States of Matter

1. Solid State
2. Liquid State
3. Gaseous State
Distinction between solid, Liquid and Gas.
Gas Laws:
The behaviour of gases is independent of nature of gas. All gases are compressible,
expand on heating, intermix with each other and exert pressure. These behaviour of gases
have been investigated by a number of scientists and certain generalizations are made on the
behaviour of gases which are called gas laws. The important gases laws are:

1. Boyle’s law – 1662 A.D.

2. Charles’s Law – 1787 A.D.
3. Avogadro’s Law – 1811 A.D.
4. Dalton’s Law of Partial Pressure – 1807 A.D.
5. Graham’s Law of Diffusion – 1832 A.D.

1. Boyle’s law – 1662 A.D.

Born - 25 January 1627

Died -31 December 1691 (aged 64)

Influenced Isaac Newton

1. Boyle’s law – 1662 A.D.

Robert Boyle, an Irish Chemist, studied the effect of pressure on the volume of given mass of
gas. So, Boyle’s law describes how the volume of given mass of gas changes with pressure at
constant temperature.
“It states that temperature remaining constant the volume of given mass of gas is inversely
proportional to the pressure”

If pressure of gas be P and volume be V then according to Boyle’s law.

𝟏
V ………………………………..(1) (When temperature is kept constant)
𝑷

𝟏
=K ……………………………..(2)
𝑷

Where, K is proportionality constant.

Rearranging equation (2), we get,

PV = K ……………………………………………………(3)
Equation (3) is the mathematical expression of Boyle’s law. Let P1 and V1 be the initial pressure
and volume of given mass of gas where as P2 and V2 be the final pressure and volume of the
given mass of gas.
According to Boyle’s Law

P1V1 = P2V2 ……………………….(4)

Where, P1 = Initial pressure of a given mass of gas.
V1 = Initial volume of a given mass of gas.
P2 = Final pressure of a given mass of gas.
V2 = Final volume of a given mass of gas.

So, by using equation (4) we can calculate the volume of given mass of gas at any other
pressure provided the initial volume and the pressure of the gas is known and the temperature
remains constant.

Experimental verification of Boyle’s Law:

Boyle’s law can be verified experimentally by determining the volume of given mass of gas at
different pressure keeping temperature constant.

The following table shows the pressure- volume data of 32 grams of Oxygen at 25 0C.
 Pressure (atm.) Volume (Liter) Pressure x Volume 1/P
(atm. x Liter)
1.00 24.45 24.45 1
0.50 48.88 24.44 2
0.20 122.25 24.45 5
0.10 244.00 24.40 10

 From above table it is quite clear that the value of product of pressure and volume is almost
constant which demonstrates the validity of Boyle’s Law.

 Boyles’s law can be experimentally varified by drawing following graphs:

 (c)

When volumes of given mass of gas are plotted against pressures ; we get a rectangular
hyperbola. This indicates that, when pressure is increased volume decreased and vice-versa as
shown in graph (a). i.e
𝟏
V 𝑷

𝟏
When volumes of given mass of gas are plotted against 𝑷 at constant temperatures, a straight
line is obtained passing through origin, this varifies the Boyle’s law shown in figure (b).

𝟏
V 𝑷
Similarly, the values of product of pressure and volume are plotted against different pressure
, a horizontal line parallel to x-axis is obtained. This indicates that the product of pressure and
volume remains constant at different pressures. This also varies the Boyle’s law
experimentally.

i.e. PV = K

Numerical problems:

1. Half a liter of air under 360 mm pressure is compressed to 200 ml. Taking the temperature
to remain constant, find the new pressure.
Here,

Initial conditions Final conditions

Volume (V1) = ½ liter = 500 ml Volume (V2) = 200 ml

Pressure (P1) = 360 mmHg Pressure (P2) = ??

From Boyle’s law

𝑷𝟏𝑽𝟏 𝟑𝟔𝟎 𝒙 𝟓𝟎𝟎
P1V1 = P2V2 Or, P2 = Or, P2 = = 900 mm Hg
𝑽𝟐 𝟐𝟎𝟎
2. A gas occupies 12.3 liters at a pressure of 40 cm of Hg . What is the volume in ml when
the pressure is increased to 600 mm?

Here,

Initial conditions Final conditions

Volume (V1) = 12.3 liters = 12300 ml Volume (V2) = ??

Pressure (P1) = 40 cm Hg = 400 mm Hg Pressure (P2) = 600 mm Hg

From Boyle’s law

𝑷𝟏𝑽𝟏 𝟏𝟐𝟑𝟎𝟎 𝒙 𝟒𝟎𝟎

P1V1 = P2V2 Or, V2 = Or, V2 = = 8200 ml
𝑷𝟐 𝟔𝟎𝟎
 𝑽𝟏
= K ……………………………(4)
𝑻𝟏

𝑽𝟐
= K ……………………………(5)
𝑻𝟐

Therefore,
𝑽𝟏 𝑽𝟐
= ……………………………(5)
𝑻𝟏 𝑻𝟐

Equation (5) can be used to calculate the volume of given mass of gas at any higher temperature,
if the initial temperature and volume are given at constant pressure.

Charles’s law can be experimentally verified by determining the volume of given mass of gas
at different temperature keeping pressure constant.
The following table shows the volume temperature data of one mole of gas at one atm. pressure.

Temperature (oC) Volume (Liter)

0 22.4
100 30.6
200 38.8
300 47.0
400 55.2
When the volume of the given mass of gas is plotted against the temperature in celsius and a
straight line is obtained which verifies the Charles’s law.

Graphs of volume of gas against temperature

It should be noted that on extrapolation the curve meets at the temperature axis at -273 oC
where the volume of the gas becomes theoretically equal to zero. Similar straight lines graphs
are obtained when volumes of given mass of gas are plotted against temperatures at different
constant pressures. It indicates that these curves meet at -273 oC where the volumes of the gas
becomes zero.
Alternative statement of Charles’s law:

French Chemist, Jacques Charles studied an effect of temperature on the volume of a given
mass of gas at constant pressure in 1787 A.D.

