A simplified, well elaborated and illustrative approach to Physical Chemistry

Gases have no Liquids have no Solids have definite

Shape definite shape. They shape, they take up shapes.
take up shape of the shape of the
container they containers they
occupy. occupy.

GASEOUS STATE OF MATTER

A gas is predicted as a random movement of atoms or molecules, not closely packed,
with very weak forces between them so that they can move about quite freely.
That is why gases have low densities, they expand to occupy any container and are easily
compressed.

The gaseous state in terms of kinetic theory of matter

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According to the kinetic theory;
1. The gas molecules occupy only a tiny fraction of the volume of the container in which
they are contained. The intermolecular distance is many times larger than the diameter
of the molecules. A sample of a gas is nearly empty space and the molecules are
scattered throughout this space.
2. The gas molecules are constantly moving in straight lines until they collide with each
other and with the walls of the container, exerting no force upon one another. The
collisions made are perfectly elastic, meaning that the molecules bounce apart with no
loss of energy.
3. The average kinetic energy of the molecules is proportional to absolute temperature,
therefore at a certain temperature; all gases have the same average kinetic energy.

AN IDEAL GAS
An ideal gas is also called a perfect gas.
An ideal gas is a gas that obeys all gas laws accurately at all temperatures and
pressures, has no intermolecular forces of attraction and occupies a negligible volume.
However there are known examples of ideal gases and the concept is just a theoretical
one.
Gas pressure
This is the pressure exerted by a gas per unit area. The main unit of pressure is
.
is called a .
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Other units of pressure are and

.

Gas laws
Boyle‟s law
Boyle‟s law states that; at a constant temperature, the volume of a given mass of a gas
is inversely proportional to the pressure.
Or at a constant temperature, the pressure of a given mass of a gas is inversely
proportional to the volume.

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Therefore if a gas has a volume at a pressure and the pressure is changed to , the new
volume , , at a constant temperature is given by the equation;

Real gases do not fully obey Boyle‟s law. The deviations from the law particularly occur
at high pressures and low temperatures, and for gases which are easily liquefied.
The deviations from the law occur due to interactions between the molecules in a gas. If
such interactions did not exist, then a gas would obey Boyle‟s law (would be ideal or
perfect)
Real gases approach the ideal or perfect behaviour at low pressures and high
temperatures.
Charles‟ law
Charles‟ law states that; at a constant pressure, the volume of a given mass of a gas is
directly proportional to the temperature in Kelvin.
Or at a constant pressure, the volume of a given mass of a gas is directly proportional
to the absolute temperature.
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Therefore if a gas has a volume at a temperature and the temperature is changed to , the
new volume , , at a constant pressure is given by the equation;

Real gases also deviate from Charles‟ law as they do for Boyle‟s law.
Combined gas laws
When Boyle‟s law and Charles‟ law are combined, one equation is obtained. This is
called the equation of state for an ideal gas. The equation relates pressure, volume and
the temperature of a gas.
From Boyle’s law;
If a given mass of a gas has a volume of at a pressure of , it will a volume at a
pressure at a constant temperature.

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From Charles’ law;
If now the temperature at which the volume of the gas, is measured is changed from to
, the new volume will be given by;

Equating equations and yields;

Multiplying through by yields;

and in a more general form, this can be expressed as

and the temperature expressed in Kelvin.
The equation of state of an ideal gas helps us to calculate the effect of a change in
temperature and pressure on the volume of a gas. We cannot compare gas volumes unless
they are stated at the same temperature and pressure. Gas volumes are usually compared
at 273K and 101325Pa (standard temperature and pressure).
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Examples on calculations involving gas laws

In these calculations, it is very crucial to remember to change the temperature to the
Kelvin scale. The pressure may be left in its units so long as they are the same on both
sides throughout the calculation.
1. If the volume of a gas at standard temperature and pressure is 51 , calculate
the volume of the gas if it is collected at 60 and 105 kPa.

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( )

2. A closed bulb contains a certain volume of a gas at 21 and 755mmHg.

Calculate the pressure of the gas if the temperature is raised to 51 .

( )

Ideal gas law

Boyle‟s law and Charles‟ law can be combined to form a single equation which
represents the relationship between pressure, volume and kelvin temperature of a given
mass of a gas under different conditions.

By combining the two gas laws;

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When the quantity of gas is one mole, the constant in this equation is called the molar gas
constant, represented by .
Therefore for 1 mole of a gas;
And for moles of a gas;

The above equation is known as the ideal gas equation because it only holds when gases behave
as ideal or perfect gases.
The molar gas constant is commonly used as when the units of pressure,
volume and temperature are and Kelvin respectively.
Recall that;

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( )

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Examples
1. Calculate the volume occupied by 200g of carbon dioxide gas at a temperature
30 and a pressure of 98.65 kPa.

2. 0.539g of a vapourised sample of gas X occupies 200 at a temperature of

373K and a pressure of 0.938 atm. Calculate the relative molecular mass of X.

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Questions
1. A certain mass of a gas has a volume of 241 at 18 and a pressure of 100400 Pa.
determine its volume at s.t.p.
2. A gas occupies a volume of 1500 at 27 and 102,700 pressure. What
would be its volume at s.t.p?
3. A certain gas has a volume of 75 at 15 and 104 kPa. What would be its
volume at 27 and ?
4. A sealed flask contains oxygen at 17 and 99.3 . What would be the
pressure of the oxygen if the temperature was lowered to ?
5. At s.t.p, a certain mass of a gas has a volume of 1 litre. At 30 atm, the volume is 31.2
and at 60 atm, the volume is 14.9 . Explain whether the gas shows ideal
behaviour.
6. (a) 1 mole of hydrogen iodide gas at 25 was introduced into a container of volume
20 litres. Calculate the pressure of the gas assuming ideal behaviour.( 1 mole of an
ideal gas occupies 22.4 litres under standard conditions)
(b) The sample of hydrogen iodide, considered above was raised to a temperature of
300 and it decomposed into hydrogen and iodine. Calculate the pressure of the
equilibrium mixture at 300 assuming no change in volume.
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7. Calculate the volume occupied by 200g of chlorine gas at a temperature 15 and a

pressure of 54.71 kPa.
8. 1212.5 of a gas J has a mass of 0.88g at 50 and a pressure of 115000 .
Calculate the relative molecular mass of the gas.
9. A gas Q contains 30.43% nitrogen and the rest being oxygen. 0.23g of Q occupied
154.11cm3 at 150 and 840mmHg. Determine the;
(i) Empirical formula of Q
(ii) Molecular formula of Q.

More of the application of this concept is covered in empirical and molecular

formula.
Graham’s law of gaseous diffusion
The concept of diffusion is not a new one to us at this level since you already have an
idea from Ordinary level.

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The rates at which different gases diffuse are not equal. A lighter gas diffuses more
rapidly than a heavier one. After carrying out a number of experiments on the rates at
which gases mix together, Graham(1832) came up with Graham‟s law which states that;
At constant temperature and pressure, the rate of diffusion of a gas is inversely
proportional to the square root of its density.

√
Consider two gases and which diffuse at rates and respectively. If the densities of the
gases are and respectively;

√ √

√ √
Dividing equation (i) by equation (ii) yields;

√
√
√ √
√
√
√
√
If the volume is kept constant, then density is directly
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proportional to the relative molecular mass of the gas. We then have;

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√ √

√ √
Dividing equation (i) by equation (ii) yields;
√
√
√
√
√
√
Graham‟s law can therefore also be stated as; at constant temperature and pressure, the
rate of diffusion of a gas is inversely proportional to the square root of its relative
molecular mass.
Rate of diffusion of a gas can also be expressed as a reciprocal of the time taken for the

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gas to diffuse. Therefore;
√
√
√ Similarly;
√ √
√ √
⁄
√

Rate of diffusion of a gas can also be expressed in terms of volume of the gas and time
taken by the gas to diffuse.

Avoid the common mistake done by students during most of these calculations by
forgetting that most gases are diatomic. This should be observed when calculating molar
masses of gases.
Examples
1. A given volume of gas W diffuses through a hole in 14.1 seconds while the same
volume of carbon dioxide diffuses through the same hole in 10 seconds. Calculate the
molecular mass of gas W.
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√
√
( ) √
( ) √

( )

2. A given volume of a gas X diffuses in two thirds of the time taken by an equal
volume of hydrogen chloride under the same physical conditions. Calculate the
relative molecular mass of the X.

( ) √
⁄

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( ) √

√
( )
√
( ) ( )
( )

√
√

3. Oxygen diffuses 0.9 times faster than a hydrocarbon Y. Calculate the relative
molecular mass of Y.
√
√
( )

√
√

4. The time taken for of oxygen to diffuse through a porous partition is

10 seconds. Another gas Z at the same conditions of temperature and pressure
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diffuses through the partition at the rate of in 20s. Determine the

relative molecular mass of gas Z.
( ) √
⁄
( ) √
( ) ( )
√
( )
√

5. Two pieces of cotton wool were each soaked separately in concentrated ammonia
solution and concentrated hydrochloric acid respectively and simultaneously
inserted into opposite ends of a horizontal wide glass tube. After a short time a
white ring was across the tube. If the distance between the inner surfaces of the
cotton wool plugs is 50cm.

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(i) Name the white ring
(ii) Write the equation leading to formation of the white ring.
(iii) Determine how far from the ammonia plug the white ring is formed.

(i) Ammonium chloride

(ii)
(iii)

Since ammonia gas from concentrated ammonia solution diffuses faster than hydrogen chloride
gas from hydrochloric acid, the white ring is formed nearer the cotton wool soaked in
hydrochloric acid. White ring

50cm
50-x x
Cotton wool soaked Cotton wool soaked
in concentrated in concentrated
hydrochloric acid ammonia solution

( ) √
⁄
( ) √

( ) ( )
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√
√( )
√

6. Oxygen diffuses 2.3 times as fast as a compound Z with the formula; .

Determine the molecular formula of Z.

( )

√
√
√

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√

Questions
1. Calculate the ratio of diffusion of a gas at 91 and 0 at a constant pressure.
2. A gas Q diffuses 4 times as rapidly as sulphur dioxide under the same conditions. If
the density of sulphur dioxide under the same conditions of temperature and pressure
is , calculate the density of Q.
3. 100 of oxygen diffused through a membrane in 5 minutes. 120 of an
unknown gas under the same conditions, diffused through the membrane in 10
minutes. Calculate the molecular mass of the unknown gas.
4. Oxygen diffuses 1.19 times faster than an amine, .
(i) Determine the molecular formula of the amine.
(ii) Deduce the structural formulae and names of all possible isomers of the
amine.
5. 250 of an alkene diffuse through a porous medium in 10 seconds and 716 of
oxygen diffuse through the same medium in 25 seconds under the same conditions.
Calculate the molecular mass of the alkene and deduce its structural formula.
6. Oxygen diffused through a porous partition in 1.87 minutes. Under similar conditions,
the same volume of an alkene, T diffused in 2.15 minutes.
(a) Determine the formula of T
(b) Write equation and outline mechanism for the reaction between T and benzene.
Indicate the conditions for the reaction.
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7. 141.4 of an inert gas diffused through a porous plug in the same time as it took
50 oxygen to diffuse through the same plug under the same conditions. Calculate
the relative atomic mass of the inert gas.
8. Two pieces of cotton wool were each soaked separately in concentrated amine Q and
concentrated hydrochloric acid respectively and placed at opposite ends of a 2m long
glass tube. After some time a white ring was formed at 0.96m from the end
containing concentrated hydrochloric acid. Determine the relative molecular mass of
amine Q.
9. Two pieces of cotton wool were each soaked separately in concentrated amine Y and
concentrated hydrochloric acid respectively and placed at opposite ends of a 1m long
glass tube. After some time a white ring was formed at 0.52m from the end
containing the concentrated ammine. Determine the relative molecular mass of amine
Y.
10. of gas L diffuses through a porous partition in 5s. of oxygen

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diffuses through the same partition in the same time. Calculate the molecular mass of
L.
11. Nitrogen gas diffuses 1.25times faster than gas X. calculate the relative molecular
mass of gas X.
12. 25 of gas Q diffuse through a small aperture in 48 seconds while 25 of an
alkane diffuse through the same aperture in 40 seconds.
(i) Deduce the molecular formula of the alkane.
(ii) Write equations to show how the alkane can be synthesized from
Pent-2-yne.
13. Gas X diffuses through a membrane in 20.5 minutes and under the same conditions,
an equal volume of hydrogen diffuses through the same membrane in 3 minutes.
Calculate the molecular mass of X.
14. 141.4 of gas X diffused through a porous plug in the same time it took 50
of oxygen to diffuse through the same plug under identical conditions. Calculate
the relative molecular mass of X.

