UNIVERSITY OF NAIROBI

COLLEGE OF BIOLOGICAL AND PHYSICAL SCIENCES

SCHOOL OF PHYSICAL SCIENCES

SCH 103; PHYSICAL CHEMISTRY 1

By:

Dr. John N. Wabomba

Department of Chemistry
University of Nairobi.

Email: jwabomba@uonbi.ac.ke.

1
 COURSE OUTLINE.

1. THE GASEOUS STATE

1.1. Gaseous states of matter and the gas laws.

1. 2. Using the equation of the ideal gas law; Gaseous mixtures

1. 3. Kinetic theory of gases

1. 4. Behaviour of real gases

1. 5. Determination of molar masses of gases

2. SOLUTIONS

2.1. Classification of solutions; Properties of solutions of volatile (ideal) liquids

2.2. Colligative properties of solutions

3. CHEMICAL EQUILIBRIUM

3.1. Equilibria for gaseous and heterogeneous reaction

3.2. Using equilibrium constant

3.3. Changing the reaction conditions and choosing optimum conditions for reactions.

4. IONIC EQUILIBRIUM

4.1. Acid- Base Concepts

4.2. Acid-Base Equilibrium

2
 INTRODUCTION

Physical chemistry can be defined as the study of macroscopic, atomic, subatomic, and

particulate phenomena in chemical systems in terms of laws and concepts of physics. It
applies the principles, practices and concepts of physics such as; 
 Motion
 Energy 
 Force 
 Time 
 Thermodynamics 
 Quantum physics 
 Statistical mechanics 
 Dynamics and 
 Equilibrium.

Physical chemistry can also be viewed as

the branch of chemistry concerned with the way in which the physical
properties of substances depend on and influence their chemical
structure, properties, and reactions

Investigations in physical chemistry combine tools of physics, chemistry and mathematics

to uncover information about processes ranging from for instance; the immune response of
the body to the structure and reactivity of semiconductor surfaces.

Some of the relationships that physical chemistry strives to resolve include the effects of:

1. Intermolecular forces that act upon the physical properties of materials

(plasticity, tensile strength, surface tension in liquids).
2. Reaction kinetics on the rate of a reaction.
3. The identity of ions and the electrical conductivity of materials.
4. Surface chemistry and electrochemistry of membranes.
5. Interaction of one body with another in terms of quantities
of heat and work called thermodynamics.

3
 6. Transfer of heat between a chemical system and its surroundings during change
of phase or chemical reaction taking place called thermochemistry
7. Study of colligative properties of number of species present in solution.
8. Number of phases, number of components and degree of freedom (or variance) can
be correlated with one another with help of phase rule.
9. Reactions of electrochemical cells.

THE GASEOUS STATE

Under certain conditions of pressure and temperature, most substances can exist in any of the
three states of matter i.e. solid, liquid or gas (also plasma). Water for example exists in the
solid state as ice, liquid state as water and in the gaseous state as steam. The physical
properties of a substance often depend on the state of the substance.

Molecular motion in gases is totally random, and the forces of attraction between molecules
are so small/weak that molecules move freely and independent of each other. A gas subjected
to changes in temperature and pressure behaves according to much simpler laws than do
liquids and solids.

The laws that govern this behavior have played an important role in the development of the
atomic theory of matter and the kinetic molecular theory of gases.

Pressure of a gas
Gases exert pressure on any surface with which they come in contact, because gas molecules
are constantly in motion. Pressure can be defined as force per unit area. This is the force
exerted by a gas as a result of collisions that exert force which is experienced as a steady
pressure. Pressure exerted by the atmosphere is measured with a barometer.

Units of pressure.
Pressure is one of the most readily measurable properties of a gas. In order to understand the
units of measurement of gas pressure are derived, it is good to begin with velocity and
acceleration.
Velocity is the change in distance with time i.e.

4
 Dis tan ce moved
Velocity= =m/s
Elapsed time
We know that force as defined by Sir Isaac Newton can be given as;
Force=Mass× Accaeleration
The SI unit for force is Newton, where;
2
1 N =1kg m/s
But since pressure is defined as force per unit area, then it follows that;
Force
Pr essure=
Area
The SI unit for pressure is the Pascal (Pa) which is defined as one Newton per square
meter;
2
1 Pa=1 N /m
Other units of pressure
1 atm=760 mmHg=760 torr
5
1 atm=101 , 325 Pa=1 .01325×10 Pa
Because 1000 Pa = 1 kPa (kilopascal), then;
2
1 atm=1 .01325×10 kPa
A pressure of 1 x 105 Pa (1 bar) is the standard pressure for reporting data.

Atmospheric Pressure
Atoms and molecules of the gases in the atmosphere, like those of all other matter, are subject
to Earth’s gravitational pull. As a consequence the atmosphere is much denser near the
surface of the earth than at high altitudes. This implies that the force experienced by any area
exposed to Earth’s atmosphere is equal to the weight of the column of air above it.
The atmospheric pressure is thus the pressure exerted by Earth’s atmosphere. The actual
value of atmospheric pressure depends on location, temperature and weather conditions.

Atmospheric pressure is measured using a barometer. A barometer consists of a long glass

tube, closed at one end and filled with mercury. If the tube is carefully inverted in a dish of
mercury so that no air enters the tube, some mercury will flow out of the tube into the dish,
creating a vacuum at the top. See Figure 1 bellow;

5
 Figure 1: Mercury Barometer.

The weight of the mercury remaining in the tube is supported by atmospheric pressure acting
on the surface of the mercury in the dish. Standard atmospheric pressure (1 atm) is equal to
the pressure that supports a column of mercury exactly 760 mm (76cm) high at 0 oC at sea
level. This implies that the standard atmosphere equals a pressure of 760mmHg, where mmHg
represents the pressure exerted by a column of mercury 1mm high. The mmHg unit is also
referred to as the Torr, named after Evangelista Torricelli, an Italian scientist who invented a
barometer. Thus;
1 torr=1 mmHg
Example 1
The pressure outside a jet plane flying at high altitude falls considerably below standard
atmospheric pressure. The air inside the cabin must be pressurized to protect the passengers.
What is the pressure in atmospheres (atm) in the cabin if the barometer reading is 688mmHg?

Solution
We know that; 1 atm=760 mmHg

Therefore pressure in the cabin is given by;

1 atm
Pr essure=688 mmHg×
760 mmHg
=0 . 905 atm

6
Example 2
The atmospheric pressure in Nairobi on a certain day was 732 mmHg. What was the pressure
in kPa?

Solution;
The pressure in kPa can be determined as;

1. 01325×10 5 Pa
Pr essure=732 mmHg×
760 mmHg
=9.76×104 Pa
¿97.6 kPa
Exercise
1. Convert 746 mmHg into atmospheres.
2. Convert 295 mmHg into kilopascals.

Manometer
A manometer is a device used to measure the pressure of gases other than the atmosphere.
The principle operation of a manometer is similar to that of a barometer. There are two types
of manometers; (a). Closed tube manometer and (b). Open tube manometer.
The closed tube manometer is normally used to measure pressures below atmospheric
pressure whereas the open tube manometer is better suited for measuring pressures equal to or
greater than atmospheric pressure. See Figure below;

Figure 2: Closed-end manometer (a) and open-end manometers (b and c). In (b) gas
pressure is less than atmospheric pressure; in (c) gas pressure exceeds
atmospheric pressure.

7
Nearly all barometers and manometers use mercury as the working fluid. The reason is that
mercury has a very high density (13.6 g/cm3) compared with most other liquids. This property
enables the construction of manageably small barometers and manometers.

The Gas Laws.

Gas laws as we know them today, are a product of many experiments that were carried out on
physical properties of gases over several centuries. Gas laws generally relate to the
macroscopic behaviour of gaseous substances. These laws have played a major role in the
development of many ideas in chemistry related to gases. The gas laws of particular interest
are;
1) Boyle's law,
2) Charles' and Gay-Lussac’s law, and
3) Avogadro's law.
The three laws are usually combined to form the equation of state which is very useful in
solving many problems involving gases.

In order to describe the states of gas, at least three of following variables must be specified i.e.

Table 1: Variables used in describing state of a gas

(i). The space occupied by a sample of a gas (Volume, V)
(ii). The number of molecules present in the sample (Moles, n)
(iii). Pressure (Pressure, P)
(iv). Temperature (Temperature, T)

Boyle’s Law; The Pressure - Volume Relationship

In the seventeenth century, Robert Boyles (British chemist) studied the behaviour of gases
systematically and quantitatively. Boyle investigated the pressure-volume relationship of a
gas sample using an apparatus like that shown in Figure 3 below.

Boyles noticed that when temperature is held constant, the volume (V) of a given amount (n)
of a gas decreases as the total applied pressure (P) is increased.

