A ....... (1) ( = 50 cm)


& also, Pf = 75 cm Hg + (x – ) ....... (2)
2
(2) & (1)  [75 + (x – 25)] × x = 75 × 50
 x2 + 50 x – 3750 = 0
 x = 41.14 or – 91.14
But, x can't be – ve  x = 41.14
 mercury column inside the tube = (50 – 41.14) cm = 8.86 cm Ans.

Lecture # 3
Charles law :
For a fixed amount of gas at constant pressure volume occupied by the gas is directly proportional to
temperature of the gas on absolute scale of temperature.
V  T or V = kT = k × (t + 273)

V
 constan t where ‘k’ is a proportionality constant and is
T
dependent on amount of gas and pressure.

V1 V2
 Temperature on absolute scale, kelvin scale or ideal gas scale.
T1 T2

V = a + bt Temperature on centigrade scale.

Relation : T = t + 273

 Since volume is proportional to absolute temperature, T the volume of a gas should be

theoretically at absolute zero is zero.
 Infact no substance exists as gas at a temperature near absolute zero, though the straight line
plots can be extra ploated to zero volume. Absolute zero can never be attained practically
though it can be approch only.
 By considering –273.15°C as the lowest approachable limit, Kelvin developed temperature
scale which is known as absolute scale.

RESONANCE page # 7
 Solved Examples
Example If the temp. of a particular amount of gas is increased from 27ºC to 57ºC, find final volume of the gas,
if inital volume = 1 lt and assume pressure is constant.
V1 V2
Sol. 
T1 T2
1 V2
 So V2 = 1.1 lt.
(273  27) (273  57)

Example An open container of volume 3 litre contains air at 1 atmospheric pressure. The container is heated
from initial temperature 27ºC or 300 K to tºC or (T + 273)K the amount of the gas expelled from the
container measured 1.45 litre at 17ºC and 1 atm.Find temperature t.

Sol.  T01 = 300 K

It can be assumed that the gas in the container was first heated to (T + 273), at which a volume ‘V’
escaped from the container
hence applying charles law :

3 3  V
=
300 T  273
Now, this volume ‘V’ which escapes trans the container get cooled

V 1.45
 =
T  273 290
Solve the two equations and get the value of V an a T
determine  v & calculate t that will be the answer.

Example An open container of volume V contains air at temperature 27ºC or 300 K.The container is heated to
such a temperature so that amount of gas coming out is 2/3 of
(a) amount of gas initially present in the container.
(b) amount of gas finally remaining in the container.
Find the temperature to which the container should be heated.
Sol. (a) Here , P & V are constant, n & T are changing. Let, initially the amount of gas present be n & temp

2 1 
is 27ºC or 300K. Finally amount of gas present in container = n – n =   n  & final temp. be T.
3 3 
Then using n1T1 = n2T2 , we have,

n
n × 300 = × T2 = T2 = 900K
3
i.e., final temp = 900K Ans.

2
(b) Let there be x mole of gas remaining in the container, of x comes out
3

2 5x 3n
 (x + x) = n = =n x=
3 3 5
3n
 Using n1 T1 = n2 T2 n × 300 K = × T2
5
 T2 = 500K
final temperature = 500 K Ans.

RESONANCE page # 8
Calculation of pay load :
Pay load is defined as the maximum weight that can be lifted by a gas filled ballon.
Buoyancy

balloon

M
For maximum weight that can be lifted, applying force balance
Fbuoyancy = Mballoon × g + Mpay load × g
 air v.g. = gas v.g + Mg + mg.
mass of balloon = m net force on
volume of balloon = v balloon = 0
density of air = air (at equilibrium / when balloon is incoming
density of gas inside the with constant speed)
balloon = gas

Solved Examples
Example A balloon of diameter 20 metre weights 100 kg. Calculate its pay-load, if it is filled with He at 1.0 atm
and 27ºC. Density of air is 1.2 kg m–3. [R = 0.0082 dm3 atm K–1 mol–1]

Sol. Weight of balloon = 100 kg = 10 × 104 g

3
4 3 4 22  20 
Volume of balloon = r     100 
3 3 7  2 
= 4190 × 106 cm3 = 4190 × 103 litre

PVM  w 
Weight of gas (He) in balloon =  PV  RT 
RT  M 

1 4190  10 3  4
= = 68.13 × 104 g
0.082  300
 Total weight of gas and balloon
= 68.13 × 104 + 10 × 104 = 78.13 × 104 g

1.2  4190  10 6
Weight of air displaced = = 502.8 × 104 g
10 3
 Pay load = wt. of air displaced – (wt. of balloon + wt. of gas)
 Pay load = 502.8 × 104 – 78.13 × 104 = 424.67 × 104 g

Example Find the lifting power of a 100 litre balloon filled with He at 730 mm and 25°C. (Density of air = 1.25
g /L).

Sol. Since, PV = nRT

W PVM 730 100  4
PV = RT  W= = × g
M RT 760 0.082  298
i.e., Wt. of He = 15.72 g
Wt. of air displaced = 100 × 1.25 g/L = 125 g
 Lifting power of the balloon = 125 g – 15.72 g = 109.28 g Ans.

RESONANCE page # 9
Gay-lussac’s law :
For a fixed amount of gas at constant volume, pressure of the gas is directly proportional to temperature of
the gas on absolute scale of temperature.
PT

P
= constant  dependent on amount and volume of gas
T

P1 P2
  temp on absolute scale
T1 T2
originally, the law was developed on the centigrade scale, where it was found that pressure is a linear
function of temperature P = P0 + bt where ‘b’ is a constant and P0 is pressure at zero degree centigrade.