15. State Graham‟s law of gaseous diffusion.

(b) Nickel forms a gaseous carbonyl; . Deduce the value of n if carbon
monoxide diffuses 2.46 times faster than the carbonyl compound.
(c) State the ;
(i) name of the nickel carbonyl
(ii) coordination number of nickel in the compound.
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16. (a) State Graham‟s law of gaseous diffusion.

(b) A hydride of silicon contains 9.65% by mass of hydrogen and was found to
diffuse through a porous plug at two thirds of the rate of diffusion of nitrogen.
Determine the molecular formula of the hydride.
17. A gaseous compound X contained 46.1% carbon and 53.9% nitrogen. In 20 seconds,
50 of X diffused through a porous plug and the same volume of oxygen diffused
in 15.7 seconds.
(i) Determine the molecular formula of X.
(ii) Calculate the volume of carbon dioxide that diffuses in 20 seconds under
the same conditions.
18. A compound, B has an empirical formula of . Oxygen gas diffuses 1.345 times
faster than B.
(a) (i) Determine the molecular formula of B
(ii) Write the structural formulae of all the possible isomers of B.

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(b) (i) B does not Fehling‟s solution. Using equations, show how B can be formed
from propene
(ii) Write an equation for the reaction of B with sodium hydrogen sulphite
and write the mechanism.
19. A gaseous oxide of sulphur, diffused through a porous partition in 2.68 minutes
while equal volume methane at the same temperature diffused in 1.1985 minutes.
(a) Determine the value of in the oxide
(b) The oxide in (a) above reacts with benzene via an electrophilic substitution
mechanism.
(i) State whether the oxide in (a) above acts as an electrophile or nucleophile.
Give a reason for your answer.
(ii) Write equation for the reaction with benzene and outline the mechanism.

Mole fraction of a gas,

Mole fraction of a gas is the ratio of the number of moles of the gas present to the total
number of moles of all the gases in the mixture.

Therefore for a mixture of two gases and . The mole fractions of gases and are
given respectively as
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Also from Avogadro‟s hypothesis, it follows that;

Dalton’s law of partial pressure

In a mixture of gases, each gas behaves as if it was the only gas present assuming there
are no chemical interactions between the gases. In a container in which a mixture of
gases, that not react are enclosed, the total pressure exerted is a result of the individual
pressures of each of the gases. Each of these pressures is called partial pressure.
Partial pressure of a gas is the pressure which that gas exerts if it occupies a vessel

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alone which was initially occupied by a mixture of gases.
In 1801, Dalton came up with Dalton‟s law of partial pressure which states that; in a
mixture of gases which do not react chemically, the total pressure is the sum of the
partial pressures of the components.

Let us now consider a mixture of three gases and and placed in a vessel each having
partial pressures , and respectively.
According to Dalton‟s law of partial pressures; the total pressure exerted by the gases is;

and if each of the gases has the number of moles as and and respectively,
Then the mole fractions of the gases and and are given by;

The partial pressures of each of the gases respectively are given as a product of
their respective mole fractions and the total pressure,
( )

( )

( )
Dalton came with his law experimentally but it can be deduced from the ideal gas
equation. Therefore if each of the gases has the number of moles as and and
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respectively and occupy a volume V, then, the pressures of each of the gases
respectively are given as;

The total pressure can then be expressed as

Examples
1. (a) State Dalton‟s law of partial pressures.
(b) Explain why a mixture of ammonia and hydrogen chloride does not hold for
Dalton‟s law of partial pressures.
(c) A mixture of 20% ammonia, 55% hydrogen and 25% nitrogen by volume has

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a pressure of . Calculate the partial pressure of each gas.

(b) Ammonia reacts with hydrogen chloride to form ammonium chloride. For Dalton’s law to
hold, there should be no chemical interactions between the gases.
(c) According to Avogadro‟s hypothesis;

2. 1.3g of carbon dioxide and 2.4g of oxygen were mixed in a 1 litre vessel. If the
total pressure of the mixture is 100 atmospheres, calculate the partial pressure of
each gas present in the container.
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( ) ( )

3. 50.0 of carbon dioxide at are mixed with 150 of

hydrogen at the same pressure. If the pressure of the mixture is
. Calculate the partial pressure of carbon dioxide.

( )

4. In a vessel of volume 10.0 are introduced 4.0 of methane at a

pressure of , 12.5 of ethane at a pressure of

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and 1.50 of propane at a pressure of . Calculate
the pressure of the resulting gas mixture.

( ) ( )

( )

5. A sample of air at 27 contains 0.62 g of oxygen gas, 1.34g of carbon

dioxide gas and 0.06g of nitrogen gas. Calculate;
(i) the partial pressures of each gaseous component in the mixture
(ii) the total pressure of the mixture of gases.
(i)
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(ii)

Alternatively;
( )

( )

( )

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6. At constant temperature, a vessel contains two gases, and . The partial
pressure of is and its mole fraction is 0.85. Calculate the;
(i) total pressure exerted by the mixture of gases.
(ii) partial pressure of gas .

(i) (ii)

Questions
1. A mixture of gases, at a pressure of has the volume composition of
30% carbon monoxide , 50% oxygen and 20% carbon dioxide. Calculate the partial
pressure of each gas.
2. A mixture of gases at s.t.p contains 65% nitrogen, 15% of carbon dioxide and 20% of
oxygen by volume. Calculate the partial pressure of each gas in kPa.
3. 12g of nitrogen, 0.4g of hydrogen and 9g of Oxygen are put in a 1 vessel at a
pressure of 17.02mmHg. Calculate the partial pressure of each of the gases.
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4. The partial pressures of the components of a mixture of gases are 26.64 kPa oxygen
34 kPa nitrogen and 42.66 kPa hydrogen. What is the percentage by volume of
oxygen in the mixture?
5. 400 of gas A at 2 atmospheres and 200 of gas B at 1 atmosphere are put in
a 500 container at the same time. Calculate the total pressure in the container.

Maxwell-Boltzmann distribution
According to the kinetic theory, the gas molecules are constantly moving in straight lines
until they collide with each other and with the walls of the container. As a result of these
numerous collisions within the gas, the velocities of the individual molecules vary
enormously. Most molecules within the gas have velocity close to the mean, but some
may acquire higher or lower values as a result of a series of favourable or unfavourable
collisions. The distribution of velocities amongst molecules was calculated by Maxwell
and Boltzmann, from the laws of probability and some typical results are shown below
graphically.

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c'
c
u

The graph shows the distribution of molecular velocities in a gas a temperature , , and
a higher temperature, .
At both temperatures, the number of molecules with very high or very low speeds is
small, the bulk of the molecules having intermediate speeds. The peaks of the curves
represent the most probable velocities possessed by an individual molecule at the given
temperature. The most probable velocity(c') is not the same as either the mean/ average
velocity(c) or the root mean square velocity (u). At , the most probable velocity (c'),
the mean velocity (c) and the root mean square velocity(u) are all shown.
It is noted that the distribution curve for the higher temperature, has a lower peak. It
also more spread out although the total number of molecules ( represented by areas
under the curves) remain the same. The most probable velocity, the mean/ average
velocity and the root mean square velocity are all higher, but the proportions of the
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molecules with these speeds are lower. This is because at higher temperature, there a
greater range of possible velocities.
The distribution of kinetic energy amongst the molecules follows a similar pattern. It can
be expressed as
⁄

Where is the total number of molecules and is the number having an energy greater
than the value E.
Deviation from Ideal behaviour
Previously, we discussed that Boyle‟s law is not valid over a wide range of pressures.
Deviations from the law occur at low temperatures and high pressures.
Such deviations are due to the fact that real gases are not ideal.
A real gas is a gas that does not obey gas laws accurately at all temperatures and
pressures, has intermolecular forces of attraction and occupies an appreciable volume.

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Differences between a real gas and ideal gas
Real gas Ideal gas
Possesses intermolecular forces Has no intermolecular forces
Occupies an appreciable volume Volume occupied is negligible
Collisions between particles are inelastic. Collisions are perfectly elastic ( particles
( particles lose kinetic energy on collision) do not lose any kinetic energy on collision)

Conditions under which real gases behave like ideal gases

1. Low pressure. At low pressures, molecules of a gas are far away from each other,
neither repulsive nor attractive forces are significant and the volume occupied by the
real gas becomes negligible, behaving as an ideal gas.
2. High temperature. At high temperatures, the kinetic energy of the molecules
increases, intermolecular collisions are high and are perfectly elastic, intermolecular
forces of attraction become insignificant, molecules become far away from each other
and the volume occupied by the real gas becomes negligible, behaving as an ideal gas.

Real gases are not ideal because the intermolecular forces of attraction have a significant
effect on their pressure and their volume is not negligible. At low temperatures and high
pressures, the molecules of a gas are close together and forces operate between them. At
sufficiently low temperature and high pressure, a gas liquefies. Some of the ideas of the
kinetic theory have to be modified to account for non-ideal behaviour of gases.
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An ideal gas would obey Boyle‟s law such that , known as compression or
compressibility factor( ).
Compressibility factor is a measure of deviation real gas from ideal gas behaviour.
For any ideal gas the compressibility factor is equal to one.

However, for real gases, only approaches a value of one at very low pressures as shown
in the figure below. At other pressures, may be greater than one (meaning the gas is
more difficult to compress than an ideal gas) or less than one.
The graph below shows a plot of against pressure for some gases at the same
temperature.
2

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1

Explanations
At high pressures, the molecules of a gas are close to each other, there are strong
repulsive forces between the molecules, and these hinder compression.
At moderate pressures, the forces between the molecules are attractive and favour
compression.
At very low pressures, neither repulsive nor attractive forces are significant and that is
why real gases approach ideal behaviour at low pressures.
Deviation for hydrogen and helium
For hydrogen and helium, there is a small deviation from ideal behaviour. This is because
the gases have small molecules, with small molecular masses and held by weak van der
Waals forces of attraction. The value of the compressibility factor is greater than
1 and continuously increases with increase in pressure. This is because deviation due to
molecular volume is greater than the deviation due to molecular attraction at all
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pressures. The molecules of hydrogen repel each other strongly thus this repulsion
increases the volume of a gas.
Deviation for methane, ammonia, oxygen and carbon dioxide
For methane, ammonia, oxygen and carbon dioxide, the deviation from ideal behaviour
increases in the order . This is because the gases have larger
molecules, with larger molecular masses that increase in the same order. The strength in
the van der Waals forces of attraction between the molecules increase with the increase in
molecular weight and reducing the volume occupied by the gases. For each of the gases,
the value of the compressibility factor initially decreases to a minimum. This is
because the deviation due to molecular attraction is greater than the deviation due to
molecular volume. The value of thereafter increases with increase in pressure because
the effect of molecular volume overcomes that of molecular attraction.

Questions
1. (a) What is meant by the term compressibility factor?