8
Figure 3: Boyle's Experiment Using a J-Shaped Tube to Determine the Relationship
between Gas Pressure and Volume. 

The pressure-volume data recorded for such an experiment are consistent with these
mathematical expressions showing an inverse relationship. This relationship is known as the
Boyle’s law, which states that; “the pressure of a fixed amount of gas at a constant
temperature is inversely proportional to the volume of the gas”
The mathematical expression showing the inverse relationship between pressure and volume
can be given as;
I
Pα
V , temperature (T) is constant for a given amount
of gas (n).
This expression can be re-written as;
1
P=k 1 x
V
Where; k1 is a constant called the proportionality constant.
Rearranging the above equation, we obtain
PV =k 1 =cons tan t
Thus it follows from the Boyle’s law that the product of the pressure and volume of a gas at
constant temperature and amount of gas is constant. Thus, for example, doubling the pressure
reduces the volume by half.

9
Graphical Representation of Boyle’s Law
The two conventional ways of expressing Boyle’s findings graphically are shown in Figure 4
below;

Figure 4: Boyle’s law findings (a) Graph of the equation PV =k 1 ; (b) Graph of the

equivalent equation P=k 1×1 /V

The equation of graph 4b is a linear equation of the form

y=mx +c , where b=0 and m=k 1
1
Hence it can be tested by plotting experimental values of V against P and seeing how
close the result is to a straight line.

Although the individual values of pressure and volume can vary greatly for a given sample of
gas as long as the temperature is held constant and the amount of gas does not change, P times
V is always equal to the same constant.

Therefore, for a given sample of gas under two different sets of condition at constant
temperature, we have;
P1 V 1=k 1 =P2 V 2

Or simply;
P1 V 1=P 2 V 2

10
Where; V1 and V2 are the volumes at pressure P1 and P2 respectively.

One common application of Boyle’s Law is to use the above equation to predict how the
volume of a gas will be affected by a change in pressure, or how the pressure exerted by a gas
will be affected by a change in volume.

Example
The pressure in a 50L oxygen cylinder is 15.7atm at 21 0C, what volume of oxygen can we get
from the cylinder at 210C if the atmospheric pressure is 1atm?
Solution;
Let P1 and V1 be the initial pressure (15.0atm) and initial volume (50L), and P2 and V2 be the
final pressure (1atm) and final volume (?) respectively.

It then follows that; P2 V 2=P1 V 1

V 1×P1
V 2=
Therefore; P2

When we substitute the values into this equation, we get;

15 atm
V 2 =50 L× =750 L
1 atm

Exercise:
A sample of hydrogen gas at 0oC and 700 mmHg has a volume of 4.00L. What would be the
volume of the gas if the pressure was changed to 760 mmHg at the same temperature?

Charles’ Law: Temperature – Volume Relationship

We have already seen that Boyle’s Law depends on the temperature of the system remaining
constant. But suppose the temperature changes: How does this change affect the volume and
pressure of a given gas?

The earliest investigator of this relationship was a French scientists, Jacques Alexandre
Charles (1746 – 1823). His studies showed that, at constant pressure, the volume of a gas
sample expands when heated and contracts when cooled. In 1787, Charles observed that the
volume of a fixed quantity of gas at constant pressure increases linearly with temperature.

11
The quantitative relations involved in changes in gas temperature and volume turn out to be
remarkably consistent.
At any given pressure, the plot of volume versus temperature yields a straight line. See figure

Figure 5: Plots of volume versus temperature (a) for equal-sized samples of H 2 at three
different pressures, (b) for different amounts of selected gases at 1atm
pressure, all the plots extrapolate to a value of V = 0 at −273.15°C, regardless
of the identity or the amount of the gas.

Note: The solid lines show the experimentally measured data down to −100°C, and the
broken lines show the extrapolation of the data to V = 0. The temperature scale is given in
both degrees Celsius and Kelvins. Although the slopes of the lines decrease with increasing
pressure, all of the lines extrapolate to the same temperature at V = 0 (−273.15°C = 0 K).

This is to say that, if the substance remain gaseous, the volume occupied will be zero at –
273.150C.

In 1848 Lord Kelvin realized the significance of this behaviour. He identified the temperature
–273.150C as absolute zero, theoretically the lowest attainable temperature. Then he set up an
absolute temperature scale, now called the Kelvin temperature scale with absolute zero as the
starting point. On the Kelvin scale, one Kelvin (K) is equal in magnitude to one degree
Celsius. The only difference between the absolute temperature scale and the Celsius scale is
that the zero position is shifted. A summary of the relationships between the two scales is as
follows:-

12
Table 2: Relationship between Kelvin (Absolute Temperature) and Celsius Scale
Kelvin Scale Celsius Scale
Absolute zero 0K -273.15oC
Freezing point of water 273.15 K 0oC
Boiling point of water 373.15 K 100oC

By convention we use T to denote absolute (Kelvin) temperature and t to indicate temperature

on the Celsius scale. The dependency of volume on temperature is given by;

V α T , P is cons tan t
⇒V =k 2 T

V
=k
Or; T 2

Where; k2 is the proportionality constant.

This equation is known as Charles’s Law which states that;

“The volume of a fixed amount of gas maintained at constant pressure is directly
proportional to the absolute temperature of the gas”.

Note: that the proportionality constant in the above equation (k2) is equal to nR/P .
Just as it was done for pressure-volume relationships at constant temperature, we can compare
two sets of conditions for a given sample of gas at constant pressure.
V1 V2
=k 2 =
We can write T1 T2

V1 V 2
=
Or; T1 T2

Where; V1 and V2 are the volumes of the gas at temperatures T1 and T2 (both in Kelvins),
respectively.

13
Example
A quantity of gas at 100C and 1atm pressure occupied a volume of 200cm 3. What volume will
it occupy at –200C given that its pressure is constant.

Solution
V1 V
=k 2 = 2
We know that; T1 T2

Where; V1 = 200cm3, T1 = (10 + 273) K = 283K, T2 = (-20 + 273) K = 253K, V2 =?

V 1 T 2 200 cm 3×253 K
V 2= = =178 . 8 cm3
Hence; T 1 283 K

Gay-Lussac's Law:  Pressure-Temperature Relationship

Gay-Lussac's law is also referred to variously as the Pressure Law or Amontons's law.

Guillaume Amontons (1663 – 1705) was a French scientific instrument inventor

and physicist.
Amontons investigated the relationship between pressure and temperature in gases though he
lacked accurate and precise thermometers. Though his results were at best semi-quantitative,
he established that the pressure of a gas increases by roughly one-third between the
temperatures of cold and the boiling point of water. This was a substantial step towards the
subsequent gas laws and, in particular, Gay-Lussac's law.

Joseph Louis Gay-Lussac (1778 – 850) is however credited with being the first to publish
convincing evidence (1808) that shows the relationship between the pressure and temperature
of a fixed mass of gas kept at a constant volume while building an "air thermometer".

He found out that; when the temperature of a sample of gas in a rigid container is increased,
the pressure of the gas increases as well. The increase in kinetic energy results in the
molecules of gas striking the walls of the container with more force, hence causing an
increase in pressure.

Gay-Lussac's Law states that;

14
 “The pressure of a given mass of gas varies directly with the absolute temperature
of the gas, when the volume is kept constant”.

Gay-Lussac's Law is very similar to Charles's Law, with the only difference being the type of
container. Whereas the container in a Charles's Law experiment is flexible, it is rigid in a
Gay-Lussac's Law experiment.

The law has a particularly simple mathematical form if the temperature is measured on an
absolute scale, such as in Kelvins. The law can then be expressed mathematically as

P α T , Vcons tan t
P=k 3 T
P
=k
Or; T 3

Note:
k 3 =nR /V ; and from the above equation, we can have;

For comparing the same substance under two different sets of conditions, the law can be
written as:

P1 P2
=k 3 =
T1 T2
Or;
P1 P2
=
T1 T2
Where; P1 and P2 are the pressures of the gas at temperatures T1 and T2, respectively.
k3 is a constant.

Example

The gas in an aerosol can is under a pressure of 3.00atm at a temperature of 25oC. It is

dangerous to dispose of an aerosol can by incineration. What would the pressure in the
aerosol can be at a temperature of 845oC?

Solution

We know that:

15
  P1=3.00atm
 T1=25oC = 298K
 T2=845oC = 1118K

 P2 = ?atm

Use Gay-Lussac's Law to solve for the unknown pressure (P2). That is;

P1 P 2
=
T1 T2

Rearrange the equation algebraically to solve for P2.

P1 ×T 2
P2 =
T1

Now substitute the known quantities into the equation and solve.

3 . 00 atm×1118 K
P2 = =11. 3 atm
298 K

N/B: The pressure increases dramatically due to large increase in temperature.

Example:
Find the temperature in Celsius needed to change the pressure of 10.0 liters of a gas that has a
pressure of 97.0kPa at 25oC to standard pressure. Standard pressure is 101.325kPa.

Solution: 
First, we have to convert 25oC to Kelvin (273 + 25 = 298K)
From Gay Lussac's law, we know that;
           P α T ( at constant V and n )

P1 P 2
=
        T1 T2
Here, P1= 97.0kPa;          T1= 298 K;          P2 = 101.325kPa;          T2 = ?