P
P

P0

(–273°C) O t
T

Example PV = K  V = K1/p
V
= K2  V = K2 T
T

K1
= K2T
P

K1 1
PT = = const  P  = ?
K2 T
     where are we wrong ?
This is wrong because we are varying temperature &
K1 = f(1) thus K1 will change according to temperature

K1
So K will be a function of temp & not constant.
2

Solved Examples
Example The temperature of a certain mass of a gas is doubled. If the initially the gas is at 1 atm pressure.
Find the % increase in pressure ?

P1 P2 1 P2
Sol. T1 = T2 ; =
T 2T
1
% increase = x 100 = 100%
1

Example The temperature of a certain mass of a gas was increased from 27°C to 37°C at constant volume.
What will be the pressure of the gas.

P1 P2 P P2 31
Sol. T1 = T2 ; = ; P2 = P
300 310 30

RESONANCE page # 10
 Lecture # 4
Avogadro’s Hypothesis :
For similar values of pressure & temperature equal number of molecules of different gases will occupy equal
volume.
N1  V (volume of N1 molecules at P & T of one gas)
N1  V (volume of N1 molecules at P & T of second gas)
 Molar volume & volume occupied by one mole of each and every gas under similar conditions will be equal.

O ne m ole of any gas of a com bination of gases occupies 22.413996 L of volum e at STP .
The previous standarad is stilloften used,and applies to allchem istry data m ore than decade old,in this definition
Standard T em perature and P ressure ST P denotes the sam e tem perature of 0°C (273.15K ), but a slightly higher
pressure of1 atm (101.325 kP a) .
Standard A m bient T em perature and P ressure (SA T P ), conditions are also used in som e scientific w orks. SA TP
conditions means 298.15 k and 1 bar (i.e. exactly 105 P a) A t SA TP (1 bar and 298.15 K ),the m olar volum e of an
ideal gas is 24.789 L m ol–1 (R ef.N C E R T )

Equation of State :
Combining all the gas relations in a single expression which discribes relationship between pressure, volume
and temperature, of a given mass of gas we get an expression known as equation of state.
PV
= constant (dependent on amount of the gas (n)).
T
P1V1 P2 V2
=
T1 T2
Ideal gas Equation :
PV
= constant [universal constant]
nT

=R (ideal gas constant or universal gas constant)

experimentaly

R = 8.314 J/Kmole  25/3

= 1.987 cal/mole  2
= 0.08 Latm/mole  1/12

Solved Examples
Example Four one litre flasks are separately filled with the gases, O2, F2, CH4 and CO2 under the same
conditions. The ratio of number of molecules in these gases :
(A) 2 : 2 : 4 : 3 (B) 1 : 1 : 1 : 1 (C) 1 : 2 : 3 : 4 (D) 2 : 2 : 3 : 4
Sol. According to avogadro’s hypothesis.
All the flasks contains same no. of molecules
 Ratio of no. of molecules of O2, F2, CH4 & CO2
= 1 : 1 : 1 : 1 Ans (B)
Example Some spherical balloon each of volume 2 litre are to be filled with hydrogen gas at one atm & 27°C
from a cylinder of volume V litres. The pressure of the H2 gas inside the cylinder is 20 atm at 127°C.
Find number of balloons which can be filled using this cylinder. Assume that temp of the cylinder is
27°C.
P1V1 P2 V2
Sol. =
T1 T2

1 x  2 60
= =x
300 2
x = 30 balloons

RESONANCE page # 11
 also cylinder is equivalent to 2 balloons gas will be transferred only till the time pressure in cylinder
is > outer pressure.

When pressure of cylinder = pressure of balloon.

hence only = 30 – 2 = 28 balloons will be filled.

Example A weather balloon filled with hydrogen at 1 atm and 300 K has volume equal to 12000 litres. On
ascending it reaches a place where temperature is 250 K and pressure is 0.5 atm. The volume of the
balloon is :
(A) 24000 litres (B) 20000 litres (C) 10000 litres (D) 12000 litres

P1V1 P2 V2 1 atm  12000 L 0.5 atm  V2

Sol. Using T1 = T2 ; =
300 K 250 K
 V2 = 20,000 L
Hence Ans. (B)

Lecture # 5
Daltons law of partial pressure :
Partial pressure :
In a mixture of non reacting gases partial pressure of any component gas is defined as pressure exerted by
this component gas if whole of volume of mixture had been occupied by this component only.
Partial pressure of first component gas

n1 RT
P1 
v
n2 RT
P2 
v
n3 RT
P3 
v
Total pressure = P1 + P2 + P3.
Daltons law :
For a non reacting gaseous mixture total pressure of the mixture is summation of partial pressure of the
different components gases.
PTotal = P1 + P2 + P3

(n1  n2  n3 ) RT

v

P1 n1
  x1 (mole fraction of first component gas)
PT nT

P2 n2
  x 2 (mole fraction of second component gas)
PT n T

P3 n
 3  x 3 (mole fraction of third component gas)
PT n T

RESONANCE page # 12
 Solved Examples
Example The stop cock connecting the two bulbs of volume 5 litre and 10 litre containing as ideal gas at
9 atm and 6 atm respectively, is opened. What is the final pressure if the temperature remains
same.
Sol. After the opening of the stop cock the pressure of the each bulb will remain same.