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(b) On the same axes, draw a graph to show the variation of pressure with the
compressibility factor for each of the gases; hydrogen, ammonia, propane and an ideal
gas.
(c) Explain the shape of the curve for;
(i) hydrogen
(ii) ammonia
(iii) propane
2. (a) State what is meant by an ideal gas
(b) Explain how liquefaction of a gas can be affected by;
(i) pressure
(ii) temperature
(c) The curves below show the deviation of some gases from ideal behaviour.

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(i) Explain why hydrogen shows a small deviation from ideal behaviour
compared to other gases.
(ii) Compare the deviation of oxygen and carbon dioxide from ideal gas
behaviour
(Hint; the idea of compressibility factor should not be incorporated in your
answer in this question)

3. A plot of the compressibility factor, , against pressure for one mole of methane at
273K is as shown below. Use the graph to answer the questions that follow.

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(a) Give reasons for the behavior of methane at 273K when the pressure is:
(i) lower than 200 atmospheres
(ii) higher than 200 atmospheres
(b) On the same graph, sketch graphs for ethane and nitrogen at 273K and give reasons
for your sketches.

Correction of real gas behaviour by using van der Waals’ equation

In 1873, Van der Waals replaced the simple gas equation by the equation;

( )

Where and are numerical constants.

Van der Waals argued that the actual size of the gas molecules means that the volume in
which they are free to move is less than the total volume which a gas occupies. He
replaced by
He also argued that the attractive forces between the gas molecules lower the pressure
that they can exert by lowering the frequency of impact with the walls of the containing
vessel. This also lowers the force of impact of the gas with the walls of the vessel.
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Since both these effects are proportional to gas density and inversely proportional to
volume, Van der Waals replaced by ( )

The Van der Waals‟ equation fits the experimental data better than the simple gas
equation, and the values of and for different gases can be obtained by fitting the
equation to known values of and .
Liquefaction of gases
If a gas is cooled sufficiently at atmospheric pressure, it can be liquefied. The conditions
of temperature and pressure under which gases liquefy were first investigated by
Andrews in 1869.
Andrews subjected carbon dioxide to various pressures at different temperatures and
plotted the effect of pressure on the volume.
The isothermals for carbon dioxide which are defined as curves for variation of
pressure with volume of the gas at particular temperatures were obtained as shown

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below.
D

C B

𝑽𝒐𝒍𝒖𝒎𝒆 𝒎𝟑

KEY
Permanent gas
Liquid
Vapour
Liquid and vapour
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The isothermal at shows that the volume of the gas (carbon dioxide)
decreased with increase in pressure. This isothermal is in accordance with Boyle‟s law.
At a lower temperature , the volume of the gas first decreased in accordance to
Boyle‟s law along AB until the pressure increased to about 60 atm. At this pressure, there
is a sudden break in the curve and liquid carbon dioxide forms. The pressure remains
constant along BC until all the carbon dioxide is converted into liquid form. At C,
liquefaction of the gas is complete. Any further increase in pressure causes no change in
volume of the liquid carbon dioxide along CD. ( This is in accordance with the fact the
extremely high pressures are required to compress a liquid appreciably).
Similar changes take place in the effect of change in pressure on the volume of carbon
dioxide at temperatures below , although the pressure required to liquefy the
gas becomes smaller as the temperature decreases.
Liquefaction of the gas can be brought about at all temperatures below but
above this temperature, no liquefaction occurs no matter how much pressure is increased.

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This temperature is called the critical temperature of carbon dioxide. The pressure
required to liquefy the gas at the critical temperature is called the critical
pressure and the volume of 1 mole of the substance at the critical temperature and
pressure is called the critical volume. Point is called the critical point.
Definitions;
Critical temperature is the temperature above which a gas cannot be liquefied however
much pressure is exerted on it.
Critical pressure is the minimum pressure required to liquefy the gas at critical
temperature.
The conditions for liquefaction of a gas are therefore; low temperature below critical
temperature and high pressure.
Above critical temperature, a gas is regarded as a permanent gas since it cannot be
liquefied.

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Question
1. The graph below shows isotherms of a gas.

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B C
(a) Explain what is meant by the terms
(i) Isothermal of a gas
(ii) Critical temperature
(b) What is the critical temperature of the gas?
(c) Which isothermal represents the behaviour of an ideal gas?
(d) What does the region ABC represent.
(e) Explain the shape of the isothermal at 285K
(f) On the sketch graph, show the regions under which the gas exists as;
(i) Vapour
(ii) Liquid
(iii) Permanent gas
(g) State the conditions for liquefaction of a gas to occur.

LIQUID STATE OF MATTER

The liquid state in terms of kinetic theory of matter
Most liquids are miscible like all gases. Liquids can be compressed although to a smaller
extent than gases.
According to the kinetic theory, molecules in a liquid are in a state of random motion, as
in a gas, but the motion is very much less than it is in a gas and the molecules in a liquid
are very much closer.
Liquids actually lie midway between the disorderly, scattered distribution found in a gas
and the orderly compact arrangement found in a crystalline solid.
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The random distribution of molecules found in a liquid is shown by a phenomenon of

Brownian motion. Brownian motion was first observed by a botanist Robert Brown in
1827, who found out that very small pollen grains immersed in water undergo an
irregular motion when observed under a microscope. Such motion is due to bombardment
of the pollen grains by molecules of the liquid in which the grains are suspended.
Properties of a liquid
1. Compressibility
Compressibility of a liquid ( )is the fractional change in its volume per unit increase in
pressure. Liquids have low compressibility because the particles are closer to each other
and the intermolecular forces of attraction are weaker than those in solids hence the
particles can randomly move although not as fast as in gases.
The property of compressibility of liquids is applied in;
(i) Hydraulic breaks. In a hydraulic break, there is a brake fluid whose compressibility is
affected by temperature and the presence of trapped air and moisture. When the brake

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pedal is pressed, force is exerted on the pistons causing the brake fluid to flow into a
pressure chamber. This increases the pressure in the entire hydraulic system. This
pressure effect is also exerted on the brake pads to reduce the vehicle speed.
(ii) Hydraulic car jack. The car jack is used to lift even the heaviest cars using a small
force that is applied to a fluid from one piston of the car jack. This force builds up
pressure in the fluid that then forces another piston to rise. This generated pressure lifts
the car up.
2. Viscosity
The viscosity of a liquid is the resistance to flow of a liquid. Edible oil has a greater
viscosity than water. Viscosity may be thought of as internal friction between the
molecules. Viscosity is a major factor in determining the forces that must be overcome
when fluids are used in lubrication and transported in pipelines. It controls the liquid flow
in processes like spraying, injection moulding and surface coating. The viscosity of
liquids decreases rapidly with an increase in temperature. That is why upon heating,
liquids flow more easily. The viscosities of water at 27℃ and 77℃ are
and respectively.
3. Surface tension
Molecules in the interior of a liquid are attracted equally on all sides by the molecules
around them. Molecules on the surface are only attracted inwards and sideways. As a
result, the liquid surface is always under tension and tends to contract so as to reduce the
surface area to a minimum. The mutual attraction of the molecules in the liquid surface
produces a resistance to penetration since work has to be done to force the molecules
apart. The surface has a certain amount of “hardness” which is basically similar to the
hardness of a solid metal surface. Therefore small metal objects such as a greased steel
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needle can float on water and certain insects can move freely on a water surface without
getting wet. The values of surface tension decrease with increase in temperature.
Surface tension of a liquid, , is the force in newtons acting parallel to the surface
along a line of one metre in length in the surface and at right angles to the line.
4. Diffusion
Like gases, liquids also diffuse since their molecules are also moving. The diffusion in
liquids is however slower than in gases because the molecules are more closer together
than in gases. When two miscible liquids are added together, they diffuse throughout the
whole mixture until it is homogeneous. Solids can also diffuse in liquids to form
solutions. For example copper(II) sulphate and potassium manganate(VII) crystals can
diffuse in water.
5. Vapourisation/ Evaporation
Evaporation is the change of state from liquid to gas (or vapour) at a temperature below
the boiling point of the liquid. Evaporation can take place at any temperature, the rate
increasing with increase in temperature. Some molecules in the liquid have enough

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energy to escape into the gas phase (if they are near the surface and moving in the right
direction). Because these are the molecules with higher kinetic energies, evaporation
results in a cooling of the liquid. Evaporation is an endothermic process.
The rate of evaporation of a liquid depends on a number of factors which include its
vapour pressure(which is most important), molar heat of vapourisation, molar heat
capacity and other factors. Liquids with a high vapour pressure evaporate easily than
those with a lower vapour pressure
6. Condensation
The change of a vapour or gas into a liquid. The change of phase is accompanied by the
evolution of heat i.e. it is exothermic.
The evaporation of a liquid seen above can continue until no liquid remains. However, if
the liquid is in a closed container, the molecules in the vapour state collide with the walls
of the container and some fall back into the liquid(condense). Equilibrium will be reached
when the rate at which molecules condense is equal to the rate at which molecules of
vapour condense.
7. Boiling
When a liquid is heated, its temperature increases until there are molecules with sufficient
energy to escape from the liquid surface. The temperature reaches a high enough value
and the saturated vapour pressure becomes equal to the external pressure. At this point
the liquid changes rapidly and completely into vapour. This process is called boiling and
the temperature at which it occurs is the boiling point. The boiling point of a liquid
depends on the cohesive forces in the liquid. If the cohesive forces are weak, the boiling
point is low. When the cohesive forces increase in strength, the boiling point increases.
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Boiling therefore occurs when the vapour pressure is equal to the external pressure
exerted on the liquid.
Boiling point of a liquid is the constant temperature at which its saturated vapour
pressure becomes equal to the external pressure on the liquid.
8. Vapour pressure
Vapour pressure of a pure liquid is the pressure exerted by the vapour over the liquid
surface. The vapour pressure of a liquid depends on;
(i) The temperature of the liquid
When the temperature of a liquid is raised, its molecules move more rapidly. This results
into an increase in the average kinetic energies of the molecules. At higher temperatures,
a greater number of molecules possess energy greater than the escape energy and
therefore a greater number of molecules escape as vapour. This increases the vapour
pressure of the liquid.
(ii) External pressure

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The boiling point of a liquid depends on the external pressure. At a given temperature,
vapour pressure of a liquid is equal to the external pressure. Therefore the vapour
pressure of the liquid at a given temperature increases with increase in external pressure.
A liquid therefore boils at a higher temperature than its normal boiling point when the
external pressure is increased.
(iii) Intermolecular forces
The vapour pressure of a liquid depends on the strength of its intermolecular forces. A
liquid with weak intermolecular forces acting between its molecules has a higher
tendency to escape as a vapour hence a higher vapour pressure, said to be volatile. A
liquid with stronger intermolecular forces acting between its molecules has a lower
tendency to escape as a vapour hence a lower vapour pressure, said to be less volatile or
non-volatile.
Question;
The table below shows the boiling points of different pure liquids.
Compound Boiling point( )

(a) Arrange the compound in order of increasing vapour pressure.

(b) Explain your answer in (a) above.
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(a) Vapour pressure increases in the order;

(b) The vapour pressure increases from water to ethanol to ethoxyethane to nitrogen to
hydrogen, since boiling point decreases in the same order.
The vapour pressure of a liquid depends on the strength of its intermolecular forces.
Water molecules interact through strong intermolecular hydrogen bonds which
require a high amount of energy to break. This reduces escaping tendency of water
molecules into the vapour phase hence a low vapour pressure. Ethanol has a higher
vapour pressure than water because the intermolecular hydrogen bonds in it are
weaker than in water. This is because each ethanol molecule has only one hydrogen
atom that is sufficiently partial positive hence forms only two hydrogen bonds unlike
each water molecule that forms four hydrogen bonds. Ethanol molecules therefore
have a higher escaping tendency than water molecules. Ethoxyethane molecules,

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liquid nitrogen molecules and liquid hydrogen molecules all interact through weak
van der Waals forces of attraction whose strength decrease with decrease in molecular
size and molecular weight and can easily be broken. Since molecular mass and
molecular size decreases from ethoxyethane to nitrogen to hydrogen, strength of van
der Waals forces decreases in the same order, amount of energy required to break the
forces decreases in the same order, escaping tendency of the molecules into vapour
phase increases in the same order, hence increasing the vapour pressure.
(also refer to the topic; bonding and structure)

SOLID STATE OF MATTER

A solid is a substance of definite shape, high density and with strong intermolecular
forces of attraction between its molecules.