16
Putting the above values into the equation, we will get, 

97 . 0 kPa 101 .325 kPa

=
           298 K T2

101 .325 kPa×298 K

T 2= =311. 3 K
      97 . 0 kPa
In order to get temperature in Celsius, we will have to subtract T2 by 273.15,               
o
      
T 2 =( 311. 3−273 . 15 ) C=38 . 15o C

Gay-Lussac's Law of Combining Volumes

Gay-Lussac described how the pressure of enclosed gas is directly proportional to its
temperature (1808). Gay-Lussac found out that; two volumes of hydrogen and one volume of
oxygen reacted to yield two volumes of water.

In the reaction;

2 H2(g) + O2(g) → 2 H2O(g)

2 volumes of H2 react with 1 volume of O2 to produce 2 volumes of H2O.

It can also be expressed in another way of example, 100 mL of hydrogen combine with 50 mL
of oxygen to give 100 mL of water vapour.

Hydrogen (100 mL) + Oxygen (50 mL) = Water (100 mL)

The law of combining volumes states that,

“When gases react together they do so in volumes which bear simple whole number
ratios provided that the temperature and pressure of the reacting gases and their
products remain constant”

Example 1: 
Consider the reaction: 2H2 (g) + O2 (g) → 2H2O (g)

17
 a) What volume of steam is formed from 20 cm3 of hydrogen and 20 cm3 of oxygen
mixed together?
b) What gas(s) is in excess, and by what amount?
 
Solution: 
(a) The ratio of their volumes is; 2 vols. : 1 vol. → 2 vols.

20 vols. : 10 vols.  → 20 vols.

That means, 20 cm3 of hydrogen will combine with 10 cm3 of oxygen to form 20
cm3 of steam.

(b) Oxygen is in excess by 10 cm3.

Example 2:
Some industrial processes produce toxic carbon monoxide as a by-product and this gas must
be dealt with. One way is to burn it to release heat energy for power generation. Carbon
monoxide burns in air to form carbon dioxide according to the equation:
2CO ( g ) + O 2 (g ) → 2CO 2 ( g )
(a) If carbon monoxide is produced in an industrial process at the rate of 50 dm 3 per
minute, what rate of oxygen input is required to completely burn it to harmless carbon
dioxide?
(b) However, it is expensive to use oxygen, so air is employed for the combustion
process.  If you assume air contains approximately 20% oxygen what rate of air needs
to be pumped into the reactor for the carbon monoxide combustion process?

Solution:
(a)
1. The equation reads as 2 mol CO reacts with 1 mol O2 to form 2 mol of CO2
2. Therefore 2 volumes of CO reacts with 1 volume of O 2 to form 2 volumes of CO 2 by
ratio. This implies that;
Volume of CO 2 produced Volume of CO produced/consumed
Volume of O 2 needed = =
2 2
3. Hence, for every 50 dm3 of CO produced you need 25 dm3 of oxygen to burn it.

18
 3
CO produced 50 dm /min
Volume of O2 needed = = =25 dm3 /min
2 2
4. You need to pump in oxygen at the rate of 25 dm3/min

(b)
1. If air is composed of 20% oxygen, then 1/5th of air is oxygen, so you need five times
more air than pure oxygen.
2. Therefore rate of air needed;
3 3
=5×25dm /min=125dm air /min

Avogadro’s Law; The Volume – Amount Relationship

The work of an Italian scientist Amedeo Avogadro complemented the studies of Boyles,
Charles and Gay-Lussac. Three years after Gay-Lussac’s observations on combining gas
volumes (1811), Avogadro interpreted the observations by proposing and publishing what is
currently known as the Avogadro’s law, (also known as Avogadro’s principle or Avogadro’s
hypothesis) which states that;
“The total number of atoms/molecules of a gas (i.e. the amount of gaseous
substance) is directly proportional to the volume occupied by the gas at constant
temperature and pressure.”

Avogadro’s law is closely related to the ideal gas equation since it links temperature, pressure,
volume, and amount of substance for a given gas. Avogadro, suggested that two dissimilar
ideal gases occupying the same volume at a given temperature and pressure must contain an
equal number of molecules. Avogadro’s hypothesis was not accepted until 1860.

From the hypothesis, it follows that the volume of any given gas must be proportional to the
number of molecules present in it, that is;

V α n ( at const . temperature and pressure ) ,

19
 ⇒ V =k 4 n

V
=k 4
n
Where V is the volume of the gas, n denotes the amount of gaseous substance (often expressed
in moles), and k4 is a constant (k4 = RT/P).

When the amount of gaseous substance is increased, the corresponding increase in the volume
occupied by the gas can be calculated with the help of the following formula:
V1 V2
n1
=k 4 =
n2
( k 4 = Avogadro ' s const . )

V1 V2
⇒ =
n1 n2
The above equation is the mathematical expression of Avogadro’s Law, which states that;

“At constant pressure and temperature, the volume of a gas is directly proportional
to the number of moles of the gas present”.

According to this law it can be seen that when two gases react with each other, their reaction
volumes have a simple ratio to each other. For example consider the synthesis of ammonia
from molecular hydrogen and molecular nitrogen:
3 H2(g ) N 2( g ) 2 NH 3 ( g )
+ →
3 mol 1 mol 2 mol

Because at the same temperature and pressure, the volumes of gases are directly proportional
to the number of moles of the gases present, we can now write;
3H2(g) + N2(g) 2NH3(g)
3 volumes. 1 volume. 2 volumes.
If we represent molar gas volume at some temperature and pressure by Vm, the volume
occupied by n moles of any gas at this temperature and pressure is;
V =nV m
.

Where Vm, has the same value for all gases at a fixed temperature and pressure.

20
Examples of Avogadro’s Law
1) The process of respiration is a great example of Avogadro’s law. When humans
inhale, the increase in the molar quantity of air in the lungs is accompanied by an
increase in the volume of the lungs (expansion of the lungs).
2) Another common example of Avogadro’s law is the deflation of automobile tires.
When the air trapped inside the tire escapes, the number of moles of air present in the
tire decreases. This results in a decrease in the volume occupied by the gas, causing
the tire to lose its shape and deflate.

Example 1
One mole of helium gas fills up an empty balloon to a volume of 1.5L. What would be the
volume of the balloon if an additional 2.5 moles of helium gas is added? (Assume that the
temperature and the pressure are kept constant)

Solution:
Given that;
Initial amount of helium (n1) = 1mol
Initial volume of the balloon (V1) = 1.5 L
Final amount of helium (n2) = 1mol + 2.5mol = 3.5mol
Final volume of the balloon (V2) =?

V1 V 2
=
As per Avogadro’s law; n1 n2

Therefore, the final volume of the balloon can be determined as follows;

V 1 n 2 1. 5 L×3 .5 mol
V 2= = =5. 25 L
n1 1mol
N/B: The balloon would occupy a volume of 5.25L when it contains 3.5 moles of helium gas.

Example 2
A tire containing 10 moles of air and occupying a volume of 40L loses half its volume due to
a puncture. Considering that the pressure and temperature remain constant, what would be the
amount of air in the deflated tire?

Solution:

21
Given that:
Initial amount of air (n1) = 10mol
Initial volume of the tire (V1) = 40L
Final volume of the tire (V2) = 20L
Final amount of air (n2) =?

According to Avogadro’s law, the final amount of air in the tire;

V 2 n1 20 L×10 moles
n2 = = =5 moles
V 1 40 L
N/B: The deflated tyre would contain 5 moles of air.

The Ideal Gas Equation

We have already seen that in;
1
Vα , (at cons tan t n and T )
Boyle’s law: P

Charles’s law: V α T , (at cons tan t n and P )

Gay Lussac’s law: P α T ( at n and V cons tan t )

Avogadro’s law: V α n , ( at cons tan t P and T )

All of these gas laws can be combined into a single statement/master equation for the
behaviour of gases called the Ideal Gas Law:
nT
Vα
P
nT
V =R
P
Or; PV =nRT

Where R, the proportionality constant, is called the gas constant while the equation
PV  nRT , which describes the relationship among the four experimental variables P, V, T
and n is called the Ideal gas equation.

An ideal gas is a hypothetical gas whose Pressure-Volume-Temperature behaviour can be

completely accounted for by the ideal gas equation. The molecules of an ideal gas do not

22
attract or repel one another, and their volume is negligible compared with the volume of the
container.

Although there is no such thing in nature as an ideal gas, discrepancies in the behaviour of
real pressure range do not significantly affect calculations. Thus we can use the ideal gas
equation to solve many gas problems. It is however important to note at this stage that before
we can apply the ideal gas equation to a real system, we must evaluate the gas constant R. at
0OC (273.15K) and 1atm pressure, many real gases behave like an ideal gas.

Experiments show that under these conditions, 1mole of any gas occupies 22.414L and
contains 6.023 x 1023 molecules. The condition 0oC and 1atm are called Standard
Temperature and Pressure (STP).

We can obtain the value of R from the experimental value of molar volume at (0oC, 1atm).