Charles’s law describe how the volume of the given mass of gas changes with temperature at
constant pressure.

Statement

Pressure remaining constant the volume of given mass of gas increases or decreases by
1/273 rd of it’s volume at 0 oC for every 1oC rise or fall in temperature.

Let Vo be the volume of a given mass of gas at pressure P and 0 o C. If pressure is kept
constant and gas be heated, then.
𝟏
Volume of gas at 1 oC = Vo + Vo
𝟐𝟕𝟑

𝟏
= (1 + )Vo
𝟐𝟕𝟑

𝟐
Similarly, volume of gas at 2 oC = (1 + )Vo
𝟐𝟕𝟑

𝟓
volume of gas at 5 oC = (1 + )Vo
𝟐𝟕𝟑
 𝒕
Similarly, volume of gas at t oC = (1 + )Vo
𝟐𝟕𝟑

Similarly, if gas be cooled then,

−𝟏
Volume of gas at -1 oC = Vo + Vo
𝟐𝟕𝟑

𝟏
= (1 - )Vo
𝟐𝟕𝟑

𝟐
volume of gas at -2 oC = (1 - )Vo
𝟐𝟕𝟑

𝟓
volume of gas at -5 oC = (1 - )Vo
𝟐𝟕𝟑

𝒕
Similarly, volume of gas at -t oC = (1 - )Vo
𝟐𝟕𝟑

𝟐𝟕𝟑 𝟐𝟕𝟑 −𝟐𝟕𝟑

Similarly, volume of gas at -273 oC = (1 - )Vo = ( ) Vo = 0
𝟐𝟕𝟑 𝟐𝟕𝟑

Thus, volume of given mass of gas at -273 oC becomes theoretically zero . Infact what
actually happen is all gases become liquid or solid before -273 oC is reached.
Therefore the lowest hypothetical temperature -273 oC (exactly -273.15 oC) is called absolute
zero.
This is the lowest theoretical temperature possible. At this temperature, molecules have no
kinetic energy, no velocity and occupy no volume theoretically.

A temperature scale with it’s zero at -273 oC and each degree being equal to that on Celsius
scale has been built is know as absolute scale temperature or Kelvin scale of temperature.

To convert temperature into Kelvin scale, add 273 to Celsius scale temperature.

Let t be the temperature in Celsius scale then the corresponding temperature in Kelvin scale
be T.

T = (t oC + 273) K -----------------------(1)

Let Vo, V1 and V2 be the volumes of given mass of gas at 0oC, t1 oC and t2 oC at constant
Pressure, then,
𝟐𝟕𝟑 +𝒕𝟏
V1 = (1 + t1/273) Vo = x Vo ……………………. (2)
𝟐𝟕𝟑

𝟐𝟕𝟑 +𝒕𝟐
V2 = (1 + t2/273) Vo = x Vo ……………………..(3)
𝟐𝟕𝟑

Dividing V1 by V2 we get,
 𝑻𝟏 𝑽𝟏
=
𝑻𝟐 𝑽𝟐

𝟐𝟕𝟑 + 𝒕𝟏 = 𝑻𝟏 𝒂𝒏𝒅 𝟐𝟕𝟑 + 𝒕𝟐 = 𝑻𝟐

Where T1 and T2 are the temperature in Kelvin scale.

Therefore,

V T --------------(4)

Equation 4 is an alternative statement of Charles’s law obtained from absolute scale concept.

Numerical problems:
1. 600 ml of chlorine gas at 27 0C were cooled to -23 oC at the same pressure. Calculate the
contraction in volume.
Here,
Initial conditions Final conditions

Volume (V1) = 600 ml Volume (V2) = ??

Temperature (T1) = (27 + 273) K = 300 K Temperature (T2) = (-23 + 273) K
= 250 K
 From Charles’s law

𝑽
𝑽𝟏 𝑽𝟐
𝑽𝟐 𝑽𝟏
𝑽𝟏 𝒙𝒙𝑻𝑻𝟐 𝟔𝟎𝟎 𝒙𝟐𝟓𝟎
Or, 𝟏==
Or, Or, V2 = 𝟐
== = 500 ml
𝑻𝟏𝑻𝟏 𝑻𝟐𝑻𝟐 𝑻𝟏
𝑻 𝟏
𝟑𝟎𝟎

Therefore contraction in volume = (600 – 500) ml = 100 ml

(2) At what temperature the volume of the gas be double if the pressure at the same time
increased from 700 to 800 mm? The initial temperature be 27 0C.

Combined gas equation:

Actually, Boyle’s law relates volume and pressure at constant temperature whereas
Charles’s law relates temperature and volume at constant pressure. If we combine both
Boyle’s law and Charles’s law we can see how the volume of given mass of gas change
with simultaneous change of pressure and temperature. Therefore, combined gas law may
be derived as.

According to Boyle’s law;

𝟏
V ………………………………..(1) (When temperature is kept constant)
𝑷
According to Charles’s law;

V T………………………………..(2) (When pressure is kept constant)

Combining both Boyles’s law and Charles’s law, we get,

𝑻
V ………………………….(3)
𝑷

𝑻
V = K
𝑷

𝑷𝑽
= K …………………………..(4)
𝑻

Where, K is a constant.

Let P1, V1 and T1 be the initial pressure, volume and temperature and P2, V2 and T2 be the
final pressure, volume and temperature of a given mass of gas respectively then.

𝑷𝟏𝑽𝟏
= K …………………………..(5)
𝑻𝟏
 𝑷𝟐𝑽𝟐
= K …………………………..(6)
𝑻𝟐

Combining equation (5) and (6) we get,

𝑷𝟏𝑽𝟏 𝑷𝟐𝑽𝟐 …………………………..(7)

=
𝑻𝟏 𝑻𝟐

Equation (7) is the mathematical expression of combined gas equation.