The solid state in terms of kinetic theory of matter

According to the kinetic theory, the molecules, atoms or ions in a solid are closely packed
and orderly arranged. Movement of the particles is restricted to vibration or oscillation
about mean/fixed positions. This makes solids incompressible. Attraction between the
particles is even more dominant.
The slight motion observed in a solid at ordinary temperatures is shown by the fact that
two solids when placed in close contact may diffuse very slightly into each other and also
by the fact that solids can exert a vapour pressure. The vapour pressure of a solid at
normal temperature is so small to be negligible but some solids like iodine and
naphthalene exert considerable vapour pressures at temperatures below their melting
points. On heating, they sublime (change directly to gas) and on cooling, the vapour
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Majority of solids melt into liquid when heated because the cohesive forces between their
molecules are broken and can no longer hold them together.

Phase changes in solids

1. Melting point
Melting point of a solid is the constant temperature at which the solid and liquid
phases are in equilibrium at a given external pressure.
In a solid, the particles are in a constant state of vibration. When a solid is heated, energy
is absorbed and the amplitude of vibration increases. The solid melts and the heat energy
of its particles increases sufficiently to overcome the cohesive forces which hold them
together. The process is a gradual one and the temperature remains constant even though
heat is being supplied. Solids which have covalent and ionic bonds usually require a
higher amount of energy to melt than those held by hydrogen bonds or van der Waals
forces.
2. Freezing point

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Freezing point is the constant temperature at which the liquid and solid phases are in
equilibrium at a given external pressure.
The freezing point of a substance in its liquid form is the same as the melting point of its
solid form and depends on factors such as purity of the substance and its external
pressure.
3. Sublimation
A solid which when heated changes directly into vapours without an intermediate liquid
stage, is said to have undergone sublimation. Every solid exerts a vapour pressure
although it is usually very small. The vapour pressure of solids increases with increase in
temperature. When the vapour pressure of a solid reaches the external pressure before it
melts, then the solid will vapourise before it melts (it sublimes). Such substances include
iodine, solid carbon dioxide (dry ice), naphthalene, camphor, etc.
4. Deposition
Under certain conditions, a gas can transform directly into a solid without passing
through the liquid phase by a process called deposition. Examples are conversion of
water vapour to ice and soot deposition on the walls of chimneys
Types of solids
Giant ionic solids
Ionic compounds are formed when metallic elements combine with non-metallic
elements. The ionic bonds formed in these compounds are strong electrostatic attractions
between the ions of opposite charges (cations and anions).
Each ion is surrounded by the greatest number of oppositely charged ions called the
coordination number. Examples of giant ionic solids include sodium chloride, caesium
chloride and zinc blende.
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4. Insoluble in polar and non-polar solvents. The metal-metal attractions are much
stronger than the metal-metal attractions or the metal-solvent attractions. The solvent
molecules cannot penetrate the metal lattice.

EMPIRICAL FORMULA, MOLECULAR FORMULA AND

PERCENTAGE COMPOSITION BY MASS
The percentage composition by mass of an element or a molecule in a
compound

From the formula of a compound and the relative atomic masses of the elements in it, the
percentage of each element or molecule in the compound can be determined. This is
called percentage composition by mass.

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Examples

1. The Single Superphosphate(SSP) fertilizer is common phosphatic fertilizer

chemically known as calcium dihydrogenphosphate. Calculate the percentage of
phosphorus in the fertilizer.

2. State the element with the highest percentage by mass in one mole of copper(II)
sulphate-5-water.

Therefore oxygen has the highest percentage by mass in copper(II) sulphate-5-water.

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3. Calculate the percentage by mass of water of crystallization in diammonium

iron(II) sulphate-6-water, .

4. A hydrated aluminium sulphate contains 8.1% by mass of aluminium. Calculate

the percentage by mass of the water of crystallization in it.

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Exercise
1. Calculate the percentage by mass of the named element in each of the following
compounds
(a) nitrogen in Sodium nitrate
(b) nitrogen in Ammonium sulphate
(c) magnesium in magnesium nitride
(d) bromine in calcium bromide
2. Calculate the percentage of water of crystallization in;
(a) sodium carbonate decahydrate
(b) Iron(II) sulphate heptahydrate
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3. A metal sulphate, contains 28% by mass of metal Y. Determine the relative

atomic mass of Y and the relative molecular mass of
4. Hydrated iron(III) sulphate, contains 19.9% by mass of iron. Find
the value of Y.

Empirical formulae and molecular formulae

The empirical formula is the simplest formula that expresses the simplest ratio of the
atoms present in a given compound. It is the formula obtained by experimental analysis
of a compound and it can be related to a molecular formula only if the molecular weight
is known.
The molecular formula simply gives the types and numbers of atoms present. The
formula of a compound showing the number and types of the atoms present in one
molecule of the compound, but not the arrangement of the atoms. For example,
represents the molecular formula both of ethanol and methoxymethane
. The molecular formula can be determined only if the molecular mass is

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known. The molecular mass can be obtained from the following known formulae;
(i)

(ii)

(iii)
(iv)
(v) Data from colligative properties.
The molecular formula can be got from the empirical formula using the relationship;

Molecular formula can be the same as empirical formula if

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Name of compound Empirical formula Simplest ratio Molecular formula Value of

Ethanoic acid 1:2:1
Glucose 1:2:1
Water 2:1
Ethene 1:2
Benzene 1:1
Phosphorus(V) oxide 2:5
The table above shows the empirical formula-molecular formula relationship for some
compounds.
Note; during the process of obtaining the empirical formula, the simplest ratio is obtained
as a decimal fraction. This ratio should have whole numbers only. Therefore figures of
the type 1.1, 1.2, 2.7, 3.8 and 4.9, can be rounded off to 1,1,3,4 and 5 respectively.
However, values of the type; 1.333, 2.4, 1.5, and 3.666 should not be rounded off.
Rounding them off creates a very big error. They must be multiplied by a factor to make

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them whole numbers as summarized below.
Sample calculated ratio Factor Correct ratio
1 : 1.333 3 3 : 4
1.5 : 2 2 3 : 4
2 : 2.499 2 4 : 5
1 : 3.666 : 3 3 3 : 11 : 9
3 : 2.4 2 6 : 5
Calculations on empirical formulae and molecular formulae
Examples
(a) From percentage composition
1. An organic compound Y contains 66.7% carbon, 11.1% hydrogen and the rest
being oxygen. If the vapour density of Y is 36, determine its molecular formula.
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2. A compound Q contains 54.5% carbon, 9.09% hydrogen and the rest being
oxygen.
(a) Calculate the empirical formula
(b) 0.542g of Q occupies 148cm3 at a temperature of 20 and a 740mmHg
pressure. Determine the molecular formula of Q.
(c) If Q which produces effervescence with magnesium powder, deduce its
structural formula.

(a)

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(b)

( )

(c) Hint; its carboxylic acids that form hydrogen

when reacted with magnesium.
( )
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3. A compound J contains 62.1% carbon, 10.3% hydrogen and the rest being
oxygen. If J has a density of at s.t.p;
(a) Determine the empirical formula of J
(b) Molecular formula of J
(a)

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(b)
( )

(b) From combustion data

4. When a hydrocarbon L was burnt in excess air, 14.4g of water and 13.44dm3 of
carbon dioxide were obtained at s.t.p.
(a) Determine the empirical formula of L.
(b) If the vapour density of L is 22. Determine the molecular formula of L.

(a)

( )
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(b)

5. When 0.236g of organic compound Q on combustion gave 0.528g of carbon

dioxide and 0.324g of water. If the same mass of Q at s.t.p gave 44.8cm3 of
nitrogen gas, determine the molecular formula of Q if its relative molecular mass
is 59.

( )
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(c) From other experimental data

One analytical method for determination of molecular formula of a hydrocarbon is
Eudiometry which uses Avogadro‟s hypothesis, “equal volumes of different gases at
the same temperature and pressure contain the same number of molecules”. i.e. doubling

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the number of molecules present doubles the volume at constant pressure. In this process,
an unknown volume of a gaseous hydrocarbon is exploded with excess oxygen. The
hydrocarbon completely burns to form carbon dioxide and water as the only products.
The vapour is then cooled and contraction in volume occurs due to condensation of water
vapour. The resultant volume (residual gas) left is due to carbon dioxide formed and the
unreacted oxygen. The volume of carbon dioxide is determined by adding aqueous
sodium hydroxide or potassium hydroxide. All the carbon dioxide formed is absorbed
and the diminution (reduction) in the volume of the gases is due to carbon dioxide. The
volume of gas that remains at this point is the unreacted oxygen. The volume of water
formed is regarded as negligible.

( )

Assume J cm3 of hydrocarbon was exploded in Q cm3 of excess oxygen to form V cm3 of gas. On
addition of concentrated potassium hydroxide, the volume reduced to W cm3.
Volume of carbon dioxide formed is
Volume of oxygen that reacts is
From the above equation,
Relating the volumes;

Similarly; ( )
Relating the volumes;
( )
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6. 20 cm3 of a hydrocarbon Z was exploded with 200 cm3 of oxygen. On cooling to

room temperature, the residual gases occupied 160 cm3. When the residual gases
were passed through sodium hydroxide solution, the volume reduced to 20 cm3.
(a) Write equation for the reaction between Z and oxygen.
(b) Determine the molecular formula of Z.
(c) Compound Z burns with a sooty flame. When Z was treated with hot
alkaline potassium manganate(VII) solution followed by dilute
hydrochloric acid, compound T was formed. T reacts with magnesium
ribbon liberating hydrogen gas.
(a) Identify Z and T
(b) Write equation to show how Z can be obtained from an alkyne.

(a) ( )

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(b) Volume of carbon dioxide formed is
Volume of oxygen that reacted
From the above equation,

Similarly; ( )

( )

( )

(c) Hint; burning with a sooty flame indicates Z is aromatic. On reacting it with
alkaline potassium manganate(VII) solution followed by dilute hydrochloric
acid, the compound T formed is a carboxylic acid since it liberates hydrogen
gas when reacted with magnesium.
(i) Z is
and T is

(ii) Try this on your own (convert ethyne to methylbenzene)

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7. 15 dm3 of gaseous hydrocarbon X was exploded with 105dm3 of excess oxygen.

The residual gas occupied 75dm3. On addition of concentrated potassium
hydroxide, the volume reduced by 45dm3. Determine the molecular formula of X.
( )
Volume of carbon dioxide formed
Volume of unreacted oxygen
Volume of oxygen that reacted
From the above equation,

Similarly; ( )

( )

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( )

( )

8. When 142cm3 of a hydrocarbon Y, of formula, and molecular mass 58g

was exploded with excess oxygen and cooled to room temperature, the volume of
the residual gas was 694cm3. On treatment with concentrated potassium
hydroxide solution, the volume decreased to 126cm3.
(i) Determine the molecular formula of Y.
(ii) Write the structural formula and IUPAC name of all possible isomers
of Y.

( )

(i) Volume of carbon dioxide formed is

From the above equation,
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(ii)
Structural formula of isomer Name of isomer
Butane
2-Methypropane

Questions
Note; some of the questions in this exercise will require you to apply knowledge
from either other topics or branches of chemistry. Feel free to consult those topics
or consult your teacher or wait for them to be covered and revisit the questions.