The data for evaluation of R are;

Variable Value
P 1atm
V 22.414 L
T 0OC = 273.15K
n 1 mol

We already know that;

PV
n=
RT
PV
⇒R=
nT ¿ =0.082057L.atm /( K .mol) ¿¿

(1mol) (273.15K ) ¿
=(1 atm) (22.414L)¿
¿

Note: Similarly you can calculate the values of R using the other units of pressure (i.e. Torr
(mmHg) and Pascal). Compare your answers with values in Table 3 below;

23
 Table 3: The gas constant (R) in various units
Unit of P R Units
1. Atmosphere 0.082057 L .atm / (K.mol)
2. Torr/mmHg 62.37 L. torr / (K.mol) or L.
mmHg / (K.mol)
3. Pascal 8.31441 x 103 L.Pa / (K.mol)
4. Calories 1.9872 Cal/(K.mol)
5. Joules 8.314 J/(K.mol)

Units for the Gas Constant

The gas constant R, can be expressed in units J/K.mol.
From our previous studies we know that;
force mass×acceleration
pressure= =
area area
volume×density×acceleration
=
area
=length×density×acceleration
By definition, the standard atmosphere is the pressure exerted by a column of mercury exactly
76cm high of density 13.5951g/cm3 in a place where acceleration due to gravity is
980.665cm/s2.

In order to express pressure in N/m2 we can write;

4 3
density of mercury ( ρ ) =1.35951×10 kg/m
2
acceleration due to gravity ( g )=9.80665 m/ s
The standard atmosphere is given by;

1 atm=( 0.76mHg ) ( 1.35951×104 kg/m3 ) ( 9.80665 m/s 2 )

= 101,325 kg m/m2. s2

24
Note: One newton is the force needed to accelerate one kilogram of mass at the rate
of one metre per second squared in the direction of the applied force.
This implies that; 1N = 1 kg⋅m⋅s−2

The equation can thus be expressed as;

1 atm = 101,325 N/m2

= 101,325 Pa
From our previous calculations, it was found that the gas constant R is equal to 0.082057
L*atm/K*mol.

Using the conversion factors;

−3 3
1 L=1×10 m
2
1 atm=101,325 N /m

We can write;

L atm 1×10−3 m3 101,325 N /m2

(
R= 0.082057
K mol 1L )( )(
1 atm )
Nm
=8.314
K mol
J
=8.314
K mol

And

1 L∗ atm=( 1×10−3 m3) ( 101,325N /m2 )

= 101.3 N m
= 101.3 J
Example 1:
How many grams of oxygen are there in a 50.0 L tank at 21oC when the oxygen pressure is
15.0 atm?
Solution
Mass of oxygen is related to its number of moles n. we have been given that;
P = 15.0 atm, V = 50.0 L, T = 21OC = 294 K and n = ?

25
We can use the ideal gas law to solve for n. where;
PV
n=
RT
The proper value for R to be used depends on the units of V and P. Since we have liters and
atmospheres then; R = 0.0821 L.atm/K.mol

15. 0 atm×50.0 L
n= =31.1 mol
Therefore; 0.0821 L.atm/( K .mol)×294 K
But 1 mole of O2 gas weighs 32g, therefore, 31.1 moles will weigh

32 .0g
31 .1 mol × =995. 2 g
1mol
Example 2:
Nitrogen is heated to 500 K in a vessel of constant volume. If it enters at a pressure of
100atm and a temperature of 300 K, what pressure would it exert at the working temperature
if it is assumed that nitrogen behaves as a perfect gas?
Solution
From the ideal gas equation we know that;
PV
=R
nT
For both the initial (1) and final (2) conditions, and noting that R is a constant, then we can
have;
P1 V 1 PV
=R= 2 2
n1 T 1 n2 T 2
Or;
P1 V 1 P2 V 2
=
n1 T 1 n2 T 2
The constant quantities; amount (n1 = n2) and volume (V1 = V2) cancel out and the data can
then be substituted into the resulting expression.

P1 P2
=
T1 T2

T2
⇒ P2 = ×P 1
T1

26
 500 K
P2 = ×100 atm=167 atm
300 K

Exercise;
1. Sulphur hexafluoride (SF6) is a colourless and odourless gas. Due to its lack of
chemical reactivity, it is used in electronic equipment. Calculate the pressure (in atm)
exerted by 1.82 moles of the gas in a steel vessel of volume 5.43 L at 69.5OC.
2. Calculate the volume (in liters) occupied by 2.12 moles of nitric oxide (NO) at 6.54
atm and 76oC
3 A sample of chlorine gas occupies a volume of 946 mL at a pressure of 726 mmHg.
Calculate the pressure of the gas (in mmHg) if the volume is reduced at constant
temperature to 154 mL.

The Density of a Gas

Gas density is defined as the mass of the gas occupying a certain volume at specified pressure
and temperature. Gas density is a function of the pressure and temperature conditions for the
gas. Due to its high compressibility, gas can change its volume significantly with change in
pressure. Therefore, density changes (at low pressure) can be significant. At high pressures,
the gas molecules are packed together and may approach the behavior of liquid (small
variation of density with pressure).

The ideal gas equation can be used to determine the density of a gas, its molar mass and the
volume(s) of a gas/gases formed or consumed in a chemical reaction(s). One of the
applications of the ideal gas equation, is in measuring and calculating gas density.

The ideal gas equation can be rearranged from; PV =nRT

n P
=
To; V RT
Number of moles n is given by;
m
n=
Μ
Where; m of the mass of the gas in grams and M is its molar mass of the gas in question.

27
Replacing for n in the above equation gives;
m P
=
MV RT
But since density, d, is mass per unit volume, we can write;
m PM
d= =
V RT

The density equation shows that:

(i) The density of a gas increases as the pressure is increased.
(ii) The density decreases as the temperature is raised. So long as the pressure is kept
constant the gas expands when heated.
(iii) The density of a gas increases with increasing molar mass.

Note: Gaseous molecules are separated by large distances compared to their size hence
density of gases is very low under atmospheric conditions. Gas densities are therefore
usually expressed in grams per liter (g/L) rather than grams per milliliter (g/mL)

Example 1:
Calculate the density of ammonia (NH3) in grams per litre (g/L) at 700 mmHg and 50oC.

Solution:
First, we convert the pressure into atmospheres, thus we have;
1 atm
P=700 mmHg× =0 .921 atm
760 mmHg
M PM
d= =
Using the equation V RT where; T = 273 + 50 = 323K, M = 17.03g/mol and R =
0.0821L.atm/K.mol we have;
( 0 . 921 atm )×( 17 . 03 g/mol )
d= =0 .591 g/ L
( 0 . 0821 L . atm/K . mol )×( 323 K )

Example 2: 
The volume of chlorine at 27oC is 564.3mL. It has a mass of 1.607g and pressure is 740torr.
Calculate the density of chlorine.

28
Solution: 
First, we reduce the volume to the standard conditions (STP).

564 .3 mL×273 K 740 torr

V 2= × =500 mL
300 K 760 torr

Since, the mass of the chlorine remains unchanged, we have;

M 1 . 607g
d= = =0. 003214 g /mL
V 500mL

So, the density of chlorine gas is 0.003214g/mL.

Example 3: 
Calculate the density of SO2 gas at 40oC and 730 mmHg.

Solution: 
The molecular weight of SO2 is 64 g/mol.

PM
d=
We know that; RT where; T = 273 + 40 = 313K and R = 62.4 L. mmHg / (K.mol)

730mmHg×64g/mol
d= =2 .39 g/ L .
Thus we have; 62 . 4L⋅mmHg/K⋅mol×313K

Hence, the density of SO2 gas is 2.39 g/L.

Exercise
1. What is the density (in g/L) of uranium hexafluoride (UF6) at 779mmHg and 62oC?
2. A sample of gas has a density of 0.53 g/L at 225K and under a pressure of 108.8kPa.
Find the density of the gas at 345K under a pressure of 68.3kPa.
3. A sample of gas with a mass of 26g occupies a volume of 392L at 32 oC and at a
pressure of 0.95 atm. Find the density of the gas at STP.

29
 4. A gas sample has a density of 1.77 x 10–4 g/L when the temperature is 15oC and the
pressure is 780mmHg. Find the density of the gas at STP.
5. What is the density of carbon tetrachloride vapour at 714torr and 125oC?
6. The mean molar mass of the atmosphere at the surface of Titan, Saturn’s largest moon
is 28.6g/mol. The surface temperature is -178 oC and the pressure is 1.6 earth atm.
Assuming ideal behavior, calculate the density of Titan’s atmosphere.

Molar Mass of a Gaseous Substance

In real world, chemists often deal with gaseous substances of unknown or of partially known
composition. The molar masses of these substances can nevertheless be evaluated using the
ideal gas equation. All that needed, is to experimentally determine the density value of the gas
at a known temperature and pressure.

Thus the equation;

PM
d=
RT

Can be rearranged to;

dRT
M=
P

Experimental determination of molar mass involves filling a bulb of known volume with the
gaseous substance under study. The temperature and pressure of the gas sample are recorded
and the total mass of the bulb plus gas determined. The bulb is then emptied and weighed
again. The difference in mass is the mass of the gas sample.