10 x 6
At the beginning, the no. of moles of gas in A =
RT

5x9
At the beginning, the no. of moles of gas in B =
RT

105
 total no. of mole at the beginning =
RT
Total no. of mole of gas before opening the stop cock

105
= total no. of moles of gas after opening stop cock =
RT
 pressure after the opening of the stop cock

105 RT 105
P= x V = = 7 atm
RT total 10 5

Example The partial pressure of hydrogen in a flask containing two grams of hydrogen and 32 gm of
sulphur dioxide is :
(A) 1/16th of the total pressure (B) 1/9th of the total pressure
(C) 2/3 of the total pressure (D) 1/8th of the total pressure

2g 32g
Sol. n H2 = = 1mol. nSO 2 = = 0.5 mol
2g / mol 64g / mol

nH 2 1 2
 PH 2 × PT = × PT = P.
nH2  n  SO 2
(1  0.5) 3 T

 (C)
Example Equal volumes of two gases which do not react together are enclosed in separate vessels.
Their pressures are 10 mm and 400 mm respectively. If the two vessels are joined together,
then what will be the pressure of the resulting mixture (temperature remaining constant) :
(A) 120 mm (B) 500 mm (C) 1000 mm (D) 205 mm
Sol. Let, vol of containers be V & temp be T
P1 = 10mm P2 = 400mm
P1V P2 V
 n1 = & n2 =
RT RT

(P1  P2 )  V
 n1 + n2 =
RT
After joining two containers final vol = (V+V) = 2V(for gases)

n1  n2 RT (P1  P2 )  V RT P1  P2 

 Pfinal = Vfinal = × =
RT 2V 2

10  400 mm

= = 205 mm. Ans. (D)
2

RESONANCE page # 13
Example A mixture of NO2 & CO having total volume of 100 ml contains 70 ml of NO2 at 1 atm, mixture is left
for some time and same NO2 get dimerised to N2O4 such that final volume of the mixture become
80 ml at 1 atm calculate mole fraction of NO2 in final equilibrium mixture.
Sol. Initial volume of NO2 = 70 ml
Initial volume of CO = 100 – 70 = 30 ml
Final volume of mixture = 80 ml
Let the volume of NO2 in final mixture be x
Let ‘v’ ml NO2 be converted to N2O4
2NO2  N2O4
V V/2
Hence final volume
= volume of CO + volume of NO2 left + volume of N2O4 formed
= 30 + 70 – V + V/2 = 80
V = 40 ml
Hence volume of NO2 left = 70 – V = 30 ml
Now as volume  moles
30 3
 mole fraction = volume fraction = =
80 8

Lecture # 6
Analysis of gaseous mixture :
Vapour density :
Vapour density of any gas is defined as the density of any gas with respect to density of the H2 gas under
identical conditions of temperature T and pressure P.
density of gas at T & P
vapour density = density of H under same P & T
2

m RT RT PM
P= .  P=  =
V M M RT
PMgasRT Mgas M gas
vapour density = RT PM = M =
H2 H2 2
Mgas = 2 × vapour density
Average molecular mass of gaseous mixture :
total mass of the mixture divided by total no. of moles in the mixture
Total mass of mixture
Mmix = Total no. of moles in mixture
If we have
‘n1’ , ‘n2’ and ‘n3’ are moles of three different gases having of molar mass ‘M1’, ‘M2’ and ‘M3’ respectively.
n1 M1  n 2 M2  n3 M3
Mmin = n1  n 2  n3

Solved Examples
Example Calculate the mean molar mass of a mixture of gases having 7 g of Nitrogen, 22 g of CO2 and 5.6
litres of CO at STP.

Sol. Moles of N2 = 7/28 = 1/4

Moles of CO2 = 22/44 = 1/2

Moles of CO = 5.6 / 22.4 = 1/4

n1 M1  n 2 M2  n3 M3
mean molar mass = Mmin = n1  n 2  n3 = ( 7 + 7 + 22 ) / 1 = 36

RESONANCE page # 14
 Lecture # 7
Kinetic Theory of Gases :
Postulates / assumptions of KTG :
 A gas consists of tiny spherical particles called molecules of the gas which are identical in shape &
size (mass)
 The volume occupied by the molecules is negligible in comparision to total volume of the gas.
For an ideal gas, volume of the ideal gas molecule ~ 0.
 Gaseous molecules are always in random motion and collide with other gaseous molecule & with
walls of the container.
 Pressure of the gas is due to these molecular collisions with walls of the container
 These collisions are elastic in nature
 Molecular attraction forces are negligible. Infact, for an ideal gas attraction or repulsion forces are
equal to zero.
 Newton’s laws of motion are applicable on the motion of the gaseous molecule.
 Effect of gravity is negligible on molecular motion.
 The average K.E. of gaseous molecules is proportional to absolute temp of the gas.
1
M (u 2 )  T (bar is for average)
2
Kinetic equation of gaseous state (expression for pressure of gas)

Derivation
m = mass of one molecule

U = Ux î + Uy ĵ + Uz k̂

Consider collision with ABCD

 
inital Pi = mUx î ; final Pf = – mUx î

change in momentum due to collision = 2 Ux m

2
time taken between two succussive collision with force ABCD = t = U
x
1 Ux
frequency of collision = =
t 2
Ux  Ux m U2x
change in momentum in one sec. = force = 2 m =
2 
force due to all the molecules
m
= {U2x1  U2x 2  ........  Ux N2 }

Ux 12  U2x 2  .......... .U2xN
average value of UN2 = UN2 =
N
M
Fx = 2
 {N Ux }
all the three direction are equal as the motion is totally random in all directions, hence
2
U2x = U y = U2z

2 2 2
U2 = U x  U y  U z

= 3 U2x

M 1
Fx = .N 2
 3 U
RESONANCE page # 15
 Fx 1 N
Pressure = = 2 The volume of the container ‘v’ = 3
 2
3 3 U

1
 PV = mN U2 Kinetic equation of gases
3

where U2 is mean square speed

 U12  U22  U23  ...... UN2 

root mean square speed = Urms = 2 =  
U  N 
 

Verification of Gaseous Laws Using Kinetic Equation :

1
From postulates ; PV = mN U2
3
1
m U2  T =  T Where ’‘ is a proportionality constant
2

2 1  2
PV =  m U2  N ; PV =  NT
3 2  3
 Boyle’s Law : N : constant
T : constant
PV = constant
 Charles law : N : constant
P : constant
vT
 Kinetic energy of gaseous molecule (translation K.E.)
To calculate  we have to use ideal gas equation (experimental equation)
PV = nRT
2 2
kinetic equation PV =  nRT =  (nNA) T
3 3
3 R
on comparing =× N
2 A