From equation (4)

𝑷𝑽
= K …………………………..(8)
𝑻

PV = KT ………………………………………..(9)

Where, K is a constant and it’s value depends upon the mass of gas taken. If 1 gm of the gas
is taken, then K is known as specific gas constant and it’s value differs from one gas to another.

If one mole of the gas is taken then instead of K, the symbol R is used and it’s value is the same
for all gases . This is called universal gas constant. For one mole of gas, the equation becomes,

PV = RT ………………………………………..(10)
 For n moles of gas, equation (10) can be written as,

PV = nRT ………………………………………..(10)

Equation (10) is known as ideal gas equation because it is strictly valid to ideal gas at all
temperature amd pressure. Ideal gas follows equation (10).

Standard temperature and pressure:

Temperature and pressure both affect the volume of a gas. It is therefore important to choose
some standard temperature and pressure to describe the volume of a given mass of gas.

According to international agreement, standard temperature and pressure are 0 0C or 273 K

and 760 mm of Hg respectively. This temperature and pressure are known as standard
temperature and pressure (STP) or normal temperature and pressure (NTP).Thus standard
temperature is 0 oC and standard pressure is 760 mm of Hg.
The universal gas constant ‘R’
From ideal gas equation,
PV = nRT ………………………………………..(1)
𝑷𝑽 𝑷𝒓𝒆𝒔𝒔𝒖𝒓𝒆 𝒙 𝒗𝒐𝒍𝒖𝒎𝒆
or R = =
𝒏𝑻 𝒎𝒐𝒍𝒆𝒔 𝒙 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆

𝑭𝒐𝒓𝒄𝒆 𝑭𝒐𝒓𝒄𝒆
𝒙 𝑽𝒐𝒍𝒖𝒎𝒆 𝑳𝒆𝒏𝒈𝒕𝒉 𝟐
𝒙 𝑳𝒆𝒏𝒈𝒕𝒉𝟑
𝑨𝒓𝒆𝒂
= =
𝒎𝒐𝒍𝒆𝒔 𝒙 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒎𝒐𝒍𝒆𝒔 𝒙 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆

𝑭𝒐𝒓𝒄𝒆 𝒙 𝑳𝒆𝒏𝒈𝒕𝒉
=
𝒎𝒐𝒍𝒆𝒔 𝒙 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆

= Energy k-1 mol -1

Therefore, R has the dimension of energy (work) done per degree kelvin per mol.

Calculation of pressure by Mercury column:

Pressure by Mercury column = ρgh
−𝟑
Where, ρ = Density of mercury = 𝟏𝟑. 𝟓𝟗𝟔 𝒙 𝟏𝟎𝟑 𝒌𝒈𝒎
−
g = Acceleration due to gravity = 𝟗. 𝟖𝟎𝟔 𝒎𝒔 𝟐
h = Height of Mercury column = 0.76 m
Values of R

(i) Values of R in liters x atmosphere.

It is experimentally observed that one mole of any gas occupies 22.4 liters at N.T.P.

𝑷𝑽 𝟏 𝒂𝒕𝒎 𝒙 𝟐𝟐.𝟒 𝒍𝒊𝒕𝒆𝒓𝒔

or R = =
𝒏𝑻 𝟏 𝒎𝒐𝒍𝒆𝒔 𝒙 𝟐𝟕𝟑 𝑲

= 0.0821 liter atm K-1 mol-1

(ii) Values of R in SI unit:

In SI unit, pressure is expressed in Newton per square meter (pascal) and volume in m3.

So, for one mole of gas at N.T.P

− −
𝟑 𝟐
𝑷𝑽 𝟎.𝟕𝟔 𝒎 𝒙 𝟏𝟑.𝟓𝟗𝟔 𝒙 𝟏𝟎𝟑 𝒌𝒈𝒎 𝒙 𝟗.𝟖𝟎𝟔 𝒎𝒔 𝒙 𝟐𝟐.𝟒 𝒍𝒊𝒕𝒆𝒓𝒔
or R = =
𝒏𝑻 𝟏 𝒎𝒐𝒍𝒆𝒔 𝒙 𝟐𝟕𝟑 𝑲

− −
𝟐 𝟑
𝟏𝟎𝟏𝟑𝟐𝟓 𝑵𝒎 𝒙 𝟐𝟐.𝟒 𝒙 𝟏𝟎 𝒎𝟑
=
𝟏 𝒎𝒐𝒍𝒆𝒔 𝒙 𝟐𝟕𝟑 𝑲 1 Liter = 1 dm3 = 1 x 10-3 m3

= 8.314 ( N m) K-1 mol-1 = 8.314 Joule K-1 mol-1

(iii) Values of R in c.g.s.unit:

In c.g.s. unit, pressure is expressed in dynes per square cm and volume in cm3.

So, for one mole of gas at N.T.P

− −
𝟑 𝟐
𝑷𝑽 𝟕𝟔 𝒄𝒎 𝒙 𝟏𝟑.𝟓𝟗𝟔 𝒈𝒎 𝒄𝒎 𝒙 𝟗𝟖𝟎.𝟔 𝒄𝒎𝒔 𝒙 𝟐𝟐.𝟒 𝒙 𝟏𝟎𝟑 𝒄𝒎𝟑
or R = =
𝒏𝑻 𝟏 𝒎𝒐𝒍𝒆𝒔 𝒙 𝟐𝟕𝟑 𝑲

−
𝟐
𝟏𝟎𝟏𝟑𝟐𝟓𝟎 𝒅𝒚𝒏𝒆𝒔 𝒄𝒎 𝒙 𝟐𝟐𝟒𝟎𝟎 𝒄𝒎𝟑
=
𝟏 𝒎𝒐𝒍𝒆𝒔 𝒙 𝟐𝟕𝟑 𝑲

= 8.314 x 107 ( dyne x cm) K-1 mol-1 = 8.314 x 107 ergs K-1 mol-1

(iv) Values of R in calories:

From mathematical equivalent of heat

4.183 x 107 ergs = 1 calorie

𝟖.𝟑𝟏𝟒 𝒙 𝟏𝟎𝟕
R ( calorie) = = 1.987 cal K-1 mol-1
𝟒 𝟏𝟖𝟑 𝒙 𝟏𝟎𝟕
.
Summary of values of ‘R’

(i) R = 0.0821 liter atm K-1 mol-1

(ii) R = 8.314 x 107 ergs K-1 mol-1

(iii) R = 8.314 Joules K-1 mol-1

(iv) R = 1.987 cal K-1 mol-1

Numerical problem of combined gas equation:
A steel cylinder of 50 liters capacity contains helium at a pressure of 200 atmosphere at a
temperature of 27 oC. Assume that all of the gas can be used to fill a weather balloon, which
is released in air. At a height of 100,000 ft the volume of the ballon is 200 cubic meter and
it’s temperature is -73 oC.What is the pressure of the gas inside the balloon?
Solution,
Initial conditions: Final conditions:
Volume (V1) = 50 liters
Volume (V2) = 200 cubic meter
= 200 x 100 x100 x100 cc
= 200 000000/1000 = 200000 liters.
Temperature (T1) = (27 + 273) K
Temperature (T2) = (-73 + 273) K
= 300 K
= 200 K
Pressure (P1) = 200 atm
Pressure (P2) = ???
From combined gas equation, we have

𝑷𝟏𝑽𝟏 𝑷𝟐𝑽𝟐
= Or, P2 = P1V1T2/T1V2
𝑻𝟏 𝑻𝟐
= 200 x 50 x 200/200000 x300 = 0.0333 atm.
= 0.0333 x 760 mm = 25.3 mm
Numerical problem of ideal gas equation:

A 6.00 mol sample of helium is confined in a 4.5 liter vessel. (a) What is the temperature if the
pressure is 3.0 atm. (b) What is the density of the sample.
Solution
We have
n = 6.00 moles He
V = 4.5 liters
P = 3.0 atm
T=?
R = 0.0821 liter atm K-1 mol-1

Using Ideal gas equation, we have

PV = nRT
Or T = PV/nR = 3 x 4.5 /6 x 0.0821 = 27.4 K
= (27.40 -273) = -246.6 oC
To calculate density,
We have 6 moles of helium are confined in 4.5 liters volume.
𝟔
Moles/ liter = n/V = 6/4.5 = x 4 gms/liter = 5.33 gms/liter
𝟒𝟓
.

Density of the gas = 5.33 gms/liter

An open vessel at 27 oC is heated until three fifth of the air in it has been expelled. Assuming
that the volume of the vessel remains constant, find the temperature to which the vessel has
been heated.
Solution
Let V = the volume of the vessel
Initial condition:
Temperature (T1) = 27 oC = (27 + 273) K = 300 K
The volume V of the vessel contains n1 moles of air at 27 0C
Hence, if the pressure of air in it = P

Then
PV = n1 RT1 = n1R(300) …………………………(1)
Final condition
Let the open vessel be heated upto T2 K, when three fifth of air is expelled. Since the vessel
is open, P and V remains constant.
So, PV = n2 RT
Or, PV = ( n1 - 3n1/5)RT2 = 2n1RT2/5 -----------------(2)
Equating equation (1) and (2) we get,
Or, n1R(300) = 2n1RT2/5 Or, T2 = 750 K = 477 oC
Daltons’s law of partial pressure:
Total pressure (P)
It is the pressure exerted by all the components of gas present in a mixture at constant
temperature.
For example:
Let us consider a gaseous mixture containing H2, O2 and N2, so total pressure of the
gaseous mixture.
Ptotal = pH2 + pO2 + pN2

Partial pressure (p)

It is defined as the pressure of a gas in the gaseous mixture that the individual gas would
exert if alone present in the whole container or the pressure due to any individual gas in the
gaseous mixture is known as the partial pressure.
John Dalton in 1807 gave a law to calculate the total pressure of a gaseous mixture from the
pressure of the component gases. This is actually called Dalton’s law of partial pressure.

Statement:

At constant temperature, the total pressure exerted by a mixture of gases is equal to the sum
of the partial pressure of the individual component gases.
If p1, p2 and p3 are the partial pressures of constituent gases then the total pressure Ptotal of the
gaseous mixture is given by:
Ptotal = p1 + p2 + p3

Mathematical deduction of Dalton’s law of partial pressure:

Let us consider a gaseous mixture composed of n1 moles of gas 1, n2 moles of gas 2 and
n3 moles of gas 3. Let the total volume of the gaseous mixture be V and temperature be T
Kelvin.
If nt be the total moles of the gaseous mixture then,

nt = n1 + n2 + n3 ……………………………(1)

Multiplying both sides of the equation (1) by RT/V we get,

nt RT/V = n1 RT/V + n2RT/V + n3 RT/V ………………….....(2)

But according to ideal gas law we get,

PV = nRT Or, P = nRT/V

So, p1 = n1 RT/V, p2 = n2RT/V …………………………..(3)

p3 = n3RT/V, Pt = nt RT/V
From equations (2) and (3) we get,
Pt = p1 + p2 + p3…………………………(4)
Where, Pt = Total pressure exerted by the gaseous mixture.
p1, p2 and p3 = Partial pressures of individual component gases 1, 2 and 3
respectively.

Therefore, equation (3) is the mathematical expression of Dalton’s law of partial pressure.

