Kinetic theory

Chemistry Unit I D.Hines

The kinetic theory of matter explains the extent to which particles move in solids, liquids and gases. In
solids, the intermolecular forces of attraction are strong enough to keep particles close together and
held in fixed positions. They are not easily compressed due to the lack of space between the particles.
The particles are arranged in orderly fashion which gives it a definite shape as well as volume. The
kinetic energy in the particles cause them to vibrate in their fixed positions.

Liquids have more kinetic energy than solids, the energy is enough to overcome the forces of attraction
which hold particles in fixed positions. In liquids the intermolecular forces of attraction are not as strong
as that of solids therefore, the particles can vibrate as well as rotate, giving them freedom to flow and
assume the shape of whatever container they are poured in. The particles are not regularly arranged.
The particles are almost as close together as particles in a solid hence liquids have a definite volume and
are not easily compressed.

Changing state

When a solid is heated:

 The kinetic energy of the particles increases as the temperature increases, also there is an
increase in the vibrations of the particles.
 The forces of attraction between the particles weakens
 The solid melts when enough energy is transferred to make the particles slide over each other
 The temperature remains constant during melting and this constant temperature is called
melting.
 The melting point is the temperature when the solid is in equilibrium with the liquid

When a liquid is heated:

 The energy transferred increases the movement and energy of the particles. The temperature of
the liquid increases.
 The forces of attraction between the particles weakens until they can escape the surface of the
liquid to form vapour, this process is called evaporation or vaporization. Evaporation can take
place well below the boing point at a convenient temperature.
 The liquid boils when enough energy is transferred to allow an equilibrium between the liquid
and gas phase. This is when the external pressure is equal to the saturated vapour pressure.

These changes of state can be shown below on a heating curve

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General properties of gases

The particle in a gas:

 Are arranged randomly (disordered)

 Are far apart from each other
 Move rapidly and randomly

Assumptions of the Kinetic Theory and ideal gases

The kinetic theory of gases explains the extent to which the particles move in a gas. It allows us to
account for the behaviour of gases by making 5 basic assumptions:

 The gas particles are in constant random motion

 Gas particles have no volume. The molecules themselves occupy negligible volume when
compared to the volume occupied by the gas.
 Gas particles do not attract each other. The molecules exert no force on each other because
they are not close enough for intermolecular forces of attraction to exist between them
 Collisions between gas particles are perfectly elastic. When molecules collide no energy is loss.
 The average kinetic energy of the molecules is directly proportional to the absolute temperature
of the gas. As the temperature increases, the kinetic energy of the molecules increases and the
speed increases.

The Gas Laws

The gas laws are results of experiments explaining the responses of gases to changes in physical
quantities. The gases are referred to as ideal gases when they obey the gas laws under all conditions.

Boyle’s Law

Robert Boyle (1627-1691) investigated the relationship between the volume of a fixed mass of gas and
its pressure at constant temperature. The investigation indicated that the volume of a mixed mass of gas
is inversely proportional to its pressure at constant temperature.

P α 1/V

P = k/V

PV = k

P1V1 = P2V2

Initial pressure x initial volume = final pressure x final volume

Graphical representation of Boyle’s law

Example 1

A gas has a volume of 1.2 dm3, its pressure is 100 kPa. What is the volume of this gas when the pressure
is increased to 250 kPa at constant temperature?

Example 1.b

A gas has a volume of 120 cm3, its pressure is 2 atm. What pressure will this gas exert if its volume
changed to 2.5 m3?

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Charles Law

Jacques Charles (1746-1823) made detailed measurements on how the volume of a gas was affected by
changing the temperature. Charles law states that the volume of a fixed mass of gas is directly
proportional to its absolute temperature at constant pressure.

Mathematically this can be represented

VαT

V = kT

V/T = k

V1/T1 = V2/T2

Initial volume = final volume

Initial temperature final temperature

A graphical representation of Charles’s law

If we extend Charles law to extremely low temperatures, the volume of the ideal gas should become
zero. However in reality a gas would change phase or liquefy long before it reaches zero volume. The
temperature at which the volume of a gas would become zero if it did not condense is called the
absolute zero and is found from the graph above. This temperature is -273 and is called the absolute
temperature or the Kelvin.

We can convert the degrees Celsius to Kelvins by adding 273, for example 25 0C = 25 + 273 = 298K

N.B we use the Kelvin scale for calculations involving Charles law.

Example 2

At 27 0C a gas occupies a volume of 600 cm3. What volume does the gas occupy at 227 0C assuming that
the pressure remains constant.

You can combine both Boyle’s law and Charle’s law into one equation if pressure and temperature both
change.

P1V1 = P2V2
T1 T2

This is called the ideal gas equation of state.

Example 3

A gas occupies 2 m3 at 27 0C and 1.01 x 105 Pa. What volume will it occupy at 87 0C and 4.04 x 105 Pa.

Example 3.b

A gas occupies 3.5 m3 at 41 0C and 2.2 x 105 Pa. What pressure will it exert if it occupies a volume of 6.3
m3 at 332 K 0.

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The ideal gas equation

For an ideal gas we can combine Boyle’s law and Charles’ law. This gives us the ideal gas equation.