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1. Compound G, with molecular mass 237.9g, contains 24.8% cobalt, 29.8% chlorine,
the rest being water of crystallisation.
(a) Calculate the empirical formula
(b) Determine the molecular formula of G.
2. 0.464g of an organic compound Q when burnt gave 1.32g of carbon dioxide and
0.315g of water. When 0.2325g of Q was separately burnt, 7.08 cm3 of nitrogen gas at
s.t.p was produced. Determine the molecular formula and structural formula of Q if its
relative density is 46.5.
3. 1.363g of compound Y containing carbon, hydrogen and bromine on complete
combustion gave 1.10g of carbon dioxide and 0.45g of water. When 0.35g of Y was
vapourised, it occupied 39.5cm3 at 20 and 750mmHg. Calculate;
(i) the simplest formula of Y
(ii) the molecular formula of Y
(b) Y forms a compound Z when treated with a mixture of potassium hydroxide and
an alcohol under reflux. Z reacts with ammoniacal silver nitrate to form a white
precipitate Q. Identify Y, Z and Q.
(c) Write;
(i) equation for the reaction between Z and ammoniacal silver nitrate solution.
(ii) the mechanism for the reaction leading to formation of Z.
4. (a) A gaseous hydrocarbon Q contains 90% carbon. The density of Q is
at stp. Determine;
(i) the empirical formula of Q
(ii) the molecular formula of Q.
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(b) Q forms a white precipitate with ammoniacal silver nitrate solution. Identify Q.
(c) Using equations only, show how Q can be synthesized from propanoic acid.
5. (a) When 2.3g of a compound P, containing carbon, oxygen and hydrogen was burnt
in excess oxygen, 2.2g of carbon dioxide and 0.9g of water was produced. Calculate
the empirical formula of P
(b) The density of P is 2.0536 at s.t.p. Determine the molecular formula of P.
(c) P dissolves in sodium hydrogencarbonate solution with effervescence. Write the
structural formula of P.
(d) State what would be observed and write equation for the reaction that would take
place when a solution of P is treated with:
(i) acidified potassium manganate(VII) solution
(ii) Fehling‟s solution.
6. 20cm3 of a gaseous hydrocarbon W were exploded with 120cm3 of Oxygen. After the
explosion, the volume of gases remaining was 90cm3 and this decreased to 50cm3 on

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treatment with aqueous potassium hydroxide. Determine the molecular formula of the
hydrocarbon.
7. 30cm3 of a gaseous hydrocarbon Z was mixed with 140cm3 of oxygen and exploded.
After cooling to room temperature and pressure, the residual gas occupied 95cm3. On
absorption with concentrated potassium hydroxide solution there was a fall in volume
by 60cm3. Determine the molecular formula of Z.
8. 15 cm3 of a gaseous hydrocarbon were exploded with 105 cm3 of oxygen in a sealed
vessel after cooling, the residual volume occupies 75cm3. On addition of caustic
potash, there was a diminution of volume to 30cm3 Determine the molecular mass of
a hydrocarbon.
9. 30cm3 of a gaseous hydrocarbon Z was exploded with 200cm3 of oxygen, which was
in excess. The residual gas volume was found to be 155cm3 on cooling to room
temperature. The volume of the residual gas reduced to 35cm3 on treatment with
concentrated potassium hydroxide solution.
(a) (i) Write the general equation for the reaction between Z and oxygen
(ii) Calculate the molecular formula of Z.
(b) When Z was treated with ammoniacal copper(I) chloride solution, a red precipitate
was formed.
(i) Identify Z
(ii) Write equation for the formation of the red precipitate.
(c) Z was reacted with water in the presence of dilute sulphuric acid and mercury(II)
sulphate at 60℃. Write equation for the reaction and the accepted mechanism.
(d) Write equations to show how Z can be synthesized from but-1-ene.
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10. When 20cm3 of a gaseous alkyne P, , was exploded with 135cm3 of excess
oxygen and on cooling to room temperature, the residual gas occupied a volume of
105cm3. When the residual gas was passed through concentrated sodium hydroxide
solution, the volume decreased by 80cm3.
(a) (i) Write the equation for combustion of P.
(ii) Determine the molecular formula of P.
(b) Write the structural formulae and names of possible isomers of P.
(c) P reacts with sodium metal in presence of liquid ammonia to form compound Q.
Identify;
(i) P
(ii) Q.
(d) P was bubbled through ammoniacal silver nitrate solution.
(i) State what was observed
(ii) Write equation for the reaction

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(e) Write equation and suggest a mechanism for the reaction between;
(i) P and bromine water
(ii) Q and 1-bromopropane
(f) With the aid of an equation, describe how P reacts with water.
11. A compound Z, whose molecular mass is 142, contains 16.9% magnesium, 33.8%
carbon, 45.1% oxygen, and the rest being hydrogen.
(a) (i) Determine the empirical formula of Z.
(ii) Work out the molecular formula of Z.
(b) On heating, Z decomposes to form a white residue, X and a gas Y that forms a
yellow precipitate with 2,4-dinitrophenylhydrazine in acidic medium.
(i) Deduce the chemical formula of Z.
(ii) Identify X and Y.
(c) Write equation for the reaction that;
(i) takes place when Z is heated.
(ii) leads to formation of the yellow precipitate.
(d) (i) State what will be observed when dilute sulphuric acid is added to X.
(ii) Write equation for the reaction between dilute sulphuric acid and X.
(e) Write;
(i) the mechanism for the reaction in (c)(i)
(ii) equation(s) for conversion of Y to ethene.
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12. A solid inorganic sulphate contains 9.76% of magnesium 13.00% of sulphur and
51.22% of water.
(a) Determine the empirical formula of the compound.
(b) Hence determine the molecular formula of the compound (the molecular mass of
compound is 245)
(c) Name the reagent(s) that can be used to confirm the ions present in the compound.
In each case state what is observed.
13. An organic compound Y consists of 48.6% carbon, 8.1% hydrogen and the rest being
oxygen.
(a) Determine the empirical formula of Y.
(b) 0.453g of a vapourised sample of Y occupied 200cm3 at 100℃ and 95.0kPa
pressure.
(i) Calculate the molecular mass of Y.
(ii) Determine the molecular formula of Y.

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(c) Y reacts with magnesium metal with evolution of a gas. Write;
(i) the structural formula of Y
(ii) the equation for the reaction between Y and magnesium.
14. (a) An organic compound, Z, contains carbon 80%, hydrogen 6.7%, the rest being
oxygen. Calculate the empirical formula of Z.
(b) 0.25g of Z when vapourised at 150℃ and 760mmHg occupies .
Determine the:
(i) molecular mass of Z
(ii) molecular formula of Z
(c) Z burns with a yellow sooty flame and forms a yellow-orange solid with
Brady‟s reagent. Z also reacts with a solution of iodine in sodium hydroxide to
form a yellow solid.
(i) Identify Z
(ii) Write the mechanism for the reaction between Z and Brady‟s reagent.
15. (a) A compound Y contains 22.6% by mass of oxygen, 8.57% by mass hydrogen and
the rest being carbon.
(iii) Calculate the empirical formula of Y.
(iv) When 0.3g of Y was vapourised at ℃ and 700mmHg , it occupied a
volume of . Determine the molecular formula of Y.
(b) Y forms a yellow precipitate with 2,4-dinitrophenylhydrazine and does not react
with Tollen‟s reagent.
(c) Write equation for the formation of the yellow precipitate in (b).
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16. (a) A compound P contains carbon, hydrogen and oxygen. 0.0291g of P on

combustion gave 0.0581g of carbon dioxide and 0.0239g of water.
(i) Calculate the empirical formula of P.
(ii) When 0.14g of P was vapourised at 20℃ and 740mmHg pressure, it
occupied a volume of 39.5 . Determine the molecular formula of P.
(b) When P was treated with sodium bicarbonate, effervescence of a colourless
gas occurred. Identify P.
(c) P was treated with iron(III) chloride solution. State what was observed and
write equation for the reaction that takes place.
17. A compound Q contains 63.7% lead, 14.8% carbon, 1.8% hydrogen and the rest being
oxygen. When vapourised, 0.225g of Q occupy 15.5 cm3 at standard temperature and
pressure.
(a) (i) Calculate the empirical formula of Q.

(ii) Deduce the molecular formula of Q.

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(b) Compound Q decomposed on heating to form a yellow residue on cooling and a
colourless vapour that turned limewater milky and formed a yellow precipitate
with 2,4-dinitrophenyl hydrazine in presence of sulphuric acid.
(i) Write the name and formula of Q.
(ii) Write equation leading to formation of the yellow precipitate.
18. A compound P contains 52.2% carbon, 13.0% hydrogen and the rest being oxygen.
(a) Determine the empirical formula of P
(b) When vapourised, 0.1g of P occupied 78.8 cm3 at 157℃ and a pressure of
740mmHg.
(i) Calculate the formula mass of P
(ii) Determine the molecular formula of P.
(c) Write the structural formulae of all possible isomers of P
(c) P does not react with sodium metal. Identify P.
(d) Write an equation to show how P can be prepared from methanol.
19. (a) An organic compound A contains carbon, hydrogen and oxygen only. On
combustion, 0.463g of A gave 1.1g carbon dioxide and 0.563g of water. Determine
the empirical formula of A
(b) When vapourised, 0.1g of A occupies at ℃ and . Determine
the molecular formula of A.
(c) A reacts with sodium metal with evolution of a gas. Write the structural formula
of all possible isomers of A.
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(d) A reacts with anhydrous zinc chloride and concentrated hydrochloric acid to give a
cloudy solution in about 5 minutes.
(i) Identify A
(ii) Show how A could be synthesised from but-2-ene
20. A solid inorganic nitrate contains 9.37% by mass of magnesium, 10.93% nitrogen and
42.18% of water. Determine the molecular formula of the nitrate if its molecular mass
is 256.
21. When 0.203g of hydrated magnesium chloride, , was dissolved in water
3
an titrated with 0.1M silver nitrate solution, 20.0cm of the silver nitrate solution was
required for complete reaction. A sample of the hydrated chloride lost 53.2% of its
mass when heated in a stream of hydrogen chloride gas. Calculate the value of x and
n.
22. A compound Z contained 19.1% nitrogen, 43.6% oxygen and the rest being
manganese.

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(i) Calculate the empirical formula of Z
(ii) 10g of Z in 1000g of water lowered the freezing point of water by 0.127oC.
Calculate the molecular formula of Z ( for water is )
(b) When Z was strongly heated, brown fumes were given off. Z dissolved in water
to form a pink solution which decolourises acidified potassium manganate(VII)
solution. Identify Z.
(c) State what would be observed and write equation(s) for the reaction(s) that took
place when to the solution in (b) was;
(i) added concentrated nitric acid and lead(IV) oxide and the mixture boiled.
(ii) sodium carbonate solution was added
23. (a)When 0.1g of aluminium was vapourised at 350 oC and a pressure of 1 atmosphere,
19.2 cm3 of vapour was formed.
(i) Calculate the relative molecular mass of aluminium chloride.
(ii) Write the structural formula and molecular formula of aluminium chloride
in the gaseous state at 350 oC.
(b) Aluminium chloride is normally contaminated with traces of iron(III) chloride.
(i) Name one reagent that can be used to detect the presence of iron(III) ion in a
contaminated solution of aluminium chloride.
(ii) State what would be observed if the contaminated aluminium chloride solution
was treated with the reagent you have named in (b)(i)
(iii) Write equation for the reaction leading to the observation you have stated in
(b)(ii)
(c) Water was added drop wise to aluminium chloride.
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(i) State what was observed.