Calculation of partial pressure from mole fraction:

If we divide partial pressure of a particular component gas by the total pressure of the gaseous
mixture of gases, we get the mole fraction of that particular component. For example.
So, p1 = n1 RT/V …………………………(1)
Pt = nt RT/V ………………………….(2)

Dividing equation (1) by (2) we get,

𝒏𝟏𝑹𝑻
𝑽 = n1/nt
Or, p1/Pt =
𝒏𝒕 𝑹𝑻 𝑽
/

Therefore, p1/Pt = n1/nt Or, p1 = Mole fraction of gas 1 x Pt

Partial pressure of a gas in a mixture = Mole fraction of a gas in a mixture x total pressure

Mole fraction of component gas 1 = n1/nt

Numerical problems of Dalton’s law of partial pressure.
(1) 40 cc of oxygen at 650 mm pressure, 300 cc of nitrogen at 700 mm of pressure and 10 cc
of Hydrogen at 760 mm pressure are mixed together in a separate vessel, whose capacity
is 80 cc. Find out the partial pressure of each gas, and the total pressure of the mixture.
Solution

Here, we can use Boyle’s law to calculate the partial pressure that each gas would exert after
Mixing.
For oxygen, P1 V1 = P2V2
650 x 40 = P2 x 80
Or, P2 = 325 mmHg
Partial pressure of Oxygen = 325 mmHg
Similarly for Nitrogen gas,
P1 V1 = P2V2
700 x 300 = P2 x 80
Or, P2 = 262.5 mmHg

Partial pressure of Nitrogen = 262.5 mmHg

 Similarly for Hydrogen gas,
P1 V1 = P2V2
60 x 10 = P2 x 80
Or, P2 = 95 mmHg
Partial pressure of Hydrogen = 95 mmHg

The total pressure of the gaseous mixture P total = pO2 + pN2 + pH2

= 325 + 262.5 + 95 = 682.5 mmHg

(2) Three volumes of oxygen and two volumes of chlorine are mixed together. What will be the
partial pressure of each be when the barometer stands 760 mmHg.
Solution

We have, from formula, partial pressure = Total pressure x mole fraction.

So, partial pressure of Oxygen (pO2) = 760 x 3/5 = 456 mmHg.

And partial pressure of Chlorine (pCl2) = 760 x 2/5 = 304 mmHg
 (3) A 10.0 liters flask contains 0.2 mole of Hydrogen, 0.3 mole of Nitrogen and 0.4 mole of
Carbondioxide at 25 oC. Find (a) the partial pressure of each of the components gas exert
(b) the total pressure inside the flask.

(4) Calculate the mass of oxygen gas whose volume is 320 ml at 17 oC at 2 atm pressure.
(HSEB 2062)

Graham’s Law of Diffusion:

Diffusion:
Diffusion is a natural phenomenon by virtue of which two or more than two gases intermix
with each other irrespective of gravitational force of attraction without aid of any external
agency.

Or Diffusion is a natural phenomenon by virtue of which gases moves from higher

concentration to lower concentration.

Effusion:
Effusion is a process by virtue of which a gas enclosed in a container under pressure is
allowed to pass through a small opening or porous partition or hole or orifice.
Graham’s Law of Diffusion:
Statement:
Under similar condition of temperature and pressure, the rate of diffusion of gases are
inversely proportional to the square roots of their densities.
Mathematically,

r 𝟏 …………………..(1)
𝒅

Where, r = rate of diffusion

and d = density of gas

Let r1 and r2 be the rate of diffusion of two gases of densities d1 and d2 respectively then
according to Graham’s law of diffusion

r1 𝟏
𝒅𝟏

r2 𝟏
𝒅𝟐
 𝑑2
r1 /r2 = .. …………………………….(2)
𝑑1

Equation (2) is a mathematical equation of Graham’s Law of diffusion.

As we know,
Molecular weight = 2 x Vapour density
M = 2d
Therefore, d = M/2 …………………………(3)

From equation (2) and (3) we get,

𝑀2/2..
r1 /r2 =
𝑀1 2
/

𝑀2
= …………………………….(4)
𝑀1

Equation (4) is another mathematical form of Graham’s law of diffusion.

Equation (4) shows that under similar condition of temperature and pressure the rates of
diffusion of gases are inversely proportional to the square root of their molecular weights.
As we know rate of diffusion is defined as the volume of gas diffuse in unit time.
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒈𝒂𝒔 𝒅𝒊𝒇𝒇𝒖𝒔𝒆
Rate of diffusion (r) = = V/t
𝑻𝒊𝒎𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏

Let t1 and t2 be the time taken to diffuse V ml of two different gases then

𝑽/𝒕𝟏 𝑀2
r1/r2 = =
𝑽
𝑀1
𝒕𝟐

𝑀2
Therefore, t2/t1 = ……………………….(5)
𝑀1

Equation (5) is another mathematical form of Graham’s law of diffusion.

Numerical problems:

1. A gas X diffuses five times as rapidly as another gas Y. Calculate the ratio of molecular
mass of X and Y. (HSEB 2057)

Solution

Rate of diffusion of gas Y ( r2) = x

Rate of diffusion of gas X ( r1) = 5x
Ratio of molecular mass of X and Y (M1/M2) = ??
According to Graham’s law of diffusion

𝑀2
or, r1/r2 =
𝑀1

𝑀2
or, 5x/x =
𝑀1

Squaring on both sides of equation, we get

Or, 25/1 = M2/M1

M1/M2 = 1/25
2. 5 gm of hydrogen diffused through a porous membrane in 30 minutes. Find the time
required to diffuse the same amount of SO2 gas at identical conditions. (HSEB 2064).

Solution

In H2 gas In SO2 gas

Density (D1) = 1 Density (D2) = 32

Time (t1) = 30 x 60 sec Time (t2) = ??