3 R
= K where K = N = Boltzmann constant
2 A
1
Average K.E. of molecules = m U2 = T
2
3
Average K.E. = K T (only dependent on temperature not on nature of the gas.)
2
1 2 3 3
Average K.E. for one mole = NA  m U  = K NA T = RT
 2  2 2

Root mean square speed

3kT 3R T
Urms = U2 = = m NA Where m-mass of one molecule
m
 Dependent on nature of gas i.e mass of the gas
3R T
Urms = molar mass must be in k/mole.
M
Average speed
Uav = U1 + U2 + U3 + ............ UN
8RT 8KT
Uav = = K is Boltzmman constant
M m

RESONANCE page # 16
  Most probable speed : The speed possesed by maximum number of molecules at the given temperature
2 RT 2 KT
UMPS = =
M m

Solved Examples
Example In a container of capacity 1 litre there are 1023 molecules each of mass 10–22 gms. If root mean
square speed is 105 cm/sec then calculate pressure of the gas.
1
Sol. PV = MN U2
3
P=?
V = 10–3 m3
m = 10–25 kg
N = 1023
5 3
U2 = 10 cm/sec = 10 m/sec

U2 = 106 m2 /sec2
1
P × 10–3 = × 10–25 × 1023 × 0 × 106
3
1
P= × 10–2 × 106 × 103
3
1
P= × 107 pascals
3

Example (i) Calculate the pressure exerted by 1023 gas molecules, each mass 10–22 g in a container of volume
one litre. The rms velocity is 105 cm/sec.
(ii) What is the total kinetic energy (in cal) of these particles ?
(iii) What must be the temperature ?
Sol. (i) Here N = 1023 molecules m = 10–22g , V = 1L = 1000 cm3
rms velocity = 105 cm/second
1
 PV = Nm U2
3
1
 P= Nm U2
3
1
= × 1023 × 10–22g × (105)2cm2/s2
3  1000cm 3
= 3.33 × 107 dyne/cm2 Ans.
(ii) Total K . E of the molecules
1
= Nm U2
2
1
= × 1023 × 10–25 kg × (103m/s)2
2
10000 J
= = 5000 J  1195.0 Cal Ans.
2

RESONANCE page # 17
 1 3
(iii) Avg K . E of one molecule = 2 = kT
2 U 2
1 mU2
 T= ×
3 k
2
1 10 –25 Kg  10 3 m / s  6.023  10 23
   R 
= × K  k  
3 8.314  NA 
= 2414.8 K Ans.

Example If for two gases of molecular weights MA and MB at temperature TA and TB ; TAMB = TBMA, then which
property has the same magnitude for both the gases.
(A) Density (B) Pressure (C) KE per mol (D) RMS speed
TA TB
Sol. Given that TA MA = TB MA  M = M
A B

3RT
But, r.m.s. =
M

3RTA 3RTB
 r.m.sA = MA & r.m.sB = MB
 r.m.sA = r.m.sB  Ans. (D)

Example It has been considered that during the formation of earth H2 gas was available at the earth. But due
to the excessive heat of the earth this had been escaped. What was the temperature of earth during
its formation?
(The escape velocity is 1.1 x 106 cm/s)
Sol. Escape velocity of H2 should be equal to avg velocity of H2.
 Avg velocity of H2 = 1.1 × 106 cm/s = 1.1 × 104 m/s

8RT
But, avg. velocity =
M

8  8.314  T
 1.1 × 104 = M  2g  2  10 – 3 kg

  2  10 – 3 H2

4 2
1.1 10     2  10 –3
 T= K = 11430.5 K = 11157.5oC Ans.
8  8.314

Lecture # 8
Maxwell’s distributions of molecular speeds :
Postulates/Assumptions of speed distributions
 It is based upon theory of probability.
 It gives the statistical averages of the speed of the whole collection of gas molecules.
 Speed of gaseous molecules of may vary from 0 to . The maxwell distribution of speed can be
plotted against fraction of molecules as follows.

RESONANCE page # 18
  The area under the curve will denote fraction of molecules having speeds between zero and infinity
 Total area under the curve will be constant and will be unity at all temperatures.
 Area under the curve between zero and u1 will give fraction of molecules racing speed between 0 to
u1 . This fraction is more at T1 and is less at T2 .
 The peak corresponds to most probable speed.
 At higher temperature, fraction of molecules having speed less than a particular value decreases.
 For Gases with different molar masses will have following graph at a given temperature.

Lecture # 9
Graham’s Law of Diffusion/Effusion :
Diffusion :
Net spontaneous flow of gaseous molecule from region of high concentration (higher partial pressure) to
region of lower concentration or lower partial pressure

flow will be from both sides, N2 will try to equalise its partial
pressure in both the vessels, and so will O2.

Graham’s Law :
“Under similar condition of pressure (partial pressure) the rate of diffusion of different gases is inversely
proportional to square root of the density of different gases.”
1
 rate of diffusion r  d = density of gas
d

r1 d2 M2 V . D2
r2 = d1
=
M1
=
V . D1
V.D is vapour density

dVout
r = volume flow rate =
dt
dn out
r = mole flow rate =
dt
dx
r = distance travelled by gaseous molecule per unit time =
dt
RESONANCE page # 19
  The general form of the grahams law of diffusion can be stated as follows, when one or all of the
parameters can be varied.
P
rate  A
TM
P – Pressure, A – area of hole, T – Temp. , M – mol. wt.

 If partial pressure of gases are not equal.

Then rate of diffusion is found to be proportional to partial pressure & inversely proportional to square
root of molecular mass.
rP

1
r
M

r1 P1 M2
r2 = P2 M1

Selective diffusion :
If one or more than one components of a mixture are allowed to diffuse and others are not allowed then it is
selective diffusion of those components.

O2 Diffusion will happen till the

although total pressure H2 time partial pressure of H2
Diffusion
may be different both sides.
becomes same on both sides.