PV = nRT

Where :

P is the pressure in pascals, Pa (1atm = 101325 Pa) and (1kPa = 1000 Pa)

V is the volume in cubic meters, m3 (1 m3 = 1000 dm3), (1cm3 = 1ml) and (1m3 = 1,000,000 cm3), 1m3 =
1000 L

n is the number of moles of gas, mol

R is the gas constant (8.314 J K-1mol-1)

T is the temperature in Kelvin (K)

Example 4

Calculate the volume of a gas in a weather balloon which contains 0.24 Kg of helium at a temperature of
-25 0C and a pressure of 60 kPa (Ar He = 4.0, R = 8.314 J K-1mol-1)

Example 4.b

If I have an unknown quantity of gas at a pressure of 1.2 atm, a volume of 31 liters, and a temperature
of 87 oC, how many moles of gas do I have? (R = 8.314 J K-1 mol-1)

Example 4.c

If I contain 3 moles of gas in a container with a volume of 0.06 m3 and at a temperature of 400 K, what is
the pressure inside the container? (R = 8.314 J K-1 mol-1)

Deducing relative molecular mass

We can use a simple weighing method to deduce the relative molecular mass of a gas. A large flask of
known volume is filled with gas and the mass is found. If the temperature and pressure are known, we
can substitute all the values in the ideal gas equation to find M. This is mostly used for dense gases.

Since number of moles of gas (n) = mass of gas (m) / M r

Then PV = mRT/Mr

Therefore Mr = mRT/PV

Example 5

0.035 g of a gas was found to occupy a volume of 20 cm3 at 1.09 x 105 Pa and 27 0C. What is the relative
molecular mass of the gas?

Example 6

A flask of volume 2.00 dm3 contains 3.61 g of a gas. The pressure in the flask is 100 kPa and the
temperature is 20 0C. Calculate the relative molecular mass of the gas (R = 8.314 J K -1mol-1).

Real and ideal gases

An ideal gas is one which obeys the gas laws. On examining the behaviour of gases, these assumptions
of the kinetic theory shows that such as a gas does not exist in reality. However, under conditions of
high temperatures and low pressures real gases approach ideal gas behaviour.

Limitations of ideal gas behaviour

For ideal gases, it is assumed that a gas can be infinitely compressed or cooled and it will not liquefy.
However in reality if the gas is compressed or cooled enough it will deviate from ideal behaviour.

Real gases deviate from ideal gas behaviour at

 Low temperatures
 High pressures, greater 100 atm

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These gases do not obey Boyle’s and Charles’ law exactly. The kinetic theory is not always obeyed
because:

 We cannot ignore the volume of the particles

 The attraction between the particles is not zero

At very high pressure and very low temperature:

The kinetic energy of the molecules decreases, this results in the collisions becoming less elastic and no
longer being able to overcome the intermolecular forces of attraction between the molecules. The
particles are closer together so the assumption of the kinetic theory that there are no forces of
attraction between the molecules no longer holds. Also the attractive forces of the molecules bring
them close enough so that the volume of the gas become smaller, thus the assumption that the volume
of the molecules is negligible when compared to the volume occupied by the gas becomes invalid.

Gases which do not obey Boyle’s and Charles’ law at all temperatures and pressures are called real
gases.

Gases with stronger intermolecular forces of attraction show greater deviation from ideal gases.

Hydrogen, nitrogen and carbon dioxide show deviations from Boyle’s law over a range of pressures.

Exercises

1. a. List five assumptions of the kinetic theory

b. State Charles’ law
c. Describe how the kinetic theory explains Charles’ law
d. A mass of gas occupies 1000 cm3 at a fixed pressure and temperature of 25 0C. What volume
will the gas occupy at 35 0C if it shows ideal behaviour.

2. a. What is meant by the term ideal gas?

b. Under what conditions of temperature and pressure will a real gas deviate from ideal gas
behaviour.

c. What two assumptions of the kinetic theory of gas do not hold under the conditions described
in (b) above.

d. in an analysis, 0.1 g of a sample X occupied 25 cm3 at 100 0C and atmospheric pressure.

Calculate the relative molecular mass of X

3. a. Sketch the graph showing the relationship between the volume and temperature of a gas at a
fixed pressure

b. Show on the graph the temperature at which the volume of an ideal gas become zero.

c. 1.09 g of a gas occupied 920 cm3 and 93 kPa. Calculate the relative molecular mass of the gas.

4. Use the kinetic theory of matter to explain the following:

a. the nature of the liquid state

b. the change of state from liquid to gas

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 c. gases have lower densities than liquids

5. A weather balloon containing 54 dm3 of gas at 30 0C and 2 atmosphere rises to an altitude

where the atmospheres rises to an altitude where the temperature is 20 0C and the pressure of the gas
is 1 atmosphere.

a. Calculate the change in volume of the gas in the balloon

b. Suggest a consequence of the change in volume of the gas

c. State an assumption made in your calculation.

6. June 2007 #4 [15 marks]

The safety air bags used in many vehicles are inflated on impact by a gas that is

produced from the rapid decomposition of sodium azide, NaN3.

(a) Assuming that the gas produced behaves as an ideal gas under these conditions:

(i) State TWO properties of an ideal gas. (2 marks)

(ii) Use the ideal gas equation to calculate the number of moles of gas produced

in an air bag of volume 40.0 dm3 at a pressure of 2.0 x 102 kPa and a

temperature of 30oC. (3 marks)

(iii) Given that the mass of gas produced in the air bag is 90.0 g, use the answer

from (a)(ii) to calculate the molar mass of the gas and suggest its identity.

(2 marks)

(iv) Write the equation for the decomposition of NaN3. (2 marks)

(b) (i) State the conditions of temperature and pressure under which gases deviate

from ideality. (2 marks)

(ii) Describe the property of the gas molecule that is responsible for the deviation

from ideality. (2 marks)

Total 15 marks