PROPERTIES OF GASES

1. Gaseous state is the simplest state of matter.

2. Gas particles have much more kinetic energy than those of liquid and solid.
3. The cohesive forces in gases are negligible and the particles are free to move about in
all directions (random motion).
4. A gas has no definite shape.
5. It has no definite volume but occupies the volume of its container.
6. Gas particles are relatively far apart and may be readily compressed.
POSTULATES OF KINETIC THEORY OF GASES
1. The gas molecules are in random motion and during their motion, they collide with
one another and with the walls of the container.
2. The collisions of gas molecules on the walls of the container constitute the gas
pressure exerted on the container.
3. The collisions of the gas molecules are perfectly elastic and there is no loss of kinetic
energy during collisions.
4. The actual volume occupied by the gas molecules is negligible compared to the
volume of the container.
5. The force of attraction between the gas molecules is negligible.
6. The average kinetic energy of gas molecules is directly proportional to the absolute
temperature.
7. There is no effect of gravity on the motion of gas molecules.

Note that a gas which obeys the postulates of kinetic theory of gases is known as an ideal
gas. Real gases show deviations in behaviour as given in this theory.

GAS LAWS

Boyle’s Law

This states that the volume of a fixed mass of a gas is inversely proportional to its pressure at
constant temperature.

1
V∝
P

1
 k
V=
P

PV =k

Hence, for initial and final volumes and pressures; P1 V 1=k ∧P 2 V 2=k

Therefore, P1 V 1=P2 V 2

Exercise 1: 325 cm3 of a gas has a pressure of 700 mmHg. Find its volume if the pressure is
reduced to 670 mmHg.

P1 V 1=P2 V 2

P1=700 mmHg ; P2=670 mmHg ; V 1=325 cm3

P1 V 1 700 ×325
V 2= =
P2 670

3
V 2=339.6 cm

Charles’ Law

Charles’ Law states that the volume of a fixed mass of a gas is directly proportional to the
absolute temperature at constant pressure.

V αT

V =kT

V
=k
T

V1 V2
Hence, for initial and final volumes and temperatures; =k , =k
T1 T2

V1 V2
Therefore, =
T1 T2

Exercise 2: At 25 oC, a sample of hydrogen gas occupies 145 cm3, what will be the volume at
114 oC if the pressure is constant?

2
V1 V2
=
T1 T2

3
V 1=145 cm ; T 1=25+ 273=298 K ; T 2 =114+273=387 K

V 1 T 2 145× 387
V 2= =
T1 298

3
V 2=188.3 cm

Avogadro’s Law

This states that equal volumes of all gases at the same temperature and pressure contains the
same number of molecules. This experimentally-determined number is called the Avogadro’s
number and the value is 6.02 × 1023. One mole of any gas contains 6.02 × 1023 molecules and
mathematically, Avogadro’s Law is given as,

V ∝n

General gas equation

P1V 1 P2V 2
=
T1 T2

Exercise 3: The pressure of 100 cm3 of oxygen at 35 oC is 750 mmHg. What will be the
volume of the gas if the pressure is reduced to 120 mmHg at 27 oC?

P1V 1 P2V 2
=
T1 T2

P1 = 750 mmHg; V1= 100 cm3; T1= 35 + 273 = 308 K; P2 = 120 mmHg; T2 = 27 + 273 = 300
K.

P1 V 1 T 2 750 ×100 ×300

V 2= =
P2 T 1 120 ×308

V2 = 608.8 cm3

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Standard temperature and pressure

Because of the variations in pressure and temperature of gases in different

locations/countries, scientists decided that standard temperature is 0 oC or 273 K and standard
pressure is 1 atm or 760 mmHg or 101325 Nm-2 or Pa.

Exercise 4: If a gas occupies a container of volume 146 cm 3 at 18 oC and 0.971 atm, what is
its volume at s.t.p?

P1V 1 P2V 2
=
T1 T2

P1 = 0.971 atm; V1 = 146 cm3; T1 = 18 + 273 = 291 K; P2 = 1 atm; T2 = 273 K.

P1 V 1 T 2 0.971 ×146 ×273

V 2= =
P2 T 1 1 ×291

V2 = 132.9 cm3

Dalton’s Law of partial pressure

This states that the total pressure of a mixture of non-reacting gases is equal to the
sum of the partial pressures of the individual gases that make up the mixture at constant
temperature and volume. If a mixture of gases contains individual gases, A, B, C, then the
total pressure, Ptotal = PA + PB + PC. Where, PA, PB and PC are the partial pressures of the
individual gases. If a gas is collected over water, it is likely to be saturated with water vapour
and the total pressure becomes: Ptotal = Pgas + Pwater vapour.