Pt membrane

 Platinum allows only H2 gas to pass through

Effusion : (forced diffusion) a gas is made to diffuse through a hole by application of external pressure.

Solved Examples
Example In is a tube of length 5 m having 2 idendical holes at the opposite ends. H2 & O2 are made to effuse
into the tube from opposite ends under identical conditions. Find the point where gases will meet for
the first time.

r1 ax dt m2 dx1 32
Sol. r2 = × = m1 = dx 2 =
dt dx 2

RESONANCE page # 20
 dx1 dis tan ce travelled by H2
dx 2 = 4  dis tan ce travelled by O 2 = 4
x
=4
(5  x )
x = (5 – x) 4
x = 20 – 4x
5x = 20
x = 4 from H2 side

Example 5 ml of H2 gas diffuses out in 1 sec from a hole. Find the volume of O2 that wil diffuse out from the
same hole under identical conditions in 2 sec.
5ml
Sol. Rate of diffusion of H2 = = 5ml/s = rH 2 (say)
15
1 1
 ro 2 = rH 2 × = 5ml/s ×
4 4
 Volume of O2 diffused in 2.0 seconds
5
= × 2 ml = 2.5 ml Ans.
4

Example A vessel contains H2 & O2 in the molar ratio of 8 : 1 respectively. This mixture of gases is allowed to
diffuse through a hole, find composition of the mixture coming out of the hole.

rH2 nH 2 MO 2
Sol. Here, nH2 : n O 2 = 8 : 1 & =
rO 2 nO2 MH2

rH2 8 32 32
 rO 2 = 1 × 2
=
1

no. of moles of H2 co min g out  / t

32
 no. of moles of O 2 comin g out  / t =
1
 Required composition of H2 : O2 coming out = 32 : 1 Ans.

Example The rate of diffusion of a sample of a ozonized oxygen is 0.98 times than that of oxygen. Find the %
(by volume of ozone in the ozonized sample.
Sol. Let, rate of diffusion of ozonized oxygen be rg
& Let, reat of diffusion of oxygen be rO 2

rg
 r = 0.98 (given) ......... (1)
O2

1/ 2
rg  MO 2 
but r =   (mean molar mass of ozonized oxygen = Mg)
 Mg
O2



32
Form (1)  0.98 = Mg

32 32
 (0.98)2 = M  Mg =
g 0.98 2 = 33.32
Let % of O3 be x  % O2 = (100 – x) in ozonized oxygen.
48 x  100 – x   32
 = 33.32
100
132
 3200 + 16x = 33.32  x = = 8.25 %
16
i.e. % of O3 = 8.25 % Ans.

RESONANCE page # 21
Example Assume that you have a sample of hydrogen gas containing H2, HD and D2 that you want to separate
into pure components (H = 1H and D = 2H). What are the relative rates of diffusion of the three
molecules according to Graham’s law ?
Sol. Since D2 is the heaviest of the three molecules, it will diffuse most slowly, and we’ll call its relative
rate 1.00. We can then compare HD and H2 with D2.
Comparing HD with D2, we have

Rate of HD diffusion Mass of D 2 4.0 amu

Rate of D 2 diffusion = Mass of HD = 3.0 amu = 1.15
Comparing H2 with D2 we have

Rate of H2 diffusion Mass of D 2 4.0 amu

= Mass of H = 2.0 amu = 1.41
Rate of D 2 diffusion 2

Thus, the relative rates of diffusion are H2(1.41) > HD (1.15) > D2(1.00).

Lecture # 10 & 11
Eudiometry : The analysis of gaseous mixtures is called eudiometry. The gases are identified by absorbing them
in specified and specific reagents.

Some Common Facts :

 Liquids and solutions can absorb gases.
 If a hydrocarbon is burnt gases liberated will be CO2 & H2O. [H2O is seperated out by cooling the
mixture & CO2 by absorption by aqueous KOH]
 If organic compound contains S or P then these are converted into SO2 & P4O10 by burning the
organic compound.
 If nitrogen is present then it is converted into N2.
[The only exception : if organic compound contains – NO2 group then NO2 is liberated]
 If mixture contains N2 gas & this is exploded with O2 gas, do not assume any oxide formation unless specified.
 Ozone is absorbed in turpentine oil and oxygen in alkaline pyragallol.

Solved Examples
Example Carbon dioxide gas (CO2) measuring 1 litre is passed over heated coke the total volume of the gases
coming out becomes 1.6 litre. Find % conversion of CO2 into carbon monoxide.
Sol. CO2 + C  2CO CO2 CO
1 0 at time t 1–x 2x
Initial volume = 1 litre
final volume = 1.6 litre no of litres = (1 + x) litres
1 + x = 1.6
x = 0.6
x = 0.6
0 .6
× 10 = 60% of CO2 will be converted into CO
1

Example 100 ml of hydrocarbon is mixed with excess of oxygen and exploded on cooling the mixture was
reported to have a contraction of 250 ml the remaining gas when passed through a solution of
aqueous KOH the mixture shows a further contraction of 300 ml. Find molecular formula of the
hydrocarbon.
 Y y
Sol. Cx Hy +  x   O2  x CO2 + H2 O
 4  2
y
100 ml x 100  100.
2

RESONANCE page # 22
Example. 100 ml of an hydrocarbon is burnt in excess of oxygen in conditions so that water formed gets
condensed out the total contraction in volume of reaction mixture was found to be 250 ml when the
reaction mixture is further exposed to aqueous KOH a further contraction of 300 ml is observed find
molecular formula of hydrocarbon.
Sol. Cx Hy + O2  CO2 + H2O
100 ml excess 300 ml
By POAC on ‘C’ atoms
x × 100 = 300
x=3
POAC on ‘H’ atoms
y × 100 = 2 × moles of H2O
POAC on O atoms
2 × v = 2 × 300 + 1 × H2O {v = volume of O2 consumed}
2 × v = 600 + 50 y
600  50 y
v= volume of O2 consumed
2
The total volume contraction is 250 ml.
Hence, 100 + v – 300 = 250
– 200 + v = 250 = 450
2 × 450 – 600 = 50 y
300
=y=6
50
Hydro carbon will be C3 H6

Alternative :
Using balanced chemical equation
xy y
Cx Hy +   O  xCO + HO
 4  2 2
2 2
t=0 100 ml v ml 0 0
xy 100 y
t 0 v – 100   100 x ml
 4  2
volume remained
250 = (volume of reactants) – (volume products – volume of unused reactant)
100 y
= (100 + v) – {100 x + + v – 100 {x + y/4}} ...(1)
2
volume of CO2
100 x = 300  x=3
The above two equations can be solved to get the required answer.