(ii) Write equation for the reaction that took place.
(d) State one use of aluminium chloride in organic synthesis.
24. When 0.13g of a chloride of iron was vapourised at 600K and 1 atmosphere, 20 cm3
of a vapour was formed.
(a) Calculate the relative molecular mass of the chloride of iron.
(b) Determine the;
(i) Molecular formula of the chloride of iron,
(ii) Structural formula of the chloride of iron in vapour phase.
25. An organic compound, Q contains 58.8% carbon, 9.8% hydrogen and the rest
oxygen.
(a) Calculate the empirical formula of Q.
(b) Determine the molecular formula of Q
(c) (i) Q reacts with aqueous sodium hydroxide under reflux to produce propan-1-ol

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

as one of the products. Identify Q.
(ii) Write an equation to show how R can be synthesized from propan-1-ol
and indicate a mechanism for the reaction.
26. A compound Q contains 60.0% carbon, 13.3 % hydrogen and the rest being oxygen.
(a) Calculate the simplest formula of Q.
(b) When 0.698g of Q was dissolved in 100g of a solvent, there was 0.19 oC
depression in freezing point of the solution. ( Kf of the solvent = 1.630C)
Calculate;
(i) The empirical formula of Q
(ii) The molecular formula of Q
(c) Write the names and structural formulae of all possible isomers of Q.
(d) When Q was reacted with iodine in aqueous sodium hydroxide, a yellow precipitate
was formed.
(i) Identify Q
(ii) Write equation for the reaction between Q and iodine in aqueous sodium
hydroxide.
(iii) State what would be observed when Q is reacted with acidified potassium
dichromate(VI) solution and name the major organic product.
(e) When Q was heated with excess concentrated sulphuric acid, a gas W which turned
the purple solution of acidified manganate(VII) to colourless was evolved. Write
equation for the reaction between:
(i) Q and sulphuric acid and suggest a mechanism for the reaction.
(ii) W and acidified manganate(VII) ions and name the product.
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(f) Suggest a plausible mechanism for the reaction between Q and hot concentrated
sulphuric acid.
27. A compound Q contains 76.32% carbon, 6.38% hydrogen and the rest being oxygen.
A solution of Q in water is acidic but does not liberate carbon dioxide from
carbonates. A solution of 1.50g of Q in 20.90g of benzene freezes at 1.3℃ while pure
benzene freezes at 5.50℃.
(a) Determine;
(i) the empirical formula of Q.
(ii) the molecular formula and write the structural formula of Q.
(
(b) Explain why a solution of Q in water is acidic.
(c) Describe the reaction between Q and bromine water.
(d) Write equation and outline mechanism for the reaction between Q and;
(i) ethanoylchloride

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(ii) chloromethane in presence of sodium hydroxide.
(e) Write equations to show how Q can be;
(i) Prepared from benzene and propene.
(ii) Converted to methylbenzene.
28. (a) An organic compound Z contains by mass 51.90% carbon, 4.86% hydrogen and
the rest being bromine. Determine the empirical formula of Z.
(c) When 0.8g of Z was vapourised at 80℃ and a pressure of 700mmHg, it occupied a
volume of 136 cm3. Determine the molar mass of Z.
(d) Deduce the molecular formula of Z.
(e) When Z was heated with excess sodium hydroxide solution, it formed a
compound Y. On heating Y with acidified manganese(IV) oxide, a substance W
was formed. W formed a yellow precipitate with 2,4-dinitrophenylhydrazine in
presence of dilute sulphuric acid but gave no observable change with aqueous
ammonia in the presence of silver nitrate solution.
(i) Write the chemical equation leading to formation of substances Y and W
indicating all reagents and conditions.

(ii) Write the chemical equation for the reaction between substance W and
semicarbazine in presence of dilute sulphuric acid. Outline the mechanism for the
reaction.
(iii) Write equation(s) to show how compound Y can be synthesized from benzene.
Indicate the necessary conditions and reagents.
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29. 8.15g of a saturated bromocompound X, with a general formula of

contains 49.08% by mass of bromine.
(a) (i) Determine the molecular formula of X.
(ii) Write the name and structures of possible isomers of X.
(b) When X was heated with sodium hydroxide , a product Y was formed.
When Y was heated with concentrated orthophosphoric acid, cyclohexene was
formed.
(i) Name X and Y.
(ii) Write equation for the reaction between X and sodium hydroxide and
that for formation of cyclohexene.
(c) Discuss the reactions between X and;
(i) Sodium hydroxide
(ii) Silver ethanoate
(iii) Phenol

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(Your answer should include conditions and mechanisms for the
reactions)
30. (a) A gaseous hydrocarbon X contains 11.11% by mass of hydrogen.
(i) Calculate the empirical formula of X.
(ii) If the vapour density of X is 27, determine the molecular formula of X.
(iii) Write the structural formulae and IUPAC names of all possible isomers of X.
(b) 1 mole of X reacts completely with 1 mole of hydrogen gas in the presence of
nickel catalyst at 150℃. Identify X.
(c) When X was warmed with a mixture of concentrated sulphuric acid and water,
substance Y was formed. Y was readily oxidised to compound Z when treated
with hot acidified potassium dichromate solution. Identify;
(i) Y
(ii) Z
(d) Write equation for the reaction and suggest a mechanism for the reaction when;
(i) X was warmed with a mixture of concentrated sulphuric acid and water
(ii) Z was reacted with acidified solution of semicarbazide.
31. An organic compound ,T , on complete combustion yielded 13.2g of carbon dioxide
and 2.7g of water. When 4.7g of T was vapourised at standard temperature and
pressure, it occupied a volume of .
(a) (i) Calculate the empirical formula of T
(ii) Determine the molecular formula of T.
(b) T burns with a sooty flame. Identify T
(c) Discuss the reactions of T with;
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(i) Bromine
(ii) Propene
(iii) Ethanoylchloride.
(Your answer should include conditions for the reactions and
mechanisms for the reactions where applicable)
(d) Write equation to show how T can be synthesized from benzaldehyde.
32. A compound Y contains by mass 61.02% carbon, 15.25% hydrogen and the rest
being nitrogen.
(a) Determine the empirical formula of Y
(b) Compound Y has a density of at s.t.p. Determine the molecular
formula of Y.
(c) Write the structural formula of possible isomers of Y.
(d) Compound Y forms yellow oils when reacted with cold concentrated hydrochloric
acid and sodium nitrite.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) Identify Y
(ii) Write equation for the reaction that took place.
(e) (i) Name the reagent that can be used to confirm the functional group in compound
Y.
(ii) State the observation made
(iii) Write equation for the reaction for the reaction that takes place when the
named reagent in (e)(i) is reacted with compound Y.

Questions 22, 26 and 27 will be simpler after covering colligative properties in Phase
equilibria and gaining more knowledge of organic chemistry.

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CHAPTER TWO
ATOMIC STRUCTURE AND THE PERIODIC
TABLE
Fundamental particles of the atoms and radioactivity
Historical development of the atomic theory
It was the Greek philosophers Democritus and Leucippus who first considered the idea
that matter is made up of particles in about 400BC. This was later supported by Boyle
and Newton. The idea was however not accepted because there was no experimental
evidence for it.

In 1808, a Manchester school teacher, John Dalton restated and extended the older

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concepts. He gathered experimental evidence with which people were convinced. In his
Atomic Theory, Dalton said that “matter is made up of atoms”. Dalton, however never
dreamt that anyone would be able to see an atom.

Modern instruments like X-ray diffraction and advanced microscopes have provided
direct evidence for existence of atoms

Modern theory of the atom

(a) John Dalton’s atomic theory
The main points in Dalton‟s Atomic theory can be summarized as follows;

 All matter is made up of tiny particles called atoms.

 The atoms are chemically indivisible, indestructible and cannot be created.
 All the atoms of any one element are identical i.e. they have the same mass, same
volume and the same chemical properties.
 Atoms of different elements have different mass, volume and chemical properties.
 Chemical combination occurs between elements by atoms joining in small whole
numbers to form a small group of atoms chemically combined together. Dalton
called such a group “a compound atom”. It is now called a molecule.
By using Dalton‟s theory, we can clearly understand that;

When a reaction occurs in a closed vessel, all the atoms present before the reaction are
still present after the reaction. They just merely become rearranged. Since the masses of
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the atoms are constant, the total masses of the substances before and after the reaction
should be the same.

Point of thought; What can make us disagree with Dalton on the

question whether atoms can be created or destroyed or split?

(b) The J.J Thomson model of an atom

Although John Dalton had thought that the atom could not be broken down into anything
simpler, physicists further investigated whether atoms could be made of smaller particles.
In 1895, Crookes, through his experiments on the discharge of electricity through gases at
low pressure, he discovered that a beam of rays was given off by the cathode (the
negative electrode). He called them cathode rays. He also showed that cathode rays
behave like negatively charged particles.

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In 1897, Sir Joseph John Thomson, as a result of experimental work still on the
conduction of electricity through gases at low pressure, measured the velocity of cathode
rays and the value of charge to mass ratio of the cathode rays. He obtained the same value
of ⁄ regardless of which gas he used.

 J.J. Thomson therefore deduced that negatively charged particles were present in
all matter.
 The negatively charged particles were named electrons and were recognized as
particles of which an electric current is composed
 He described an atom as a sphere of positive electricity in which negative electrons
are embedded

Point of thought; What is the main difference between this J.J.Thomson’s

model and Dalton’s model?
J.J. Thomson‟s atomic model is popularly known as the plum pudding model. However,
it had to be abandoned in 1911 on both theoretical and experimental grounds in favour of
Rutherford‟s atomic model.
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(c) Ernest Rutherford’s atomic model

In 1909, Rutherford and colleagues found out that when particles from a Radium
source were directed to a very thin sheet of gold or platinum foil;

 The particles penetrated the gold foil

 A great majority of the particles passed through the foil without change in
direction.
 A small fraction (about 1 in 20,000) of the particles were scattered deflected
through large angles( as high as or more)
Scattered particles

Undeflected particle

Nucleus

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To explain the above facts; Rutherford deduced that;

 Since particles are positively charged, the few deflections that occurred were
because the protons of the atom are collected in a heavy, small positively charged
central nucleus which makes up just a tiny fraction of the atom.
 Since most of the particles passed through the gold foil undeflected, most of the
atom is empty space and the electrons rotate in this space around the nucleus in the
in the same way planets rotate around the sun
The analysis led Rutherford to propose a model in which an atom consists of a very small
positively charged nucleus, in which most of the mass of the atom is concentrated,
surrounded by negatively charged electrons, so that the atom is electrically neutral.

Fundamental particles of the atom

The fundamental particles of an atom include the; protons, neutrons and electrons.

The discovery of the fundamental particles of the atom

The existence of electrons in atoms was first suggested by J.J.Thomson, as a result of
experimental work on the conduction of electricity through gases at low pressures which
produces cathode rays and X-rays, and a study of radioactivity.
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An atom is electrically neutral. This means that if it contains negatively charged

electrons, it must also contain some positively charged particles. These positively
charged particles are the protons and they were discovered after Rutherford‟s
experiments after bombardment of elements with and rays given off by
radioactive elements.

The neutron was discovered by Sir James Chadwick in 1932, by bombarding beryllium
with rays. Chadwick found out that particles which had properties quite different
from those of protons and electrons were given off. They were not deflected at all by
electric and magnetic fields and therefore possessed no charge. The particles had almost
the same mass as a proton. Since they were neutral particles, they were called neutrons.
Later experiments showed that all atoms contain neutrons apart from that of hydrogen.