Exercise 5: A certain mass of hydrogen gas collected over water at 6 oC and 765 mmHg
pressure has a volume of 35 cm 3. Calculate the volume when it is dry at s.t.p (saturated
vapour pressure of water at 6 oC = 7 mmHg).

The true pressure of the hydrogen gas = (765 - 7) mmHg = 758 mmHg

P1V 1 P2V 2
=
T1 T2

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P1 = 758 mmHg; V1 = 35 cm3; T1 = 6 + 273 = 279 K; P2 = 760 mmHg; T2 = 273 K.

P1 V 1 T 2 758 ×35 ×273

V 2= =
P2 T 1 760 ×279

V2 = 34.2 cm3.

Graham’s Law of diffusion of gases

It states that at constant temperature and pressure, the rate of diffusion of a gas is
inversely proportional to the square root of its density (or its molecular mass).

1 1
R∝ ;R∝
√ρ √M

This implies that

R1
R2 √
ρ
= 2
ρ1
and
R1
R2
=
√
M2
M1

1 t
But rate ¿ , Hence, 1 =
t t2
M1
M2 √
Where, R1 and R2 are the rates of diffusion; t1 and t2 are time taken and M1 and M2 are relative
molecular masses.

Exercise 6: A gas X diffuses twice as fast as gas Y under the same conditions. If the relative
molecular mass of X is 28, calculate the relative molecular mass of Y.

RX = 2 RY (because rate of diffusion of X is twice that of Y)

RX
Ry
=
MY
MX√
2 RY
Ry
=
MY
28 √
MY = 112

Exercise 7: A given volume of CH4 diffuses in 20 s. How long will it take the same volume
of SO2 to diffuse under the same conditions? (C = 12; H = 1; S = 32; O = 16)

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Relative molecular mass of CH4 = 12 + (1 × 4) = 16

Relative molecular mass of SO2 = 32 + (16 × 2) = 64

t CH
t SO
4

2
=
√ M CH
M SO
4

20 s
t SO
=
16
64
2
√
t SO =40 s
2

Ideal gas equation

This is a combination of Boyle’s Law, Charles’ Law and Avogadro’s Law.

nT
V∝
P

PV =nRT (1)

Where P is pressure, V is volume, n is number of moles, R is universal gas constant and T is

absolute temperature.

m reacting mass
n= =
M molar mass

mRT
Equation (1) becomes, PV =
M

PM = ( mV ) RT =ρRT
m
Recall that density, ρ=
V

Exercise 8: 2 moles of an ideal gas are at a temperature of -13 oC and a pressure of 2 atm.
What volume will the gas occupy at that temperature? (R = 0.082 atm dm3 mol-1 K-1)?

PV =nRT

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 nRT
V=
P

P = 2 atm; n = 2 moles; T = -13 + 273 = 260 K; R = 0.082 atm dm3 mol-1 K-1

2 ×0.082 ×260 3
V= =21.32 dm
2

Exercise 9: Calculate the density of chlorine gas at s.t.p. (Cl = 35.5)

Relative molecular mass of chlorine gas, Cl2 = 35.5 × 2 = 71

At s.t.p, P = 1 atm and T = 273 K

P×M 1× 71
ρ= = =¿ 3.17 g dm-3
R× T 0.082× 273

Deviations from the ideal gas equations

Ideal gases obey the gas laws under all conditions of temperature and pressure. Ideal
gas is theoretical because no gas obeys the gas laws or the ideal gas equation under all
conditions of temperature and pressure. Real gases deviate from the ideal behaviour and all
gases are real gases. Real gases obey ideal gas equation and other gas laws at high
temperature and low pressure.

The kinetic theory assumptions of negligible volume and forces of attraction are true
if the distance between the gas molecules is large, which is possible only if the pressure is
low and the temperature is high. But if the pressure is high and the temperature is low, the
distance between the gas molecules is less and they come closer to one another. Under these
conditions, the volume occupied by the gas molecules is not negligible compared to the total
volume of the gas container, and the forces of attraction or repulsion between the gas
molecules may not be negligible. In order to get an equation relating P, V and T, which is
obeyed by the real gases over a wide range of temperatures and pressures, appropriate
corrections have to be applied so as to take into account: the volume of the gas molecules and
the forces of attraction between the gas molecules.

van der Waal’s equation

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This is the modification of the ideal gas equation by the incorporation of correction terms for
volume and force of attraction.