Molecular mass (M1) = 2 Molecular mass (M2) = 64

Volume (V1) = Mass/Density = 5 Volume (V2) = Mass/Density = 5/32

According to Graham’s law of diffusion,

𝑀2
Or, V1/t1 x t2/V2 =
𝑀1

t2 = 318 second = 5.30 minutes

3. Two gram of hydrogen diffuses from a container in 10 minutes. How many grams of oxygen
would diffuse through the same container in the same times under similar conditions??
(HSEB 2055) [ Mass of O2 gas = 8 gm)

4. How long will it take 600 ml of H2 gas to diffuse through a porous partition, if 300 ml of O2
diffuse through it in 10 minutes under identical conditions?? (HSEB 2056)

solution

In H2 gas In O2 gas

Volume (V1) = 600 mL Volume (V2) = 300 mL

Time (t1) = ? Time (t2) = 10 mins. = 10 x 60 = 600 sec

Molecular mass (M1) = 2 Molecular mass (M2) = 32

According to Graham’s law of diffusion

𝑀2
Or, V1/t1 x t2/V2 =
𝑀1 Therefore, t1 = 2 x 600/4 = 5 minutes.
32
Or 600/t1 x 600/300 = 2
5. How long will it take 500 ml of hydrogen gas to diffuse through a partition, if 250 ml of
oxygen diffuse in 50 minutes under identical conditions (HSEB 2061) Ans = 25 mins

6. The rates of diffusion of a saturated (CnH2n+2) gas is 1.206 times that of SO2 gas under
identical conditions. Find the molecular mass and the value of n for the gas (molecular
mass of SO2 = 64). (HSEB 2060)
Solution,

In SO2 gas In hydrocarbon CnH2n+2

Rate of diffusion (r1) = x Rate of diffusion (r2) = 1.206 x

Molecular mass (M1) = 64 Molecular mass (M2) = 12n + 1(2n+2)
= 14n +2
According to Graham’s law of diffusion

𝑀2 (14𝑛+2) Or, 8/1.206 = (14𝑛 + 2)

or, r1/r2 = Or, x/1.206x =
𝑀1
64

By Squaring on both side of above equation we get,

(14n +2) = 8 x 8/1.206 x 1.206 Or, n = 3

Therefore, molecular mass of CnH2n+2 = 12 x3 + 2x3 +2 = 44

Numerical problems Graham’s law of diffusion contd.

7. What are relatives diffusion rates of Methane and SO2?If these two gases are
simultaneously introduced into opposite ends of 100 cm tube and allowed to diffuse
towards each other, at what distance from the SO2 ends will the molecules of two gases
meet? (HSEB 2058).

Solution 100 cm

In case of methane (CH4) 2x cm x cm

Molecular weight (M1) = 16
Rate of diffusion (r1) = ??
Incase of SO2 gas
Molecular weight (M2) = 64
Rate of diffusion (r2) = ??
CH4 gas Phase where
SO2 gas
Two gases meet
According to Graham’s law of diffusion with each other

𝑀2 64
or, r1/r2 = = =2
𝑀1
16
 Therefore, rate of diffusion of CH4 : SO2 = 2:1
If SO2 covers x cm, then CH4 covers distance of 2x cm.

Or, x + 2x = 100 cm
Or, 3x = 100 cm
Or, x = 33.33 cm

Thus, SO2 covers a distance of 33 .33 cm and CH4 covers a distance of 2x 33.33 = 66.66 cm
Therefore molecules of both of the gases meet at a distance of 33.33 cm from SO2 end.

8. A vessel of volume of 100 ml contains 10 % of O2 and 90 % of unknown gas. The gases

diffuse in 86 sec through a small hole of the vessel. If pure oxygen under the same condition
diffuses in 75 sec. Find the molecular mass of unknown gas (HSEB 2059).
Solution Rate of diffusion of gaseous mixture (r1) = V1/t1
= 100/86
Rate of diffusion of pure oxygen (r2) = V2/t2

= 100/75

(Pure oxygen means all the gas in the mixture is only oxygen)

According to Graham’s law of diffusion

 𝑑2
or, r1/r2 = 𝑑1

Where, d1 = density of gaseous mixture

And d2 = density of oxygen gas

𝑑2
Or, V1/t1 x t2/V2 = 𝑑1
[Density of O2 = Mol. Weight /2 = 32/2 = 16]
16
Or 100/86 x 75/100 = 𝑑1

d1 = 21.04

Mass of mixture = Mass of Oxygen + Mass of unknown gas

(Volume x density) of mixture = (Volume x density) of oxygen + (Volume x density) of unknown gas

100 x 21.04 = 10 x16 + 90 x dunkown gas

dunknown gas = 21.6

Molar mass = 2 x dunknown gas = 2 x 21.6 = 43.2

Hence molecular mass of unknown gas = 43.2

9. A mixture of Ozone and Oxygen containing 20 % by volume of ozone diffused through a
porous plug in 172 seconds, while the same volume of pure oxygen took 164 seconds to
diffuse through the same plug. Calculate the relative density of ozone.

Solution

Total volume of gaseous mixture = X mL

Volume of ozone = X x 20% = X/5

Volume of Oxygen = X x (100 – 20)% = X x 80% = 4X/5

Density of oxygen (d2) = 32/2 = 16

Rate of diffusion of gaseous mixture (r1) = V1/t1 = X/172

Rate of diffusion of oxygen (r2) = V2/t2 = X/164

According to Graham’s law of diffusion

𝑑2
or, r1/r2 = 𝑑1

𝑽/𝒕𝟏 𝑑2 𝑿/𝟏𝟕𝟐
Or, = Or = 16 Or dmixture = 17.59
𝑽 𝑑1 𝑿 𝟏𝟔𝟒
/
𝑑𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝒕𝟐
The density of gaseous mixture = 17.59
Total mass of gaseous mixture = Mass of ozone + Mass of oxygen
(Density x volume) of gaseous mixture = (Density x volume) of ozone + (Density x volume) of oxyg en

17.59 x X = D x X/5 + 16 x 4X/5

𝟔𝟒𝑿
𝟏𝟕.𝟓𝟗 𝑿 − 𝟓 𝟓
Density of Ozone (D) = = 23.95
𝑿

Therefore, the density of ozone = 23.95

10. In a smoke ring experiment, dry ammonia gas (NH3) and dry hydrogen chloride gas (HCl)
are released inwards at the same time from the opposite ends of a glass tube 1.5 m long.
At what distance from HCl end would the formation of the smoke ring start?