Properties of the fundamental particles of the atom

Property Electron Proton Neutron

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Approximate relative charge
Have equal but opposite charges
Approximate relative mass ⁄
Actual mass (kg)
Have almost equal masses
Charge (C)

RADIOACTIVITY
Discovery
The discovery of radioactivity took place over several years beginning with the discovery
of X-rays in 1895 by Wilhelm Conrad Roentgen. The work continued with Henri
Becquerel who had learnt of Roentgen‟s discovery of X-rays through the fluorescence of
some materials.
In 1896, a year following the discovery of X-rays, A.H. Becquerel found out that
Uranium and Uranium compounds would also emit a penetrating radiation capable of
affecting wrapped photographic plates. He was experimenting on salts which fluoresced(
glowed in the dark). One day he developed a photographic plate which had been left
wrapped in a drawer of his working table to be used the next day. To his surprise, he
found that the plate had been exposed. Since he knew that no light could penetrate the
wrapping, he perhaps thought the plate was penetrated by some rays coming from the
Uranium salts. He though it wise to investigate this mysterious radiation and gave the
problem to a young research worker called Marie Curie.
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Marie Curie later found out that this strange effect happened with all Uranium salts and it
depended on the amount of Uranium present in the compound. She realized that the
ability to give off the radiation was a property of the atoms of uranium and that it was a
completely new type of property quite different from a chemical reaction. Marie Curie
called this property of the Uranium atom radioactivity.
In 1898, Marie Curie‟s husband left his own research work and joined her with this
exciting discovery. They discovered two new radioactive elements. They called one
Polonium, after Marie‟s native country Poland and the other as Radium.
The naturally occurring elements now known to be radioactive are polonium, radon,
radium, actinium, thorium, protactinium, francium and uranium. Elements that are not
naturally radioactive can also be induced to undergo artificial radioactivity.
In 1903, Rutherford put forward the theory that radioactivity was caused by
disintegration or decay of the large heavy atoms of Radium, Uranium etc., into simpler
atoms of other elements.

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Definition;

Radioactivity is the spontaneous disintegration of heavier unstable nuclei to form

lighter stable nuclei with emission of radioactive particles such as alpha particles, beta
particles and gamma rays.

Types of radiations and their discovery

When an atom splits, the nucleus divides and the protons and neutrons in it form two new
nuclei. The electrons divide themselves between the two. Radioactive substances
therefore have unstable nuclei.

Three types of radiation are given off by radioactive substances. They include the beta
rays ( ), gamma rays ( ) and alpha rays ( ). All these radiations
cause certain substances such as zinc sulphide to luminesce. They also ionize gases
through which they pass.

Radiation Symbol Nature

Beta rays are streams of high speed electrons emitted by
unstable nuclei
Beta( ) rays N.B. These electrons do not come from the extra-nuclear
part of the atom. Beta particles are distinguished from
electrons by their source and high energy.
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Alpha rays are a stream of helium nuclei called alpha

particles and are emitted with high energies from
Alpha( ) rays radioactive nuclei.
An alpha particle is a positively charged particle
consisting of two neutrons and two protons and is
identical to the nucleus of a helium atom.
Gamma ( )rays Gamma rays are light rays(electromagnetic radiations) of
extremely high energy therefore very short wave lengths

A comparison between the characteristics of the different types of

radiations
Radiation
Property Beta rays Alpha rays Gamma rays
Make up High speed electrons Helium nuclei Electromagnetic
radiations
Mass number Negligible
Charge

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Velocity that of light of that of Same as that of light
light
Effect of Deflected towards the Deflected towards the Not deflected
electric field positive pole negative pole
Effect of Deflected much more Deflected in a direction
magnetic field readily and in an opposite that shows that they
direction to that of alpha consisted of positively Not deflected
particles charged particles
Tissue 1 0.01 100
penetration
Penetrating Higher penetrating power very low penetrating Very high penetrating
power than alpha particles power power
(can pass through 0.01m (cannot penetrate more (can pass through 0.1m
of a metal) than through 0.01mm of of a metal)
a metal)
Ionizing power Lower ionizing power Have high ionizing A very low ionizing
than beta particles power power

Some other important particles involved in radioactivity

Particle Symbol
Neutron
Proton
Deuterium
Tritium
Positron
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Balancing nuclear reaction equations

When balancing nuclear reaction equations, the sum of nucleon numbers (mass
numbers) should be the same on both sides. The sum of the proton numbers (atomic
numbers) should also be the same.

Examples
1. Reactions involving emission of the, alpha particles, beta particles ,gamma rays and
some other particles
(i) Emission of an alpha particle
Consider the reaction;

To balance the equation;

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The equation becomes;
Emission of an alpha particle therefore reduces proton
number(atomic number) by 2 units and reduces the mass
number by 4 units

(ii) Emission of a beta particle

Consider the reaction;

To balance the equation;

The equation becomes;

Emission of a beta particle therefore has no effect the mass
number on and increases proton number(atomic number)by 1 unit

(iii) Emission of gamma rays

Consider the reaction;

To balance the equation;

The equation becomes;

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Emission of a gamma ray therefore has no effect on both

proton number(atomic number) and mass number

(iv) Emission of a neutron

Consider the reaction;

To balance the equation;

The equation becomes;

Emission of a neutron therefore has no effect on the proton
number(atomic number) and reduces mass number by 1 unit

(v) Emission of a positron

Consider the reaction;

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To balance the equation;

The equation becomes;

Emission of a positron therefore reduces the proton
number(atomic number) by 1 unit and has no effect on mass
number.

2. Bombardment by particles
(i) Bombardment of nitrogen-14 by an alpha particle to form oxygen-17

Let the other particle emitted be

To balance the equation;

The particle with atomic number 1 and mass number 1 is a proton.

The equation becomes;

(ii) Name the particle that must bombard with Cadmium-113 to convert it to
Cadmium-114 with expulsion of a gamma ray
Let the bombarding particle be

To balance the equation;

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The particle with atomic number 0 and mass number 1 is a neutron.

The equation becomes;
(iii) Alpha bombardment of element Y produces two neutrons and astatine-211.
Identify Y.

To balance the equation;

N.B. Strictly use the atomic number and not the mass number to identify the element
from the Periodic Table

The element with atomic number 83 is .

3. A nuclear reaction can be written in the form;

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This in detail means

The reactions shown in the bombardments above can therefore be represented as;
(i)
(ii)
(iii)
4. Other problems
(i) Complete the equation
........
Let the mass number and atomic number of the other product be x and y respectively.

Note that the atomic number got is 0. But there is no element in the Periodic table with
atomic number 0. Therefore this should be the particle but multiplied by 4
The equation therefore becomes;
4
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(ii) Balance the equation

2
Let the mass number and atomic number of the other product be x and y respectively.

The element with atomic number 36 is

The equation therefore becomes;
2

(iii) Determine the number of alpha particles and beta particles that must be
emitted for to transform to .
Let the number of alpha particles and beta particles emitted be x and y respectively
Note that atomic numbers of the elements can be obtained from the Periodic Table

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Therefore 2 alpha particles and 3 beta particles must be emitted
(iv) A series of radioactive decays can be represented as;
→ → →
(a) Name the particles 1 and 2
(b) Identify elements X , Y and Z.
(c) State the groups to which X, Y and Z belong.
Equations;

(a) 1 is beta particle

2 is alpha particle
(b) X;
Y;
Z;
(c) X;
Y;
Z;

Questions
1. Explain with use of suitable examples; the terms;
(i) Atom
(ii) Ion
(iii) molecule
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2. (a) Explain what is meant by each of the following terms;

(i) Radioactivity
(ii) Radioactive isotopes
(iii) Nuclear reaction
(iv) nucleons
(b) State the differences between a nuclear reaction and a chemical reaction.
3. (a) Explain the difference between;
(i) a and an
(ii) a proton and a deuteron
(iii) and a helium atom
(b) Explain why when alpha particles are directed to thin metal foils, most of them
pass through and a few are scattered backwards.
(c) State the effect of emission of each of the following on the nucleus of an atom;
(i) a positron

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(ii) a neutron
(iii) an alpha particle
(iv) a beta particle
(v) a gamma ray
4. Identify the unknown elements in each of the
following equations using the Periodic Table. Add mass numbers and atomic numbers
wherever they are missing.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
5. Complete each of the following equations
(i)
(ii)
(iii)
(iv)
(v) ........
(vi)
(vii)
(viii)
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(ix)
(x)
(xi)
(xii)
(xiii)
(xiv)
(xv)
6. Naming the particle involved in each case, complete each of the equations.
(i)
(ii)
(iii)
(iv)
(v)
(vi)

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7. State the atomic number and mass number of the new element formed when;
(i) emits a neutron
(ii) emits a positron
(iii) emits a beta particle
(iv) emits gamma rays
(v) emits an alpha particle
(vi) emits 3 alpha particles and 4 beta particles
(vii) emits 4 alpha particles and 2 beta particles
8. Write well balanced equations for the following nuclear reactions;
(i) (v)
(ii) (vi)
(iii) (vii)
(iv)

9. Write well balanced equations for the following nuclear reactions;

(i) Decay of radioactive phosphorus-30 to form silicon-30 with emission of a
positron.
(ii) Proton bombardment of lithium-7 to form alpha particles
(iii) Fusion of deuterium and tritium to form an alpha particle and a neutron
(iv) Bombardment of nitrogen with and alpha particle to form a proton and
oxygen-12
(v) Uranium loses first one and then a second .
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(vi) Uranium loses first one and then a second .

(vii) loses five .
(viii) loses two .
10. Find the;
(i) the number beta particles and alpha particles that must be emitted for
to transform to .
(ii) the number beta particles and alpha particles that must be emitted for to
decay to .
(iii) the number beta particles and alpha particles that must be emitted for to
decay to .
(iv) the number beta particles and alpha particles that must be emitted for to
transform to .
(v) the number beta particles and alpha particles that must be emitted for to
transform to .

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(vi) the number beta particles and alpha particles that must be emitted for to
transform to .
11. (a)A series of radioactive decays can be represented as;
→ → →
State the mass number and atomic number of element Z. Show your working
(b) In a radioactive emission, actinium loses an alpha particle and the product
loses another alpha particle. The product also loses one beta particle. Calculate the
mass number and atomic number of the element that is finally formed.

RADIOACTIVE DECAY
The rate at which a radioactive isotope decays cannot be speeded up or slowed down by
any physical or chemical means. The rate depends on the identity of the isotope and the
amount of isotope present. Radioactive isotopes do not decay at the same rate. Some
decay very rapidly in a few millionths of a second and others can even take billions of
years to decay.

All radioactive decay processes follow first order kinetics.

The rate of radioactive decay at time is directly proportional to the number of

radioactive atoms present. The rate of decay therefore decreases and continues to
decrease as more and more atoms break up.

Therefore if represent number of atoms, then;

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∫ ∫

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[ ] [ ]

( )

Equation can also be written in the form shown below

( )

( )
Any of the equations (i) or (ii) can be used any of the unknown values it by substitution
so long as all the others are known.

Since Activity is proportional to number of We can also express the equations in terms of
radioactive atoms present, we can also have the counts per unit time
equations in the form;

( ) ( ) ( ) ( )
We can also express the equations in terms of mass
( ) ( )

Activity of a radioactive sample is the number of disintegrations per second of a

radioactive sample.
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The decay constant is the proportionality between the number of radioactive atoms and
the rate at which the radioactive atoms decay.

Half life
The time taken for a number of radioactive atoms to decay to ⁄ atoms is called the

half-life. The half-life of Radium is about 1600 years. This means that 1g of Radium
decays to 0.5g in 1600 years. 0.5g decay to 0.25g in a further 1600 years, and so on.
Half-life is the time taken for the amount of a radioactive sample to decay to half its
original value.
Derivation of expression for half life
It can be derived using any of the equations (i) or (ii) above
( ) ( )
when decays to half its original value, then at when decays to half its original value, then

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⁄ and at ⁄ and

( ) ⁄ ( ) ⁄

⁄ ⁄

⁄
⁄
⁄
⁄

The equation ⁄ can be used to find half life when the decay constant is known or the
decay constant when the half life is known.

Examples
1. A radioactive isotope decays from an initial count of 160 counts per minute to 20
counts per minute in 27 days. Calculate its half-life.