1. Correction for volume: If there are n moles of gas placed in a container, the actual
volume available to gas molecules for their free movement is less than the volume of
the container, V. Hence, the actual volume for the free movement of gas molecules
would be V ideal =V −nb (1)
Where n = number of moles and b = excluded volume or effective volume per mole of
gas. The excluded volume is characteristic for each gas.
2. Corrections for forces of attraction: For a real gas, the pressure, P is less than the
ideal pressure. So a correction term, P0 is added to the measured pressure, P in order
to obtain the ideal pressure.
Pideal =P+P0 (2)
The pressure depends on the frequency of collisions with the walls and the force of
each collision. Both factors are reduced by the attractive forces.
2
n
The correction term, P0 ∝( )
V
a n2
P0= (3)
V2

Where ‘a’ is a constant of proportionality

Substituting equation (3) in equation (2),

2
an
Pideal =P+ 2 (4)
V

Since the ideal gas equation is Pideal V ideal =nRT , it implies that; if the values for P ideal
and Videal from equations (4) and (1) respectively, are substituted in the above equation, then,

( )
2
an
P+ 2 ( V −nb )=nRT (5)
V

Equation (5) above is known as the van der Waals equation for n moles of a gas. The
constants ‘a’ and ‘b’ are called van der Waals constants. The van der Waals equation is an
improvement over the ideal gas equation and explains the deviations of real gases from ideal

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behaviour. It is valid over a wide range of temperatures and pressures. Van der Waals
equation fails at very high pressures and near critical temperature.

Significance of van der Waals constants

(i) ‘a’ is a measure of the intermolecular forces of attraction in a gas. Gases which can be
easily liquefied have larger values of ‘a’. Moreover, the value of ‘a’ increases with ease of
liquefaction of gases.

SO3 > NH3 > HCl > CO2 > N2 > O2 > H2 > He

(ii) ‘b’ is the effective volume of the gas molecules. A gas with a small value of ‘b’ will
occupy lesser volume and hence will be more compressible.

Exercise 10: 10 moles of NH3 occupy a volume of 25 × 10-3 m3 at 25 oC. Calculate the
pressure exerted using the van der Waals’ equation, given that a = 0.417 N m 4 mol-2 and b =
0.037 × 10-3 m3 mol-1, R = 8.314 J K-1 mol-1.

( )
2
an
P+ 2
( V −nb )=nRT
V

2
nRT an
∴ P= −
(V −nb) V 2

n = 10 moles; R = 8.314 J K -1 mol-1; T = 25 + 273 = 298 K; V = 25 × 10 -3 m3; a = 0.417 N m 4

mol-2; b = 0.037 × 10-3 m3 mol-1

2
10 × 8.314 ×298 0.417 ×10
P= −3 −3
− −3 2
25 ×10 −(10 × 0.037 ×10 ) (25 ×10 )

P = 9.39 × 105 Nm-2 or 9.39 × 105 Pa

Exercise 10b: Compare the pressure gotten from van der Waals’ equation with that from
ideal gas equation.

PV =nRT

9
 nRT
P=
V

10 ×8.314 × 298
P= −3
=9.91 ×105 N m−2
25 ×10

Liquefaction of gases

Gases can be liquefied when subjected to high pressures and low temperatures; because under
these conditions, the kinetic energy of the gas molecules decreases and as a result, molecules
come close to one another. The volume occupied by the gas molecules also decreases. If the
lowering of temperature is continued, at some stage, the gas liquefies. This is because of the
increase in the intermolecular forces of attraction between them.

Joule-Thomson (J-T) effect

The effect is named after James Prescott Joule and William Thomson (Lord Kelvin). It
describes the increase or decrease (mostly) in the temperature of real gases or a liquid when
allowed to expand freely through a valve under adiabatic conditions (no heat transfer). The J-
T effect is an isenthalpic process (the enthalpy of the system is constant). Most gases (except
H, He, Ne) are cooled by J-T effect at room temperature; while H and He can be cooled at
low temperatures. Note that real gases are cooled by J-T effect at temperature lower than their
inversion temperature.

Applications of J-T effect

1. In refrigerators and air-conditioners.

2. It is used to liquefy gases in petrochemical industries.
3. In many cryogenic applications (example for the production of liquid nitrogen,
oxygen, argon etc.).

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