The density of the gas is equal to its mass divided by the volume of the bulb. Once the density
of the gas is known, it becomes possible to calculate its molar mass using the above equation.

Note: Although nowadays the mass spectrometer has become the dominant instrument for
determining molar mass, determination of molar mass by the density method is still
useful.

30
Example 1:
A chemist has synthesized a greenish-yellow compound of chlorine and oxygen and finds that
its density is 7.71 g/L at 36oC and 2.88 atm. Calculate the molar mass of the compound and
determine its molecular formula.

Solution
We can determine the molar mass of the gaseous compound using the equation;
dRT
M=
P
Where; M = Molar mass of the gas, d = density, R = gas constant, T = absolute temperature
and P = pressure.

We have been given that; d = 7.71 g/L, R = gas constant, T = 36OC = 309K, P = 2.88 atm
M=?

This implies that;

( 7. 71 g/ L )×( 0 . 0821 L⋅atm/ K ⋅mol )×( 309 ) K

M= =67 . 9 g/mol
2. 88 atm

Note that:
1. Molecular formula of the compound can be determined by trial and error method
2. We know the molar masses of chlorine (35.45 g) and oxygen (16.00 g).
3. If for instance the compound contains one atom of chlorine and one atom of oxygen
then the molar mass will be 51.45 g which appears to be too low.
4. If on the other hand the compound is made up of two chlorine atoms and one oxygen
atom, the molar mass will be 86.90 g which in this case will be too high.
5. The compound most likely contains one chlorine atom and two oxygen atoms and has
the formula ClO2 with molar mass of 67.45 g.

Example 2:
A sample of chloroform gas weighing 0.494 g is collected in a flask with a volume of 129
cm3 at 99.6 °C when the atmospheric pressure is 742.1 mm Hg. What is the approximate
molar mass of chloroform?

31
Solution

m PV
M= and n=
Since;  n RT

Where; M = Molar mass, m = weight of gaseous substance and n = number of moles.

Substituting and rearranging the above equation gives;

mRT ( 0 . 494 g )×0 . 08206 L⋅atm/molK ×372. 8 K

M= = =120 g /mol
PV 0 . 976 atm×0 .129 L

Exercise
1. The density of a gaseous organic compound is 3.38 g/L at 40OC and 1.97 atm. What is
its molar mass?
2. A sample of phosphorus that weighs 3.243 × 10 -2 g exerts a pressure of 31.89kPa in a
56.0ml bulb at 550°C. What are the molar mass and molecular formula of phosphorus
vapor? (124g/mol P4 )

Dalton’s Law of Partial Pressures (Pressure of a Mixture of Gases)

Unless if gases chemically react with each other, individual gases in a mixture of do not affect
each other’s pressure. Each individual gas in a mixture exerts the same pressure that it would
exert if it were present alone in the container (See Figure 6 below).

Figure 6: If equal-volume cylinders containing gas A at a pressure of 300kPa, gas B at a

pressure of 600kPa, and gas C at a pressure of 450kPa are all combined in the
same-size cylinder, the total pressure of the mixture is 1350kPa.

32
The pressure exerted by each individual gas in a mixture is called its partial pressure.

In 1801 a famous English chemist John Dalton made critical observations on gaseous
mixtures and formulated a law, currently known as Dalton’s law of partial pressures.

Dalton’s law of partial pressures states that;

“The total pressure of a mixture of gases is just the sum of the pressures that each gas
would exert if it were present alone”.

This law can be expressed using the following equation;

PTotal =P A +P B+PC +¿⋅¿⋅¿ ∑i Pi

In the equation PTotal is the total pressure of a mixture of gases, PA is the partial pressure of gas
A; PB is the partial pressure of gas B; PC is the partial pressure of gas C; and so on.

If for example, we have two gases A and B in a container of volume V, the pressure exerted
by gas A according to the ideal gas equation is;
n A RT
P A=
V

Where nA is the number of moles of gas A present. Similarly, the pressure exerted by gas B is
n B RT
PB =
V
In the mixture of gases A and B, the total pressure P T is the result of the collisions of both
types of gas molecules with the walls of the container. Thus according to Dalton’s law,

PT =P A +P B
n A RT nB RT
= +
V V
RT
= n +n
V ( A B)
nRT
=
V
Where n, is the total number of moles of gas present.

33
In general, the total pressure of a mixture of gases is given by;
PT =P1 +P 2 +P3 +¿⋅¿⋅¿ ¿
Where; P1, P2, P3…… are the partial pressures of components 1, 2, 3, …….

One can be made to understand how each partial pressure is related to the total pressure by
considering the case of a mixture of two gases A and B.

When we divide the partial pressure of A (PA) by the total pressure of the gas mixture (PT) we
obtain;
PA n A RT /V
=
PT ( n A +n B ) RT / V
nA
=
( n A +n B )
¿XA

Where XA is the mole fraction of A. Mole fraction is a dimensionless quantity and in general,
the mole fraction of component i in a mixture is given by;
ni
Xi=
nT
Where ni and nT are the numbers of moles of component i and the total number of moles
present respectively.
In the study of air pollution for instance one may be interested in the pressure-volume-
temperature relationship of a sample of air, which contains several gases. In this case and all
cases involving mixtures of gases, the total gas pressure is related to partial pressures that is
the pressures of individual gas components in the mixture.

Note: The mole fraction of a gas in a mixture is always less than 1 whereas the sum of mole
fractions for a mixture of gases must be unity.

nA nB
X A + X B= + =1
Thus; n A + nB n A +n B

The partial pressure of A can be expressed in terms of mole fraction as;

34
 P A= X A P T
And that of B as;
P B = X B PT

The most direct method of measuring partial pressures is using a mass spectrometer. The
relative intensities of the peaks in a mass spectrum are directly proportional to the amounts
and hence to the mole fractions, of the gas present. From mole fractions and total pressure
(which can be measured using a manometer) one can calculate the partial pressures of
individual components.

Example 1:
A mixture of gases contains 4.46 moles of neon (Ne), 0.74 moles of argon (Ar), and 2.15
moles of xenon (Xe). Calculate the partial pressures of the gases if the total pressure is 2.00
atm at a certain temperature.

Solution
We know that:
P i= X i P T
Where Pi is the partial pressure of gaseous component i in the mixture, Xi is its mole fraction
and PT is the total pressure of the gas mixture.
Considering neon in the mixture we can write;
PNe =X Ne PT
Mole fraction of neon is given as;
n Ne 4 . 46 mol
X Ne= = =0 .607
n Ne +n Ar +n Xe 4 . 46 mol+0. 74 mol+2 .15 mol
It then follows that;
PNe =X Ne PT =0 . 607×2. 00 atm=1.21 atm

Likewise;
P Ar= X Ar PT
=0 .10×2. 00 atm
=0 .20 atm

35
And,
P Xe =X Xe PT
=0 .293×2.00 atm
=0 .586 atm
Note: Always make sure that the sum of partial pressures is equal to the given total pressure.

Example 2:
1.00g of air consists of approximately 0.76g of nitrogen and 0.24g of oxygen. Calculate the
partial pressures and the total pressure when this sample occupies a 1.00L vessel at 20oC.

Solution:
The data needed for use are;
PN =? nN =? V =1 . 00 L T =293 K
2 2

PO2=? nO2 =? V =1. 00 L T = 293 K

nN nO
The number of 2 and 2 can be obtained from the masses and molar masses
(28.02g/mol for N2 and 32.00g/mol for O2).
1 mol N 2
Moles of N2 = 0 .76g N2 ׿ =0 . 0271 mol N2
28 .02 g N 2
1 mol O 2
Moles of O2 = 0 . 24 g O2 ׿ =0 . 0075 mol O2
32. 00 g O2
But we know that for any given gas A in a mixture;
n A RT
PA =
V
0 .08206L .atm 293K
PN =0 . 0271 mol N 2 ¿ × =0. 65 atm N 2
2 1K. mol 1 . 00L
0 . 08206L. atm 293K
PO =0 . 00750 mol O2 ¿ × =0 .18 atm O2
2 1K . mol 1 . 00L
The total pressure is the sum of these partial pressures hence;
PT =0 . 65 atm+0 . 18 atm=0 .83 atm

Example 3:
A 10.0L vessel contains 2.50 × 10−3 mol of H2, 1.00 × 10−3 mol of He, and 3.00 × 10−4 mol of
Ne at 35 °C.

36
(a) What are the partial pressures of each of the gases?
(b) What is the total pressure in atmospheres?
Solution:

(a) The gases behave independently, so the partial pressure of each gas can be determined
from the ideal gas equation, using;

nRT
PV =nRT ⇒ P=
V

( 2. 50×10−3 mol ) ( 0 . 08206 L⋅atm⋅mol−1 K −1 ) (308 K )

PH 2 = =6 .32×10−3 atm.
10. 0 L

( 1 .00×10−3 mol ) ( 0. 08206 L⋅atm⋅mol−1 K −1) ( 308 K )

PHe= =2. 53×10−3 atm .
10. 0 L

( 3.00×10−4 mol ) ( 0. 08206 L⋅atm⋅mol−1 K −1 ) ( 308 K )

PNe = =7 . 58×10−4 atm .
10 .0 L

(b) The total pressure is given by the sum of the partial pressures:

PT =P H +PHe +P Ne =( 0 . 00632+0. 00253+0 . 00076 ) atm=9 .61×10−3 atm .