Example. A sample of water gas has a composition by volume of 50% H2, 45% CO and 5% CO2. Calculate the
volume in litre at STP at water gas which on treatment with excess of steam will produce 5 litre H2.
The equation for the reaction is :
CO + H2O  CO2 + H2
Sol. If x L CO in needed then
 x   x 1 x
volume of H2 in water gas =   50%  L =   L  L
 0.45   0.45 2  0 .9

But, from equation : CO + H2O  CO2 + H2

& Gay-Lussac’s law, we get, that the volume of H2
produced = volume of CO taken.
 Volume of H2 due to reaction = x L
 x  1 .9 x
 Total volume of H2 =   x L = 5 L  =5L
 0 .9  0 .9
0. 9  5
 x=
1 .9
x 0 .9  5
 Volume of water gas = L L = 5.263 L Ans.
0.45 1.9  0.45

RESONANCE page # 23
Example. One litre of oxygen gas is passed through a ozonizer & the final volume of the mixture becomes 820
ml. If this mixture is passed through oil of turpentine. Find final volume of gas remaining.
Sol. The reaction that takes place in ozonizer as 3O2  2O3.
2
If Vml of O2 out of 1000 ml is ozonized then vol of O3 obtained = V
3
 Final vol of ozonized oxygen
2
= (1000 – V + V) mL = 820 mL
3
1
 1000 – V = 820
3
V
 = 180  V = 540
3
 O2 remaining = (1000 – 540) mL ( O3 is absorbed in oil of turpentine)
= 460 mL Ans.

Example. A gaseous mixture containing CO, methane CH4 & N2 gas has total volume of 40 ml. This mixture
is exploded with excess of oxygen on cooling this mixture a contraction of 30 ml is observed & when
this mixture is exposed to aqueous KOH a further contraction of 30 ml is observed .find the composition
of the mixture.
Sol. Let vol of CO be x mL
vol of CH4 be y mL
vol of N2 be z mL
On explosion with excess of oxygen the following reactions takes place

1
CO(g) + O (g)  CO2 (g) (By Gaylussac`s law of combing volume)
2 2
x mL x mL
CH4(g) + O2(g)  CO2(g) + 2H2O(g)
y mL y mL 2 ymL
N2 remains unreacted
On cooling H2O (g) liquifies hence volume reduction of 30 mL is observed
 2y = 30  y = 15
But, vol of CO2 obtained = (x + y) mL
This is absorbed in KOH & vol reduction of 30 mL is observed.
 x + y = 30  x = 30 – y = (30 – 15) = 15
and, x + y + z = 40  z = 40 – x – y = 40 – 15 – 15 = 10
 Composition of mixture is
vol of CO = 15 mL Ans.
vol of CH4 = 15 mL Ans.
vol of N2 = 10 mL Ans.

Lecture # 12 & 13
Real Gases :
 Real gases do not obey the ideal gas laws exactly under all conditions of temperature and pressure.
 Real gases deviates from ideal behaviour because
 Real gaseous molecules have a finite volume.
{since on liquefaction real gases occupy a finite volume}
 Inter molecular attraction focus between real gas molecules is not zero.
{Real gases can be converted into liquid where as ideal gases cant be}
 Deviation of real gases from ideal behaviour can be measured by using compresibility factor : (Z)

(PV )real
Z = (PV ) (PV)ideal = nRT
ideal

RESONANCE page # 24
 PV PVm
Z= = VM is volume of one mole or molar volume.
nRT RT
Vm
Z= V
m ideal

Variation of Z with pressure at constant temperature :

NH3 /CO2
N2
He/H2
Z=1 ideal

P
Variation of Z with pressure at different temperature (for a gas ) :

Conclusions :
Z = 1 for ideal gas
Z > 1 at all pressures for He/H2
Z < 1 at low pressure (for alll other gases)
Z > 1 at high pressur (for alll other gases)

Vander Waal Equation of real gases :

The ideal gas equation does not considetr the effect of nattractive forces and molecular volume.
vander Waal corrected the the ideal gas equation by taking the effect of
(a) Molecular volume (b) Molecular attraction
 Volume correction :
Ideal gas equation :
Pi Vi = nRT ; In the equation ‘Vi’ stands for the volume which is available for free movement of the molecules.
Videal = volume available for free movement of gasesous molecule
hence, Vi = V – {volume not available for free movement} For an ideal gas
Vi = V {V = volume of container}
but for a real gas
Vi  V , as all the volume is not available for free movement

Molecules have finite volume :

1  4  ( 2r )3  r r
Excluded volume per molecule =   = Co-volume per molecule. 1 2
2 3 
The volume that is not available for free movement is called excluded volume.
let us see, how this excluded volume is calculated.
Excluded volume
(not available for free momement)
RESONANCE page # 25
 For example 2, the entire shaded region is excluded, as its centre of mass cannot enter this region.
If both molecules were ideal, then they would not have experienced any excluded volume but not in the case,
of real gas as the centre of mass of ‘2’ cannot go further.
Hence for this pair of real gas molecules.