11.One liter of a gaseous mixture containing methane and hydrogen effused in 5 minutes
while one liter of oxygen takes 10 minutes. Calculate (a) the density of the gaseous mixture
(b) percentage by volume of each gas in the mixture.
Problems of ideal gas:

1. A flask of 0.3 L capacity was weighted after it had been evacuated. It was then filled with a
gas of unknown molecular mass at 1.0 atm. pressure and temperature of 300 K. The increase
in mass of the flask was 0.977 gm. Calculate the molecular mass of the gas. (HSEB 2066)

Solution

Volume of a flask (V) = 0.3 L

Mass = 0.977 gm
R = 0.0821 Liter atm mol-1 K-1
Pressure (P) = 1.0 atm.
Temperature (T) = 300K
Weight of the gas (w) = 0.977 gm
Molecular mass of gas = ???

By applying ideal gas equation,

PV = nRT
PV = Mass x RT/Molecular Mass
1 x 0.3 = 0.977 x 0.0821 x 300/Molecular mass

Therefore, molecular mass = 0.977 x 0.0821 x 300/0.3 = 80.1

2. An evacuated glass vessel weighs 50 gm when empty, 148 gm when filled with a liquid of
density of 0.98 gm/cc and 50.5 gm when filled with an ideal gas at 760 mm Hg and at 300
K.Determine the molecular mass of gas.

Solution

Weight of empty vessel (x) = 50 gm

Weight of glass vessel with liquid (y) = 148 gm
Weight of glass vessel with an ideal gas (Z) = 50.5 gm
Density of the liquid (D) = 0.98 gm/cc
Pressure (P) = 760 mm of Hg = 1 atm.
Temperature (T) = 300 K
Molecular mass of gas (M) = ??
Now, weight of liquid (y-x) = (148 -50)gm = 98 gm
Weight of the ideal gas = (Z-x) = (50.5 -50) = 0.5 gm
For liquid,
Density (D) = Mass/ Volume
0.98 = 98/Volume
Therefore, volume = 98/0.98 = 100 cc

So, Volume of liquid (V2) = 100 cc

Now, volume of ideal gas is same as the volume occupied by liquid.
So, volume of gas (V) = 100 cc
By using ideal gas equation
PV = nRT
Or, PV = mass x RT/ Molar mass
Molar mass = mass x RT/ PV
= 0.5 x 0.0821 x 300/ 1 x 100/1000 = 123.15

Therefor, molecular mass of the gas = 123.15

(3) 0.50 gm of a volatile liquid was introduced into a globe of 1000 ml capacity. The globe
was heated to 91 0C, so that all the liquid vaporized exerted a pressure of 190 mm of Hg.
Calculate the molecular mass of the liquid. (R = 0.0821 liter atm mol-1 K-1). (Ans = 59.76)

4. One mole of gas occupies a volume of 1 liter at 27 0C.What will be the pressure of gas??
( HSEB 2055).
Given Number of moles (n) = 1 mole
Volume (V) 1 liter
Temperature (T) = 27 0C = (273 + 27) = 300 K
R =0.0821 liter atm. mol-1 K-1
Pressure (P) = ??
We know from ideal gas equation,
PV = nRT
P = nRT/V = 1 x 0.0821 x 300/1 = 24.63 atm.
5. A ballon can hold 1000 cc of air before brusting. The ballon can hold 975 cc if air reach at 5
oC. Will it brust when it is taken a hiuse at 25 oC? Assume that the pressure of the gas in

the ballon remains constant. (HSEB 2054)

Solution

The capacity of ballon to hold the gas = 1000 cc

Volume of air in the ballon (V1) = 975 cc
Initial temperature (T1) = 5 oC = (273 + 5) oC = 278 K

Final temperature (T2) = 25 0C = (273 + 25) = 298 K

Final volume of the ballon (V2) = ???
By applying combined gas equation
We get,

Or, P1V1/T1 = P2 V2/T2

Since at constant pressure, P1 = P2
So
V1/T1 = V2/T2
Or, V2= V1T2/T1 = 975 x 298/278 = 1045.14 cc
 6. A vessel contains 12 gm of an ideal gas at t 0C temperature and 1 atm. pressure. When
the temperature is increased by 10 OC at the same volume, the pressure increases by 10 %.
Calculate the volume and initial temperature.

Solution

We know from ideal gas equation, PV = nRT

At initial conditions

PV = Weight in gram x R xT/Molecular weight

1 x V = 12 x R x (t +273) K/Molecular weight
V = 12 x R x (t + 273)K/Molecular weight …………………………………….(1)

When temperature is increased by 10 oC at the same volume, the pressure increased by 10 %

PV = nRT
( 1+ 1 x 10/100) V = weight x R x (t + 273 + 10) K/Molecular weight

1.1 x V = 12 x R x (t + 283)K/Molecular weight

Or, V = 12 x R x (t + 273)K/Molecular weight x 1.1………………………........(2)

From equation (1) and (2) we get,

12 x R x (t + 273)/Molecular weight = 12 x R x (t + 283)/Molecular weight x 1.1

0r, (t + 273)K = (t+283)K/1.1

Or, 1.1 t +(273 x 1.1)K = t+283 K
Or, 1.1t –t =(283-300.3)K
or, 0.1 t = -17.3 K
or, t = -17.3/0.1 K = -173 K
Some numerical problems:

1. A carbondioxide fire extinguisher of 3 L capacity contains 4.4 kg of carbondioxide. What

volume of gas could this extinguisher deliver at NTP? (HSEB 2052, ans 2237 liters of CO2)

2. A gas cylinder containing cooking gas can withstand up to pressure 14.9 atm. The pressure
gauge of cylinder indicates 12 atm at 27 0C. Due to sudden fire in the building, it’s
temperature starts rising. At what temperature will the cylinder explode? (HSEB 2057, ans
372.5 K or 99.5 oC).