2

Exercise:
1. A sample of natural gas contains 8.24 moles of methane (CH 4), 0.421 moles of ethane
(C2H6) and 0.116 moles of propane (C3H8). If the total pressure of the gas is 1.37atm
what are the partial pressures of the gases?
2. A 5.73L flask at 25 °C contains 0.0388 mol of N2, 0.147 mol of CO, and 0.0803 mol
of H2. What is the total pressure in the flask in atmospheres?
3. What is the pressure of a mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar in a
container with a volume of 2.00 L at 20 °C?
4. A gas mixture used for anesthesia contains 2.83 mol oxygen (O 2), and 8.41 mol
nitrous oxide (N2O). The total pressure of the mixture is 192kPa.
(a) What are the mole fractions of O2 and N2O?
(b) What are the partial pressures of O2 and N2O?

37
Collecting Gases over Water
Dalton’s law of partial pressure has a practical application in calculating volumes of gases
collected over water. A simple way to collect gases that do not react with water is to capture
them in a bottle that has been filled with water and inverted into a dish filled with water. The
pressure of the gas inside the bottle can be made equal to the air pressure outside by raising or
lowering the bottle. When the water level is the same both inside and outside the bottle
(Figure 7), the pressure of the gas is equal to the atmospheric pressure, which can be
measured with a barometer.

Figure 7: Collection of a Gas above Water.

The trapped gas is a mixture of the gas produced by the reaction and water vapour. If the
collection flask is appropriately positioned to equalize the water levels both within and
outside the flask, the pressure of the trapped gas mixture will equal the atmospheric pressure
outside the flask.
As a gas is collected over water, it becomes saturated with water vapor and the total pressure
of the mixture equals the partial pressure of the gas plus the partial pressure of the water
vapor.
The pressure of the pure gas is therefore equal to the total pressure minus the pressure of the
water vapor. This is referred to as the “dry” gas pressure, that is, the pressure of the gas only,
without water vapour.

38
The vapour pressure of water, which is the pressure exerted by water vapor in equilibrium
with liquid water in a closed container, depends on the temperature (Figure 8). At room
temperature the vapour pressure of water is only about 20torr.

Figure 8: Graph of Vapor Pressure (Torr) of Water At Sea Level as a Function of

Temperature (oC).

Oxygen gas is mostly prepared in the laboratory using this method. Oxygen collected in this
manner is not pure because water vapour is also present in the same space. The total gas
pressure is equal to the sum of the pressure exerted by the oxygen gas and the water vapour,
which can be measured with a barometer whereby;
PT =PO +P H O
2 2

Example:
Oxygen gas is generated when potassium chlorate is heated (See Figure 9 below) to
decomposition and collected over water according to the equation;
2 KClO 3( s)→2 KCl( s)+3 O2( g )

39
Figure 9: Generation and collection of oxygen over water.
The volume of oxygen collected at 24 oC and atmospheric pressure of 762 mmHg is 128mL.
Calculate the mass (in grams) of oxygen gas obtained. The pressure of the water vapour at
24oC is 22.4 mmHg.

Solution:
First we calculate the partial pressure of O2. We know that;
PT =PO + P H O
2 2

Therefore,

PO =PT −P H 2 O
2

=762 mmHg−22. 4 mmHg

=740 mmHg
From the ideal gas equation we write

m
PV = nRT = RT
M
Where m and M are the mass of O2 collected and the molar mass of O2, respectively.
Rearranging the equation we obtain;

PVM (740/760)atm ( 0 .128 L ) ( 32. 00 g/mol )

m= = =0. 164 g
RT ( 0 . 0821 L⋅atm/ K⋅mol )( 273+24 ) K

Exercise:
1. Hydrogen gas generated when calcium metal reacts with water is collected over water.
The volume of gas collected at 30oC and pressure of 988 mmHg is 641mL. What is the

40
 mass (in grams) of the hydrogen gas obtained? The pressure of water vapour at 30 oC is
31.82mmHg.

2. A sample of oxygen collected over water at a temperature of 29.0°C and a pressure of

764torr has a volume of 0.560L. What volume would the dry oxygen have under the
same conditions of temperature and pressure?

Kinetic Theory of Gases

The gas laws help us to predict the behaviour of gases, at macroscopic levels (pressure,
volume, temperature changes) but they do not explain the behaviour of gases in the
microscopic world (properties of molecules). Starting in the 1850s, a number of physicists
like Ludwig Boltzmann (Germany) and James Maxwell (England) found that the physical
properties of gases could be explained in terms of the motion of individual molecules.

The findings of Maxwell and Boltzmann and others resulted in a number of generalizations
about gas behaviour that have since been known as the kinetic - molecular theory of gases or
simply the kinetic theory of gases.

The postulates of kinetic theory are approximations, but they work under “normal”
conditions. Under extreme conditions (very high pressures, very low temperatures, etc.) the
behavior of the gases can no longer be modeled very well by kinetic theory, and we have to
use more complicated, statistics based models.

Postulates of the Kinetic-Molecular Theory

The kinetic-molecular theory is based on the following assumptions:

1. The size of the gas particles is negligibly small compared to the total volume of the
gas. Most of the volume of a gas is empty space.

2. Gas particles move constantly and randomly in straight lines until they collide with
another particle or the walls of the container. The collisions of the particles with the
walls of the container are the cause of the pressure exerted by the gas.

3. The average kinetic energy of the gas particles is directly proportional to the
temperature of the gas in Kelvins.

 There is a distribution of velocities in a sample of gas; some particles are

moving faster and some are moving slower but the higher the temperature, the
greater the average kinetic energy is. (EK = ½mv2 )

41
  For a sample of helium and a sample of argon at the same temperature, the
average kinetic energy of the particles of both gases are the same, but the
particle of helium must move faster, because it is lighter, to have the same
kinetic energy as the particles of argon.
4. The collisions of particles with each other or with the walls of the container are
completely elastic. When the particles collide, they exchange energy, but there the
total kinetic energy of the gas particles is constant at constant

5. Each gas molecule acts independently of the other molecules in the sample, and do not
attract or repel each other.

Qualitative Interpretation of the Gas Laws Using the Kinetic Theory

Using the assumptions of kinetic-molecular theory, it is possible to understand why each of

the gas laws behaves the way it does. According to the kinetic theory, the pressure of a gas
results from bombardment of the walls of a container by molecules and the pressure is
determined by:-
(i) The concentration of molecules (number per unit volume) which in turn determines
the frequency of collision.
(ii) The average force exerted by of the molecules determines the average force of a
collision.
We can interpret the gas laws in terms of kinetic theory as follows: -

The Kinetic Theory and Boyle’s Law (P α 1/V):

Pressure is a measure of the number and forcefulness of collisions between gas particles and
the walls of their container. If the gas particles are crowded into a smaller space, and the
temperature does not change, they move around at the same speed, but hit the walls of the
container more often, raising the overall pressure. Thus, pressure increases as volume
decreases.

Suppose the volume of a gas is increased, what would happen? This decreases the
concentration of molecules and so decreases the frequency of collisions per unit wall area.
The pressure decreases.

The Kinetic Theory and Charles’ Law (V α T):

42
If temperature increases at constant volume, the average kinetic energy of the gas particles
increases. For the pressure to remain constant, the volume must increase to spread the
collisions out over a greater area. The volume of the gas will expand until the gas pressure is
balanced by the constant external pressure. Thus, volume increases as temperature increases.

The Kinetic Theory and Gay-Lussac’s Law (P α T):

If temperature increases at constant volume, the average kinetic energy of the gas particles
increases, causing them to collide harder with the walls of the container. Thus, pressure
increases as temperature increases.

The Kinetic Theory and Avogadro’s Law (V α n):

The more gas particles there are, the more volume the particles need at constant P and T to
avoid increasing the number of collisions with the walls of the container. Thus, volume
increases as the moles of gas increase.

For two different volumes of gas to have the same temperature (same average molecular
speed) and the same pressure, there must be the same number of molecules per unit volume
(i.e. when P1 = P2, T1 = T2 and V1 = V2), it follows that n1 = n2, which is a mathematical
expression of Avogadro’s law.

The Kinetic Theory and Dalton’s Law (PTotal = P1 + P2 + P3 + ...):

The identity of the gas particles is irrelevant. The total pressure of a fixed volume of gas
depends only on the temperature T and the total number of moles of gas n. Adding more gas
particles, even if they’re different gases, has the same effect as adding more particles of the
first gas.

If molecules do not attract or repel one another, then the pressure exerted by one type of
molecule is unaffected by the presence of another gas. Consequently, the total pressure is
given by the sum of individual gas pressures.