1  4  (2r )3  4 3 
Excluded volume per molecule =   = 4  r 
2  3  3 
4 3 
excluded volume per mole of gas b = NA 4   r 
3 
= 4 x NA x Volume of individual molecule
for n moles excluded volume = nb

Vi = V – nb volume correction

 Pressure correction or effect of molecular attraction forces :

Molecule in middle of container

Due to these attraction speed during collision will be reduced

Momentum will be less
Force applied will be less
Pressure will be less.
Pideal = P + {correction term}
Correction term  no. of molecule attracting the colliding molecule. (n/v)
Correction term  density of molecules (n/v).
n
no. of collision  density of molecules  
v
n n an 2
net correction term      = 2
v v v
‘a’ is constant of proportionality
and this is dependent on force of attraction
Stronger the force of attraction greater will be ‘a’ (Constant)
an 2
Pi = P +
v2
Vander waal’s equation is
2
 P  an
 
 (v – nb) = nRT

 v2 


VERIFICATION OF VANDER WAAL’S EQUATIONS

Variation of Z with P for vander wall equation at any temp.

Vander waal equation for 1mole

 P  a  (V – b) = RT
 
 2
 Vm 

 AT LOW PRESSURE (at separate temp.)

At low pressure Vm will be high.
a
Hence b can be neglected in comparision to Vm. but cant be neglected as pressure is low
Vm2

RESONANCE page # 26
 Thus equation would be

 P  a  V = RT
 
 2 
 Vm  m
a
PVm + = RT
Vm
PVm a
+ =1
RT V mRT
a
Z = 1 – V RT Z<1
m

Real gas is easily compressible in comparision to an ideal gas.

 AT HIGH PRESSURE (moderate temp.)
VM will be low
so b cant be neglected in comparision to Vm
a
but 2 can be neglected in comparision to much high values of P..
Vm
Then vander Wall equation will be
P(Vm – b) = RT
PVm – Pb = RT
PVm Pb
= +1
RT RT
Pb
Z= +1 Z>1
RT
If Z > 1 then gas is more difficult to compress in comparision to an ideal gas.

 At low pressure and very high temperature.

Vm will be very large
a
hence ‘b’ can be neglected and 2 can also be neglected as Vm is very large
Vm
PVm = RT (ideal gas condition)

 For H2 or He a ~ 0 because molecules are smaller in size or vander wall forces will be very weak,
these are non polar so no dipole-dipole interactions are present in the actions.
P(Vm – b) = RT
Pb
so Z=1+
RT
 ‘a’ factor depends on inter molecular attraction forces.

 ‘a’ factor for polar molecule > ‘a’ factor for non polar molecule.

Example Arrange following in decreasing ’a’ factor (H2O, CO2, Ar)

H2O > CO2 > Ar
polar
For non polar molecules :
Greater the size surface area greater will be vander wall forces so greater will be ’a’ constant.
Example Arrange following gases according to ‘a’
He , Ar, Ne, Kr.
aKr > aAr > aNe > aHe
More ‘a’ factor means high boiling point.
 liquification pressure :
Is the pressure required to convert gas into liquid.
for easy liquefaction a and P

When Z < 1, Vm < Vm, ideal  easily liquifiable

Z < 1, Vm < Vm, ideal  more difficult to compress.

RESONANCE page # 27
Example Arrange the following according to liquification pressure.
n-pentane ; iiso pentane , neo pentane.
an-pentene > aiso pentane > aneo pentane
liquification pressure = LP
L Pn  pen tan e < L P iso pen tan e < L Pneo pen tan e
 b is roughly related with size of the molecule. (Thumb rule)

4 3 
b = NA 4   r 
3 

Solved Examples
Example Two vander waals gases have same value of b but different a values. Which of these would occupy
greater volume under identical conditions ?

Sol. If two gases have same value of b but different values of a, then the gas having a larger value of a will
occupy lesser volume. This is because the gas with a larger value of a will have larger force of
attraction and hence lesser distance between its molecules.

Virial Equation of state :

It is a generalised equation of gaseous state all other equation can be written in the form of virial equation of
state.
 1 
Z is expressed in power series expansion of P or  V 
 m
B C D
Z = 1 + V + 2 + 3 + .....................
m Vm Vm

B – second virial coefficient , C – third virial coefficient , D – fourth virial coefficient

Vander wall equation in virial form :

P  a 
 
 2  (Vm – b) = RT
 Vm 

RT a
P = ( V  b) – 2
m Vm
RESONANCE page # 28
 PVm Vm a 1 a
Z= = ( V  b ) – V RT = (1  b / V ) – V RT
RT m m m m

1
= 1 + x + x2 + x3 + ..........
1 x
2 3
1  b  b  b  ......... 
 
a 1  a  b2 b3
Z=   – =1+ V  b   + 2 + 3 + .................
 Vm Vm2 Vm3  Vm RT m  RT  Vm Vm
comparing with virial equation
according to vander walls equation
a
B=b– , C = b2, P = b3
RT
at low pressure : Vm will be larger
1 1
hence , ................ can be neglected
Vm2 Vm3
1  a 
Z = 1 + V b  
m  RT 
 a  a
If b   =0  at T=
 RT  Rb
Z=1 (ideal gas)
a
so at Z = gas will behave an ideal gas (or follows boylesley)
Rb
a
But at constant temperature ideal gas equation is obeying Boy’es law as T = , so the temp is called
Rb
Boyl’es temp.

a
TB =
Rb

a
Z = 1 – V RT
m
for a single gas if we have two graphs as above we must conclude T2 < T1 at Boyle’s temperature ‘a’ factor
is compensated by factor so Z = 1.

