ELEMENTAL CHEMISTRY

CHEMISTRY NOTES
FORM 3

These are special notes prepared in order to demystify the concept that chemistry is hard,
as observed in previous national performance it is my hope that you find them helpful
and will help the to unravel the mystery of chemistry as it is core discipline in many
careers. However, these notes should be used together with KSCE referential (KLB).
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 [PREVIEW]

BY THE END OF THE CHAPTER, THE LEARNER SHOULD BE ABLE TO:

(a) Describe how nitrogen is isolated from air.

(b) Describe how nitrogen is prepared in the laboratory and state its
properties and uses.

(c) Describe the laboratory preparation and state the properties and uses
of nitrogen oxides.

(d) Describe the laboratory preparation of ammonia and state its properties
and uses.

(e) Explain the differences in chemical reactions of ammonia gas and its
aqueous solution.

(f) Describe the industrial manufacture of ammonia.

(g) Calculate the percentage of nitrogen in nitrogen-containing fertilizers.

(h) Describe the laboratory preparation and manufacture of nitric(V) acid

and state its uses.

(i) Explain dilute and concentrated nitric(V) acid reactions.

(j) Identify the products formed when different nitrates are heated.

(k) State and explain the pollution effect of nitrogen compounds in the
environment
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INTRODUCTION

Nitrogen is non-metal belonging to group (V) of the periodic table. It has atomic number of 7 and
electronic configuration of 2.5 Nitrogen exists in air as a free diatomic gas constituting of about 78% in
air.

Nitrogen also occurs in combined states such as sodium

nitrate, potassium nitrate, and in proteins in both plants and
animals. Moreover, nitrogen gas dilutes the air thus slowing
down processes that need oxygen like rusting, respiration
and burning.

The two atoms of nitrogen in the molecule are firmly held by

strong triple covalent bonds which need a lot of heat to be
broken. This makes nitrogen gas relatively inert and does not take place in many chemical reactions.

PREPARATION OF NITROGEN

a. Isolation From Air

In the laboratory, nitrogen can be prepared through isolation of air. This method is done by taking out
other components of air so as to obtain nitrogen gas. The set up below is used to demonstrate this
process.

When water is passed into the aspirator, it displaces the air. The displaced air then passes through
concentrated sodium hydroxide or concentrated potassium hydroxide which removes/absorbs the carbon
(IV) oxide gas.

KOH (aq) + CO2 (g) KHCO3 (aq)

Or
2KOH (aq) + CO2 (g) K2CO3 (aq) + H2O (l)

The carbon (IV) oxide free air is then passed over heated copper turnings. It reacts with oxygen to form
a black copper (II) oxide solid. Oxygen is removed.

2Cu (s) + O2 (g) 2CuO (s)

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 The remaining air is mainly nitrogen and it is collected by overwater method because it is slightly
soluble in water.

N/B : The nitrogen so obtained using this method is not pure as it contains noble gases as impurities.

If nitrogen is required dry, the gas is passed through concentrated sulphuric (VI) acid

ii. Production Of Nitrogen Through Isolation Method

Nitrogen is obtained on a large scale by fractional distillation of liquid air. Dust particles are first
removed from air through electrostatic precipitation. The dust-free air is then passed through
concentrated sodium hydroxide solution to remove carbon(IV) oxide gas. The remaining air is passed
into a condensation chamber and cooled to –25°C. Water vapour separates out as ice.

The residual gas is compressed to a pressure of 200 atmospheres. Repeated expansion and
contraction of the air cools it to a liquid at a temperature of –200°C. The main constituents of liquid air
at this stage are nitrogen and oxygen whose boiling points are –196°C and –183°C respectively.
Nitrogen has a lower boiling point and therefore distills out first followed by oxygen.

-196

-183

b. Laboratory Preparation Of Nitrogen Gas.

Nitrogen is prepared in the laboratory by action of heat on ammonium nitrite.

The ammonium nitrite used in this procedure is prepared by the double decomposition method.
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i.e Sodium nitrite and ammonium chloride are mixed, dissolved in water and the mixture heated gently
to yields ammonium nitrite and sodium chloride.
NH4Cl (aq) + NaNO2 (aq) NH4NO2 (aq) + NaCl (aq)

The resulting Ammonium nitrite is unstable and decomposes to form nitrogen and steam on heating

NH4NO2 (aq) Heating N2 (g) + 2H2O (g)

Other Methods Known For Preparing Nitrogen Gas Include:

i. Reduction of copper (II) oxide or lead (II) oxide by ammonia.

3CuO (s) + 2NH3 (g) N2 (g) + 3Cu (s) + 3H2O (l)
3PbO (s) + NH3 (g) N2 (g) + 3Pb (s) + 3H2O (l)
ii. Action of chlorine on excess ammonia. Ammonia burns spontaneously in chlorine yielding
nitrogen gas.
Cl2 (g) + 8NH3 (g) N2 (g) + 6NH4Cl(s)
iii. Reductions of oxides of nitrogen by heated copper
Cu(s) + N2O (g) CuO(s) + N2 (g)
2Cu(s) +2NO (g) 2CuO(s) + N2 (g)
4Cu(s) + 2NO2 (g) 4CuO(s) + N2 (g)
N/B Nitrogen gas prepared this way is much pure because it does not contain water vapour, noble gases
and dusts.