The Ideal Gas Law from Kinetic Theory

43
One of the key features of kinetic theory is its ability to explain the ideal gas law. To show
how we can get the ideal gas law from kinetic theory, we will first find an expression for the
pressure of a gas.

According to kinetic theory, the pressure of a gas P, will be proportional to the frequency of
molecular collisions with a surface and to the average force exerted by a molecule in
collision.

P α Frequency of collisions× Average force

The average force exerted by a molecule during a collision depends on its mass m and its
average speed u that is, its average momentum Mu. In other words, the greater the mass of
the molecule and the faster it is moving, the greater the force exerted during collisions.

The frequency of collision is also proportional to: -

- Average speed u
- The number N of molecules in the gas
And inversely proportional to

- The gas volume V, because the larger the volume, the less often a given molecule
strikes the container walls.

Putting these factors together gives

1
(
Pα u× ×N ×mu
V )
Multiplying out and bringing volume to the left, we get

PV α Nmu2
Recall that average kinetic energy of a molecule of mass m and average speed u is ½mu2, PV
is proportional to the average kinetic energy of a molecule.

- The average kinetic energy is also proportional to the absolute temperature.

- The number of molecules, N is proportional to the moles of molecules, n.

44
We therefore get; PV α nT

We can write this as an equation by inserting a constant of proportionality R, which we

identify as the molar gas constant.

PV = nRT

Distribution of Molecular Speeds and the Root Mean Square Speed

The kinetic energy allows us to investigate motion in more detail. Suppose we have a large
number of molecules of a gas, say 1 mole, in a container. As you might expect, the motion of
the molecules is totally random and unpredictable. As long as we hold the temperature
constant, the average kinetic energy and the mean square speed remain unchanged as time
passes. James Clerk Maxwell (British physicist) in 1860 showed that molecules can have a
wide range of speeds, though most are close to the average and some move at very high or
low speeds as shown in Figure 10.

A plot of the relative number of gas particles with a certain speed results in a skewed bell-
shaped curve called a Maxwell-Boltzmann distribution.

Figure 10: Maxwell-Boltzmann distribution of the number of molecules with

corresponding molecular speeds for O2, N2, H2O He and H2 at a
constant temperature.

As the temperature of the gas increases, the average velocity of the gas particles
increases and the distribution of velocities broadens.

45
 Figure 11: Maxwell-Boltzmann distribution of molecular speeds of gas particles at
different temperatures.

Note: The speed corresponding to the maximum (peak) in the curve is the most probable
speed, that is, the speed of the largest number of molecules and it increases with
temperature (the peak shifts toward the right). The curve also begins to flatten out with
increasing temperature, indicating that larger numbers of molecules are moving at
greater speed.

Root- Mean- Square Speed

One of the useful results of the kinetic molecular theory is that it enables us to relate
macroscopic quantities P and V to molecular parameters such as molar mass (M) and root-
mean-square (rms) speed (urms). One of the results of the kinetic theory of gases is that the

total kinetic energy of one mole of any gas equals . We already know that the average

1 2
mu
kinetic energy of one molecule is 2 and thus we can write;

3
KE= RT
2

NA ( 12 m u )= 32 RT
2

46
Where NA is the Avogadro’s number (6.023 x 1023), R is the gas constant in thermodynamic

units, (8.314 J K-1 mol-1) and m is the mass of a single molecule. Because N A m=M , the
above equation can be rearranged to give;

1 3
M u2 = RT
2 2

3 RT
⇒ u2=
M

Taking the square root of both sides gives;

3 RT
√ u2=urms= √ M
The above equation shows that the root-mean-square speed of a gas increases with the square
root of its temperature (in Kelvins). Since M appears in the denominator, it follows that the
heavier the gas, the more slowly its molecules move.

Example 1

Calculate the root-mean-square speeds of helium atom in m/s at 25oC.

Solution

Root-mean-square equation is given as;

3 RT
urms =
√ M
But;

R = 8.314 J/K.mol, T = (25 + 273) K = 298 K, Molar Mass for He = 4.003 g /mol

We start by converting the molar mass of helium from g/mol to kg/mol.

1 kg
M=( 4 .003 g/mol )× =4. 003×10−3 kg/mol
1000 g

47
 3×( 8.314 J/K .mol )×( 298K )
urms =
√ 4.003 ×10−3 kg/mol

= √ 1.86 × 10 6 J/kg
Using the conversion factor;

1J = 1 kgm2/S2

We get;

urms =√1.86 × 106 kgm 2 /kg. S2

= 1.36 × 103 m/s

Example 2
What is the ratio of urms values for helium versus xenon at 30oC. Which is higher and why?
Solution
There are two approaches to solve this problem: the hard way and the easy way
Hard way:
1. The urms speed of helium can be determined as;
3 RT
urms =
√ M
2 2
urms =
√
3 ×( 8.314 kgm /s K .mol )×( 303K )
4.003 ×10−3 kg/mol

= √ 1.8769 × 10 6 m2 / s2

=1.37×103 m/s
2. Convert the molar mass of xenon from g/mol to kg/mol;
1 kg
M Xe= (131 . 3 g /mol )× =0 . 1313 kg/mol
1000 g
Now, using the equation for the urms, insert the given and known values and solve for
the variable of interest.

48
 3 ×( 8.314 kgm 2 /s 2 K .mol )×( 303K )
urms =
√0.1313 kg/mol

= √ 5.76 × 10 4 m2 /s 2

=2.40×102 m/ s
Compare the two values for xenon and helium and decide which is greater.

u Xe =2. 4×102 m/s

u He =1.37×103 m/s
So the ratio of RMS speeds is;
u Xe 2 .4×102 m/s
= ≈0 .18
u He 1. 37×10 3 m/s
Helium has the higher urms speed. This is in accordance to Graham's Law, because helium
atoms are much lighter than xenon atoms.
Easy Way:
Since the temperature is the same for both gases, only the square root of the ratio of molar
mass is needed to be calculated.

M He
√ √
M Xe
=
4 . 003 g/mol
131 .3 g/mol
≈0 .18

In either approach, helium has a faster RMS speed than xenon and this is due exclusively to its
smaller mass.

Exercise

1. Calculate the root-mean-square speeds of nitrogen molecule in m/s at 25oC.

2. Compare the root-mean-square speeds of helium atom and nitrogen molecule.

3. What is the root mean square velocity of the molecules in a sample of oxygen gas at 0
°C and 100 °C?

49
Real Gases
Experiments have shown that the ideal gas law describes the behaviour of real gases quite
well at moderate pressure and temperatures but not so well at high pressure and low
temperatures.

Figure 12, below shows the PV/RT versus P plot for three real gases at a given temperature.
These plots offer a test of ideal gas behaviour. According to the ideal gas equation (for 1
mole of gas), PV/RT equals 1, regardless of the actual gas pressure (when n = 1, PV = nRT
becomes PV = RT or PV/RT = 1.). For real gases, this is true only at moderately low pressure
( ≤ 5 atm).

Figure 12: Plot PV/RT versus P for 1 mole of a gas at 0oC

Significant deviations are observed as pressure increases. The attractive forces among
molecules operate at relatively short distances. For a gas at atmospheric pressure, the
molecules are relatively far apart and these attractive forces are negligible. At high pressure,
the density of the gas increases; the molecules are much closer to one another. The
intermolecular forces can become significant enough to affect the motion of the molecules,
and the gas will no longer behave ideally.

Another way to observe the non-ideality of gases is to lower the temperature. Cooling a gas
decreases the molecules’ average kinetic energy, which in a sense deprives molecules of the
drive they need to break away from their mutual attractive forces.

50
Van der Waals Equation
The non-ideality of gases can be dealt with mathematically by modifying PV =nRT , taking
into account intermolecular forces and definite molecular volumes. A Dutch physicist
Johannes Diderik (J. D.) van der Waals in 1873 made simple mathematical treatment, which
provides us with interpretation of real gas behaviour at the molecular level.

Van der Waals suggested that the pressure exerted by an ideal gas
Pideal , is related to the

experimentally measured pressure

Preal , by

an2
Pideal = Preal + 2
V
↑ ↑
Observed Correction term

Where; a, is a constant and n and V are the number of moles and volume of the gas,

an 2
respectively. The correction term for pressure
( )
V2 represents the overall effect of
intermolecular attraction towards the reduction of pressure. The intermolecular interaction
that gives rise to non-ideal behaviour depends on how frequently any two molecules approach
each other closely.

The frequency of such encounters increase with the square of the number of molecules per
2 2
unit volume ( n /V ), because the probability of finding each of the two molecules in a

particular region is proportional to n/V.

Pideal is the pressure we would measure if there
were no intermolecular attraction. The quantity a, then, is just a proportionality constant in
the correction term for pressure. The value of a, is an expression of how strongly molecules of
a given type of gas attract one another.

The Volume Correction Term

The volume correction concerns the volume occupied by the gas molecules. We note that for
the ideal gas law we assume that the molecules have negligible volume. However, each

51
molecule does occupy a finite, volume, so the effective volume of the gas becomes ( V −nb )
, when n is the number of moles of the gas and b is a constant. The term nb represents the
volume occupied by n moles of the gas.