3. Calculate the mass of oxygen gas whose volume is 320 ml at 17 oC and 2 atm. pressure.
(HSEB 2062, ans - 0.86 gm)

4. One mole of a gas occupies a volume of 1 L at 27 OC. What will be the pressure of gas?
HSEB 2055, ans – 24.63 atm.).

5. What are relatives diffusion rates of Methane and SO2?If these two gases are
simultaneously introduced into opposite ends of 100 cm tube and allowed to diffuse towards
each other, at what distance from the SO2 ends will the molecules of two gases meet?
(HSEB 2058).
10. In a smoke ring experiment, dry ammonia gas (NH3) and dry hydrogen chloride gas (HCl)
are released inwards at the same time from the opposite ends of a glass tube 1.5 m long.
At what distance from HCl end would the formation of the smoke ring start?

### 500 cc of Oxygen under 680 mm of pressure and 250 cc of Nitrogen at 720 mm pressure
were put together in a liter flask keeping the temperature constant. Find the final pressure of
the gaseous mixture [ Ans – 520 mm of Hg].
 Aqueous tension (f)

The partial pressure of water vapour is known as aqueous tension

Pmoist gas = pdry gas + pwater vapour

Therefore,
Pdry gas = Pmoist gas - aqueous tension (f)

## The volume of carbon dioxide gas collected over water at 25 oC is 680 cc with a total
pressure of 752 mm of Hg. The vapour pressure of water at 25 oC is 23.8 mm of Hg. Determine
the partial pressure of CO in container (HSEB 2053).

Solution

Total pressure of moist CO gas (Ptotal) = 752 mm of Hg

Vapour pressure (aq. tension) of water at 25 OC (f) = 23.8 mm of Hg.

Partial pressure of CO (pdry CO) = ??

Now,
Total pressure of gas (Ptotal) = Partial pressure of CO + Vapour pressure
752= pdry CO + 23.8 mm of Hg Partial pressure of CO (pdry CO ) = (752 – 23.8) mm of Hg
= 728.2 mm of Hg.
Postulates of kinetic molecular theory of gas:

Kinetic molecular theory of gas is based on both the molecular concept of matter and kinetic
concept of gas molecules. The kinetic theory of gas was put forward by Bernoulli and further
developed and extended by Clausius, Kroning, Maxwell, Boltzman and others scientists.

The fundamental postulates of kinetics molecular theory of gas are:

(1) All gases are made up of large number of minute particles called molecules.

(2) The molecules are separated from one another by large distances with a lot of empty
space between them, hence the volume occupied by the molecules is negligible compared
to the volume of the gas.
(3) The molecules are in the state of constant motion they collide with directions along
straight lines. During their motion they collide with one another and also with the wall of
the container.

(4) Molecular collisions are perfectly elastic i:e no loss of kinetic energy occurs when the
molecules collide with one another as well as with the wall of container.

(5) There are no forces of attraction between molecules i.e. intermolecular forces in gas are
negligible.
(6) The pressure exerted by the gas is due to the bombardment of the molecules of gas on
the walls of the container.

(7) The average kinetic energy of the gas molecules is directly proportional to the absolute
temperature.

Real gas and ideal gas:

Ideal gas:

All gaseous laws are strictly valid only for ideal gases.
Therefore, an ideal gas is defined as the gas which perfectly obey Boyle’s law, Charle’s law
and Avogadro’s law at all conditions of temperature and pressure.

For an ideal gas equation PV = nRT is exact

But there is n such gas which is perfectly ideal.

For all ideal gas the compressibility factor (Z) is exactly 1.

Real gas:
Those gases that are found to obey gas laws and PV = nRT only at low pressure and high
temperature. Such gases are called real gases. But under high pressure and low temperatures
real gases exhibit marked deviation from ideal behaviour.
Inorder to study the deviation or real gases from ideal behaviour, we need to make a plot of PV
versus P for some gases like N2, H2 and CO2.

The dotted line as shown in figure above is the plot for ideal gas. Actually, real gases like
H2, N2 amd CO2 at 273 K are deviating from ideal behaviour with increasing pressure.

It means real gases are showing an ideal behaviour at very low pressures and exhibiting mark
deviation from ideal behaviour with increasing pressures.
The plot of PV versus P for a single gas nitrogen at different temperatures is shown in
following figure. The plot shows that the lower the temperature, larger is the deviation
from ideal behaviour.
Causes of deviations and Vander Waal’s equation:

Dauch Scientist J.D Vander Waal, actually gave the most logical explanation for the deviation
of gases from ideal behaviours.

The deviation of real gases from ideal behaviour is due to two faulty assumptions made in
kinetic molecular theory of gas.
1. The actual volume of the molecules is negligible compared to the total volume occupied by
the gas.
2. There are no forces of attraction between the gas molecules. That is the intermolecular forces
of attractions are negligible.
By considering above facts J.D. Vander Waal made some necessary correction in pressure and
volume in ideal gas equation and gave a new equation. This is called Vander Waal’s equation
of state.
(P + an2/V2) (V – nb) = nRT, for n moles of gas.

For 1 mole of gas, n =1

Then,
(P + a/V2) (V – b) = RT
Where a and b are constants are called Vander Waal’s constant. The constant a is related to
finite volume of molecules and the constant b is related to influence of intermolecular
attractions on the pressure of gas.
1) 100 ml of a gas are enclosed in the cylinder under a pressure of 760 mm. What would the
volume be at a pressure of 1520 mm? [Ans:50ml]

2) A gas occupies 23.4 liters at a pressure of 40mm of Hg. What is the volume in ml when the
pressure is increased to 600mm?

3) A gas occupies a volume of 250 ml at 745 mm Hg pressure and 25 oC. What additional
pressure is required to reduce the volume of the gas to 200 ml at the same temperature?

4) A bulb of unknown volume “V” contains a gas at 1 atm pressure. This bulb was connected
to another evacuated bulb of volume 0.5 liter thorough a stop cock. When the stop cock
was opened, the pressure at each bulb becomes 570 mmHg while the temperature
remained constant. Calculate “V” in liters.

5) A sample of a gas is expanded at constant temperature from an initial volume of 6.0 liters
to a final volume of 9.3 liters where its pressure is 0.15 atm. What is the original pressure of
the gas?