( ) ⁄

( ) ⁄

( ) ⁄

⁄
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2. The nuclide of carbon-14 has a half-life of 5600 years. Calculate the age of a
wood from an ancient tomb, if this wood gave 10 counts per minute per gram of
carbon compared with the 15 counts that are given by the carbon from new
wood.
N.B. This is a process of carbon dating that will be seen later. The counts per minute tend to
reduce after the tree is cut and wood begins to decay. This helps us interpreted the values of and
. Mistaking them will yield a negative value of time. Time cannot be negative!!!

⁄ ( )

( )
⁄
⁄
( )

3. If the decay constant for radium is . Calculate the time

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required for 90% of a sample of radium to disintegrate.
( )

( )

( )

4. The half-life of Radium is 1590 years. How long will it take for a sample of
Radium to decay to 25% of its original amount?

⁄
⁄ ( )

⁄
( )

( )

5. The half-life of radioisotope bromine-82 is 36 hours. Calculate the fraction of a

sample of the isotope will remain after one day.
NB. In our previous calculations, you note that units for the decay constant, counts or amount and
time were not consistent but we did not change them. This is because the ratio cancels the units
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⁄
⁄

( )
⁄
( )

6. The half-life of a radioactive element is 150 seconds. What percentage of the

isotope will remain after 600 seconds?

⁄
⁄

( )
⁄

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( )

7. If a sample of a radioactive isotope has a half-life of 3.11 hours and an activity of

1000 at a certain time, calculate the activity one hour later.

⁄ ( )
⁄

( )
⁄

8. It takes 1620 years for 0.03 moles of Radium-226 to decay to 0.015 moles.
Calculate the number of moles of Radium-226 left when 26g decayed for 6 years?
( ) ( )
⁄
⁄

( )
⁄
( )
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Questions
1. A radioactive sample of caesium-136 decays from 480 counts per minute to 60 counts
per minute in 42 days. Calculate its half-life.
2. The half-life of strontium-90 is 29 years. Calculate its decay constant.
3. The disintegration constant of lead-199 is . Determine its half-life.
4. A sample of wood has an activity of . A freshly cut wooden tree has an
activity of . Calculate the age of the wood sample. The half-life of
carbon-14 is 5600 years.
5. A radioactive isotope decays at such a rate that after 68 minutes, only one fourth of its
original amount remains. Calculate its half-life.
6. The half-life of Bismuth is 19.7 minutes. Determine the time taken for 43% by mass
of Bismuth to decay.
7. A radioactive element to a count rate of 120 counts per minute. After 3 hours, it
dropped to 15 counts per minute. Determine the half-life of the isotope.

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8. The half-life of Sulphur-31 is 2.54 seconds. How long will it take for 99% of Sulphur-
31 to get converted to phosphorus?
9. 1.0g of strontium-90 was reduced to 0.953g after 2 years. Calculate the half-life of
strontium-90.
10. Radium undergoes radioactive decay according to the following equation forming
relatively stable nuclides and .
→ → →
(a) Identify the particles and .
(b) 0.02 moles of were allowed to decay for years. The half life of
Radium-226 is 1600 years. Calculate the number of atoms of Radium-226 left at
the end of years.

(c) State any two practical applications of radioactive isotopes.

11. (a) (i) The decay law is given in the expression below . State what the
symbols represent.
(ii) Using the above expression derive the expression for relating the half-life
⁄ and the decay constant.
(b) (i) Nickel (63 ) decays to copper (63 ). Name the particle emitted and write the
equation for the reaction.
(ii) Calculate the time taken for of nickel to change to copper. (The half-life
of nickel is 120 years)
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Graphical representation of radioactive decay

The decay of a radioactive substance can be represented graphically by plotting various
kinds of graphs depending on data experimental data provided.

Note that in each of these graphs can be substituted with Activity (A), amount,
Number of moles, mass or counts

( )

( )

A graph of ( ) agaist time(t) is a ( )

straight line through the origin and its slope
is from which can be obtained and

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used to find ⁄ from the expression

( )

( )

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The graph has a slightly different look if

some or all the values of are less than 1.
A graph of agaist time(t) is a straight
line with an intercept on the axis.
This intercept = and can be used to
find the initial amount, . The graph has a
negative slope = from which can be
obtained and used to find ⁄ from the
expression ⁄

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( )

A graph of ( ) agaist time(t) is a ( )

straight line through the origin and its slope
can be obtained and used to find ⁄ from
the expression ⁄

( )

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A graph of agaist time(t) is a straight The graph has a slightly different look if
line with an intercept on the axis. This some or all the values of are less than 1.
intercept = and can be used to find the
initial amount, . The graph has a negative
slope = from which can be obtained
and used to find ⁄ from the expression

The commonest graph is that of Activity or

mass or amount or number of atoms plotted
against time. The uniqueness with this
graph is that it is a curve with a negative

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slope. From this graph half-life can be got
directly from the graph and can be used to
find the decay constant using the (units)
expression ⁄ .
Half-life is got by getting the time that
corresponds to and then . The half-life
can then be got by the expression
⁄ . The values and are got
from the graph by and

It is advisable that when plotting graphs on radioactivity, the axes begin from the origin.

Questions
1. (a) State what is meant by the terms
(i) Radioactivity
(ii) Half-life
(b) The table below shows data for radioactive decay of element W.

Time (hours) 0.0 5.0 10.0 15.0 20.0 25.0 30.0

Activity (counts per minute) 25.00 23.00 21.25 19.50 18.00 16.50 15.25
(i) Plot a graph of activity against time
(ii) Determine the half-life of element W.
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(iii) Determine the decay constant and state its units.

2. A sample of bromine was irradiated in a nuclear reactor. The table below shows the
radioactivity count rates at various times
Time(hours) 0 1.0 2.0 5.0 10 25 50 75 100
Count rate 500 268 242 225 204 154 95 55 35
(a) Plot a graph of count rate against time
(b) Use your graph to determine;
(i) half life
(ii) the rate constant in
(iii) order of the reaction
3. The table below shows the results of radioactive decay of
Time(seconds) 20 40 60 80 100 120
Mass of (g) 48.2 38.5 31.5 26.0 21.0 17.2
(a) Plot a graph of against time

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(b) Use your graph to determine;
(i) initial mass of
(ii) slope and hence the decay constant of
(iii) half-life of

Nuclear energy
Nuclear energy is energy released during nuclear fission or nuclear fusion. Nuclear
energy has been increasingly used to provide electricity and to drive large ships.

Discovery
In 1935, Enrico Fermi discovered that when a radioactive substance such as Uranium was
bombarded by neutrons, it produced by-products that were not Uranium and were lighter
than the original sample.

In 1938, Otto Hahn, Fritz Strassman, Lise Meitner and Otto Frisch discovered fission.
They found out that the lighter by-products of neutron bombardment on Uranium-235
also released energy. This proved Albert Einstein‟s theory put forth 33 years earlier
that . This was the first time that all the components of fission were known. This
discovery resulted into making of the atomic bomb and nuclear power plants.

Nuclear fission
A very large amount of energy is released in splitting heavy atomic nuclei. Uranium-235
nuclei can be split into smaller elements when a controlled nuclear reaction is carried out.
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Nuclear fission is the process by which a nucleus of a heavier atom is split into nuclei
of lighter atoms, by bombardment with neutrons, with release of a large amount of
energy.

When Uranium-235 is bombarded with neutrons, it undergoes fission to form lighter

elements. The lighter elements include barium ( ), lanthanum ( ), rubidium ( ),
krypton ( ), strontium ( ), and others. Three neutrons are released per Uranium-235
fission. These neutrons produced induce three more fission reactions which release 9
neutrons. The 9 neutrons will also induce nine fission reactions and so on. Therefore a
chain reaction occurs and a large amount of energy is liberated.

The fission products and are unstable too and emit radiations until stable
isotopes are formed.

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The energy released in accordance with Einstein‟s law

Nuclear fusion
Nuclear fusion is a process of combining nuclei of lighter atoms to form heavier nuclei
at very high temperature, liberating a very large amount of energy.

The lighter elements include hydrogen, helium and lithium. The energy produced
comes from decrease in mass of the nuclides.

The fusion reactions only take place at extremely high temperature more
than . This is because a very large amount of energy is required for the
positively charged nuclei to overcome strong repulsion between them. The nuclear fusion
reactions are therefore also known as thermonuclear reactions.

Energy from nuclear fusion is used in the hydrogen bomb

Some examples of nuclear fusion reactions include;

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Nuclear power
Nuclear power is electricity created from a nuclear power plant. The heat produced
during fission of Uranium-235 is used to convert water into steam. This steam is used to
drive turbines that generate electricity.

Applications of radioactivity
Radioactive isotope Use/ application
or radiation
Radium-226 In radiotherapy for treatment of cancer
(from Taking radiographs in radiotherapy instead of X-rays
Radium or Radon)
Phosphorus-32 In radioactive tracing for the uptake of phosphorus by a plant from a
phosphate fertilizer
To elucidate the nature of photosynthesis
In carbon dating, to estimate the age of old objects. Living plants and
animals take in carbon which includes a small proportion of carbon-14.

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When a plant or animal dies, the carbon-14 present in it starts to decay.
The amount of carbon-14 in the dead object after years is determined as
. The amount of carbon-14 in the similar live object is also determined
Carbon-14 as . Using a known half-life of carbon-14, ⁄ , the decay constant ( )
is determined using the equation ⁄ . The value of is then
substituted in the rate equation ( ) to determine the age of the
object ( ) in years.
Iron-59 To study the role of iron in blood formation
Iodine-131 Diagnosis of thyroid diseases and in research on the functioning of the
thyroid gland and the kidneys
Measure thicknesses in materials. The amount of radiation passing
through a material decreases as the material gets thicker. A source of
is placed on one side of the material and a
detector on the other side. The scale reading on the detector will give a
measure of the thickness.
Cobalt-60 It gives out which are used to kill cancerous cells
Plutonium-239 Plutonium-239 which is produced from Uranium-238 in chain reacting
units is used as a fuel in some nuclear reactors.
To determine the mechanism of esterification of monocarboxylic acids
with primary alcohols. An alcohol with oxygen atom labeled with oxygen-
18 is reacted with the carboxylic acid in presence of concentrated
Oxygen-18 sulphuric acid to form an ester and water. On analysis of the ester and
water formed using a mass spectrometer, it is found that the oxygen-18 is
present in the ester and not in water. This proves that the bond in
the alcohol and bond in the acid cleaved.
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18O 18O
The reverse of esterification is acid alkaline ester hydrolysis. An ester
containing a labeled radioactive oxygen-18 atom is heated with sodium
hydroxide solution. Analysis of the products using a mass spectrometer
shows that the oxygen-18 is not in the carboxylic acid formed. This means
that the bond cleaved.

18O ̅ 18O-

NUCLEAR STABILITY
Many atomic nuclei are stable but others decay by giving out radiations. All nuclei with
atomic numbers greater than 83 are unstable and therefore radioactive.

Nuclear stability is the ability of the nucleus of an atom to resist spontaneous decay

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that would result into formation of other nuclei and emission of radiations.

A summarized comparison between stable and unstable nuclei

Stable nucleus Unstable nucleus
Number of protons is approximately equal to The number of neutrons is much greater
the number of neutrons than the number of protons or has a high
number of protons than neutrons
Does not undergo radioactive disintegration. Undergoes radioactive decay emitting
alpha and beta particles to attain stability
Those with odd numbers of both protons and Those with even numbers of both protons
neutrons are least stable and neutrons are most stable.
The stability of a nucleus is related to the ratio of the number of neutrons to the number
of protons. This ratio is represented as ( ⁄ ).

Lighter elements with mass number up to 20 have the ⁄ approximately equal to one.
After atomic number 20, addition of protons is not favoured because of the creation of
more repulsive forces in the nucleus. Addition of neutrons is favoured up to ⁄ .

Beyond this value, atomic nuclei become unstable due an increased number of protons
that lead to increased repulsive forces within the nuclei. The nuclei therefore emit
radiations to become stable and get converted to new nuclei.
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