Lecture # 14
Critical constant of a gas :
When pressure is incerases at constant temp volume of gas decreases

AB  gases
BC  vapour + liquid
CD  liquid
critical point : At this point all the phydical properties of liquid phase will be equal to phsical properties in
vapour such as
density of liquid = density of vapour

RESONANCE page # 29
 TC or critical temp :
Temperature above which a gas can not be liquidied
PC or critical pressure :
minimum pressure which must be applied at critical temp to convert the gas into liquid.
VC or critical volume :
volume occupied by one mole of gas at TC & PC

Critical constant using vander wall equations :

P  a 
 
 2  (Vm – b) = RT
 Vm 

( PVm2  a ) (Vm – b) = RT Vm2

PVm3 + aVm – PbVm2 – ab – RTVm2 = 0
 RT  a ab
Vm3 + Vm2  b   + V – =0
 P  P m P
cubic can hence there will be three roots of equation at any temperature of pressure.
At critical point all three roots will coincide and will give singles dx = VC
at critical point Vander Waal equation will be
 RTC  a ab
Vm3 – Vm2  b  P  + P Vm – P = 0 ...(1)
 C  C C
But at critical point all three roots of the equation should be equal, hence equation should be :
Vm3 – 3Vm2 VC + 3Vm VC2 – VC3 = 0 ...(2)
comparing with equation (1)
RTC
b + P = 3VC ....(i)
C

a
2
PC = 3 VC ...(ii)

ab
3
PC = VC ...(iii)

a a a
PC = substituting PC = =
3 VC2 3 (3b)2 27b 2
RTC
by (i) PC = 3 VC – b = 9b – b = 8b
8a
TC = 27 Rb
At critical point, the slope of PV curve (slope of isotherm) will be zero
 P 
 
=0 ...(i)
 Vm  TC
at all other point slope will be negative
O is the maximum value of slope.
  P 
 
=0 ....(ii)
Vm  Vm  TC
{Mathematically such points an known as point of inflection (where first two duivation becomes zero)}
using the two TC PC and VC can be calculate

by

By any two a can be calculated but a by VC and TC and a by TC and PC may differ as these values are
practical values and VC can’t be accuratly calculated so whwn we have VC TC & PC given use PC & TC to
deduce ‘a’ as thet are more reliable.
RESONANCE page # 30
Reduced Equation of state :
Reduced Temp : Temperature in any state of gas with respect to critical temp of the gas
T
Tr =
TC
P
Reduced pressure : Pr =
PC
Vm
Reduced volume : Vr =
VC
Vander wall equation

P  a 
 
 2  (Vm – b) = RT
 Vm 
Substitute values :

 Pr PC  a 
 
(V V – b) = R Tr TC

 Vr2 VC2  r C

Substiture the value of PC TC and VC

 Pr a   Pr a  a  (3b V – b) = RTr 8a
   
 27 b 2   27 b 2 V 2 (3b)2  r 27 Rb
   r 

 Pr 1
 (3 V – 1) = 8 R Tr

 
3 V  r
 r  3

 Pr  3 
 
 2  (3Vr – 1) = 8 Tr Reduced equation of state
 Vr 
Equation is independent from a, b and R so will be followed by each and every gas independent of its nature.

Solved Examples
Example The vander waals constant for HCI are a = 371.843 KPa and b = 40.8 cm 3 mol–1 find the critical
constant of this substance.

a 371 .843 10 3 371.843 10 9

Sol. The critical pressure, PC = = 2 6 = = 8.273 x 106
27b 2 27  ( 40.8) 10 27  ( 40.8)2
Pa = 8.273 MPa
8a
The critical pressure, T C =
27Rb
R = 8.314 KPa dm 3 K–1 mol–1
8a 8  371.843
TC = = = 324.79 = 324.8 K
27Rb 8.314  27  40.8  10 3
The critical volume, VC = 3b = 3 x 40.8 = 122.4 cm 3

Example The vander waals constant for gases A, B and C are as follows :
Gas a/dm6 KPa mol–2 b/dm3 mol–1
A 405.3 0.027
B 1215.9 0.030
C 607.95 0.032
Which gas has
(i) Highest critical temperature
(ii) The largest molecular volume
(iii) Most ideal behaviour around STP ?

RESONANCE page # 31
 8a
Sol. TC = Since, R is constant, higher the value of a/b higher will be critical temperature.
27Rb
VC = 3b and VC  Vm (for a particular gas) therefore higher the value of VC higher will be molar
volume of the gas.
If the critical temperature close to 273 K, gas will behave ideally around the STP. Let us
illustrate the result in a tabular form.
Gas a/dm6 KPa mol–2 b/dm3 mol–1 TC VC a/b
A 405.3 0.027 534.97 K 0.081 1.501 x 104
B 1215.9 0.030 1.444.42 K 0.09 4.053 x 104
C 607.95 0.032 677.07 K 0.096 1.89 x 104
(i) B gas has the largest critical temperature.
(ii) C gas has the largest molecular volume.
(iii) A gas has the most ideal behaviour around STP.

Vapour pressure of a liquid (aqueous Tension of water) :

Vapour pressure depends on

(a) Temperature (T   VP )
(b) Nature of the liquid
Vapour pressure is independent of amount of liquid & surface area of liquid.
Vapour pressure of the liquid is independent of pressure of any gas in the container,
Ptotal = Pgas + Pwater vapour

Solved Examples
Example In a container of capacity 1 litre, air and some liquid water is present in equilibrium at total pressure of
200 mm of Hg this container is connected to another one litre evacuated container find total pressure
inside the container when equilibrium is again stablised (aqueous tension or vapour pressure at this
temp. is 96 mm Hg).

Sol. Total pressure = 100 mm of Hg = Pgas + Pvapour water

 Pgas + 96 = 200
Pgas = 107 mm of Hg Initially
when second coataitive connected
P1 = 107 mm of Hg P2 = ?
V1 = 1 V2 = 2 litre
P1 V1 = P2 V2
107 × 1 = P2 × 2
53.5 = P2
After equilibrium is established
Ptotal = 53.5 + 93 = Pgas + Pwater = 146.5 mm of Hg at equilibrium

RESONANCE page # 32