Having taken into account the corrections for pressure and volume, we can rewrite
PV =nRT as

an2
()
P+ 2 underbracealignlc⏟
V
or ected ¿ (V −nb)underbracealignl c⏟
pres ure ¿
or ected ¿ ¿=nRT¿
volume ¿
The above equation relating P, V, T and n for a non-ideal gas is known as van der Waals
equation. The van der Waals constants a and b are selected for each gas to give the best
possible agreement between the equation and actually observed behaviour. The value of ɑ
indicates how strongly molecules of a given type of gas attract one another. Table (4) below
lists the values of a, and b for a number of gases.

From the Table, we see that helium atoms have the weakest attraction for one another,
because helium has the smallest a value. There is also a rough correlation between molecular
size and b. Generally the larger the molecule (or atom), the greater b is, but the relationship
between b and molecular (or atomic) size is not a simple one.

Table 4: Van der Waals constants for some

common gases.
a b
Gas
( ) atm⋅L2
mol 2
( molL )
He 0.03412 0.0237
Ne 0.211 0.0171
H2 0.244 0.0266
N2 1.39 0.0391

52
 Cl2 6.49 0.0562
CO2 3.59 0.0427
CH4 2.25 0.0428
NH3 4.17 0.0371
H2O 5.46 0.0305

Example:
A quantity of 3.50 moles of NH 3 occupies 5.20 L at 47oC. Calculate the pressure of the gas
(in atm.) using;
(a) The ideal gas equation and
(b) The van der Waals equation.

Solution:
(a) We have the following data
V = 5.20 L
T = (47+273) K = 320 K
R = 0.0821 L.atm/K.mol
N = 3.50 mol
Substituting the values in the ideal gas equation we have;
nRT
P=
V
( 3 .50 mol )( 0 . 0821 L⋅atm/ K⋅mol ) ( 320 K )
= =17. 7 atm
5. 20 L

(b) Van der Waals equation is given as;

an2
()P+ 2 underbracealignlc⏟
V
or ected ¿ (V −nb)underbracealignl c⏟
pres ure ¿
or ected ¿ ¿=nRT¿
volume ¿
From the table above we have;
a = 4.17 atm.L2/mol2 and
b = 0.0371 L/mol
It is convenient to calculate the correction terms for van der Waals equation. They are;

53
 2 2 2
an 2 ( 4.17 atm. L /mol ) ( 3 .50 mol )
= =1. 89 atm
V 2 ( 5.20 L )2

nb = ( 3. 50 mol ) ( 0. 0371 L /mol ) = 0.130 L

Finally, substituting these values in the van der Waals equation, we write;

( P+1.89atm ) ( 5.20 L−0.130 L )

=( 3.50mol ) ( 0.0821 L.atm/ K .mol ) ( 320K )

P=16.2 atm
Note: That the actual pressure measured under these conditions is 16.0 atm. Thus, the
pressure calculated by the van der Waals equation (16.2atm) is closer to the actual
value than that calculated by the ideal gas equation (17.7atm)

Exercise:
Using the data shown in the table, calculate the pressure exerted by 4.37 moles of molecular
chlorine confined in a volume of 2.45 L at 38oC. Compare the pressure with that calculated
using the ideal gas equation.

Diffusion and Effusion of Gases

Diffusion and effusion are two phenomena that are based on gaseous motion.
Gas Diffusion
Gaseous diffusion is the gradual mixing of molecules of one gas with those of another by
virtue of their kinetic properties. Gas diffusion can also be defined as the process whereby a
gas spreads out through another gas to occupy the space with uniform partial pressure. In
other words a gas or vapour having a relatively high partial pressure will spread out towards
region of lower partial pressure of that gas until the partial pressure becomes equal
everywhere in the space.

The diffusion of one gas into another contributes to the transport of pheromones (chemical
signals between animals) and perfumes through air. It helps to keep the composition of the

54
atmosphere approximately constant, since gases in high concentration diffuse away. Even in
the absence of wind, diffusion helps to disperse gases leaking from chemical plants.

Although the rate of diffusion depends in part on the average molecular speed, the effect of
molecular collisions makes the theoretical picture a bit complicated.

Diffusion of gases always happens gradually, and not instantly as molecular speeds seem to
suggest. Given that the root-mean-square speed of a light gas is greater than that of a heavier
gas, a lighter gas will diffuse through a certain space more quickly than will a heavier gas.

In 1832 a Scottish chemist named Thomas Graham found out that; “under the same
conditions of temperature and pressure, rates of diffusion for gaseous substances are
inversely proportional to the square roots of their molar masses”. This statement, currently
known as Graham’s law of diffusion, is expressed mathematically as;

r1 M2
r2
=
√ M1
Where r1 and r2 are the diffusion rates of gases 1 and 2 and M1 and M2 are their molar masses
respectively.

2.2.2 Gas Effusion

Whereas diffusion is a process by which one gas mixes with another, effusion is the process
by which a gas under pressure escapes from one compartment to another by passing through
a small opening. The rate of effusion is also given by Graham’s law of effusion. That is;
r2 M1
r1
=
M2 √
In practice, the rate of effusion of a gas is inversely proportional to the time it takes for the
gas to effuse through a barrier: the longer the time, the slower the effusion rate. So we can
write;
t1 r2 M1
t2
=
r1
=
√ M2
Where t1 and t2 are the time of effusion for gases 1 and 2 respectively.

55
Calculation of Separation Factor of Gaseous Isotopes
Graham’s law has practical application in the separation of isotopes. We define a quantity
called separation factor as;

r M2
S= 1 =
r2 M1 √
Thus the value of S indicates how well gases 1 and 2 can be separated from each other in one
stage effusion process. The minimum value of S is 1, which indicates the gases are
inseparable. (We assume that M2 > M1).

Separation of Isotopes by Gaseous Effusion

During the Second World War, scientists discovered that a particular isotope of uranium, 235U,
undergoes nuclear breakdown when bombarded with neutrons. The amount of energy released
in the process is so enormous that even a relatively small amount of the substance, about 500
g, can release enormous amounts of energy. Natural uranium consists of 99.27% uranium -
238 (which does not undergo fission) and only 0.72% uranium – 235 (which does undergo
fission). A Uranium fuel rod must contain about 3% Uranium – 235 to sustain the nuclear
reaction. To increase the percentage of uranium – 235 in a sample of Uranium (a process
called enrichment is undertaken). Since isotopes of the same element do not differ from each
235 238
other in chemical properties, the problem of separating U from the more abundant U
isotope was formidable indeed. The separation method finally chosen was gaseous effusion.

Uranium can be converted into uranium hexafluoride, UF 6, which is easily vaporized above
room temperature. The advantage of this compound is that fluorine consists of a single stable
235 238 235
isotope, so the separation involves only two species of UF6 and UF6. Note that UF6
238
differs from UF6 by less than 1 percent by mass. The separation factor for these two
substances is given by;

238 . 05+ ( 6×18. 998 )

S=
√ 235 . 04+ ( 6×18 . 998 )
=1 . 0043

This is a very small separation factor, but the situation was not entirely hopeless. After a
second effusion process, the overall separation factor becomes 1.0043 x 1.0043, or 1.0086, a
slight improvement. In the particular case of uranium hexafluoride, then, the separation factor
for an n-stage process is 1.0043n. If n is a large number, say 200, then it is possible to obtain
235
uranium with about 99 percent enrichment of the U isotope. This is essentially what is

56
needed. Because the UF6, molecules with the light isotopes of uranium travel about 0.4%
faster than the UF6, molecules with the heavier isotope, a sample of gas is passed through a
235
long series of porous barriers, and at last UF6 is obtained with the desired isotopic purity. In
order to achieve separation of the isotopes, as required for bomb-grade uranium, many
thousands of effusion stages are needed

Example:
A flammable gas made up of carbon and hydrogen is found to effuse through a porous barrier
in 1.50 min. under the same conditions of temperature and pressure, it takes an equal volume
of bromine vapour 4.73 min to effuse through the same barrier. Calculate the molar mass of
the unknown gas and suggest what the gas might be.

Solution:
r 1 t2 M2
We know that;
= =
r 2 t1 √
M1

From the molar mass of Br2 we write;

1.50 min M
=
√
4 .73 min 159 .8 g/mol
Where M is the molar mass of the unknown gas. Solving for M we get;
2
1.50 min
M= (
4.73 min )
×159 .8 g/mol=16 .1 g/mol

Note: Since the molar mass of carbon is 12.01 g and that of hydrogen is 1.008 g, the gas is
methane (CH4)

Exercise:
1. It requires 60 seconds for 1.5 L of an unknown gas to effuse through a porous wall
and it takes 84 seconds for the same volume of N2 gas to effuse at the same
temperature and pressure. What is the molar of the unknown gas?

2. Work out the separation factor for

a) The light and heavy isotopes of hydrogen, H2 and D2

57
b) Two isotopes of neon 20Ne and 22Ne.

58