PHYSICAL PROPERTIES OF NITROGEN

• Is a colourless and odorless gas.
• It is less dense than air.
• It is sparingly soluble in water
• It has no effect on blue or red litmus paper. It is a neutral gas.
• It does not burn or support combustion.
• It liquefies at -196°C and freezes at -210°C
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CHEMICAL PROPERTIES OF NITROGEN

Nitrogen is rather chemically inert because the triple covalent bond between nitrogen atoms in the
molecule requires a lot of heat energy to break before reacting.

At high temperatures nitrogen combines with metals to form metal nitrides. E.g. Burning magnesium
continues to burn in a gas jar of nitrogen because the bright white-hot flame of magnesium is hot
enough to break the triple bond hence causing a reaction. Magnesium nitride (white ash) is formed.

3Mg(s) + N2 (g) Mg3N2 (s)

If water is added to the white ash, magnesium hydroxide and ammonia are produced.

Mg3N2 (s) + 6H2O (l) 3Mg (OH) 2 (aq) + 2NH3 (g)

Lithium metal also forms lithium nitride (Li3N) when burnt in air. It also decomposes
water to form hydroxides and ammonia.
Li(s) + N2 (g) Li3N(s)
2Li3N(s) + H2O (l) 6LiOH (aq) + 2NH3 (g)
• Nitrogen reacts with hydrogen at 200 - 500atmospheres and 450°C in presence of iron catalyst to
form ammonia.
3H2 (g) + N2 (g) 2NH3 (g)
This is called Haber process.
Nitrogen does not react readily with non – metals and this is why there is no observable change if
burning sulphur is lowered into a gas jar of nitrogen.
However, silicon nitride is formed when nitrogen is passed over strongly heated silicon.
Si(s) + N2 (g) Si3N4 (s)
Test For Nitrogen

Nitrogen is distinguished from other gases by lack of response to tests.

Uses Of Nitrogen

• Manufacture of ammonia in Haber process.

• In light bulbs because it’s relatively inert thus prevents oxidation of filament.
• As a refrigerant. Liquid nitrogen provides a very cold (-196°C) and inert atmosphere which is
applied in storage of semen of livestock used in artificial insemination
• Nitrogen is used in flushing pipes to remove flammable vapour especially in ships.
• Nitrogen under pressure is used in oil fields to force oil from underground deposits.
• Is used to preserve packed foods where it provides inert atmosphere. This eliminates oxygen
which destroys packed food by reacting with their oils.
• It is used to fill empty oil tankers which prevent possibilities of explosions which may occur as a
result of reaction between sparks and some petrol vapours remaining in the tank.
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 OXIDES OF NITROGEN
There are three main oxides of Nitrogen: These includes
Oxidation number
Nitrogen (I) Oxide N2O +1
Nitrogen (II) Oxide NO +2
Nitrogen (IV) Oxide NO2 +4

1. NITROGEN (I) OXIDE (DINITROGEN OXIDE)

Nitrogen (I) Oxide is commonly known as dinitrogen monoxide, nitrous oxide or “laughing gas” This
gas is also an example of greenhouse gas.

Nitrogen (I) Oxide is prepared by gently heating ammonium nitrate. The reaction is exothermic and
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may cause explosions if heated strongly. As a precaution, heating is discontinued after about 3 of the
solid has decomposed.(stop heating while some of ammonium nitrate still remain in the flask to
avoid an explosion.)

Heat
NH4NO3 (s) N2O (g) + 2H2O (g)

N/B The gas is collected over warm water because its only slightly soluble in warm water.

The gas could also be prepared by heating a mixture of any ammonium salt and a nitrate e.g. ammonium
sulphate and potassium nitrate.
(NH4)2SO4 (s) + 2KNO3 (s) 2NH4NO3 (s) + K2SO4 (s)
The ammonium nitrate then decomposes giving off nitrogen (I) oxide. This method is much safer with
less likelihood of explosions compared to heating ammonium nitrate directly.

PHYSICAL PROPERTIES

i. It is a colourless gas with a faint sweet smell

ii. It is fairly soluble in cold water but insoluble in hot/warm water and that is why it is collected
over warm water.
iii. An aqueous solution of the gas is neutral to litmus paper.
iv. It is slightly denser than air. (has a density of 1.977kg/m3 while that of air is 1.2929kg/m3)
v. Has a melting point of -90.8°C and boiling point of -88.5°C
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CHEMICAL PROPERTIES

- It relights a glowing splint

Nitrogen (I) oxide itself does not support combustion but high temperature (about 600°C) decomposes
it to oxygen and nitrogen. The oxygen produced supports the combustion of various substances.

2N2O (g) 2N2 (g) + O2 (g)

It is thus distinguished from oxygen by its sweet smell.

- Burning metals and some non - metals continue to burn in the gas forming their
corresponding oxides and nitrogen gas are formed.

Magnesium continues to burn brightly because the white-hot flame decomposes the gas producing
oxygen that makes magnesium to continue burning.

Mg (s) + N2O (g) MgO(s) + N2 (g)

Ca(s) + N2O (g) CaO(s) + N2 (g)

When the gas is passed over heated copper metal, nitrogen gas and copper (II) oxide are formed.

Cu(s) + N2O (g) CuO(s) + N2 (g)

Sulphur continues to burn in nitrogen (I) oxide with a blue flame. An acidic gas with a strong choking
smell is liberated

S(s) + 2N2O (g) SO2 (g) + 2N2 (g)

Carbon and phosphorus also continue to burn in the gas

C(s) + 2N2O (g) CO2 (g) + 2N2 (g)

2P(s) + 5N2O (g) P2O5 (g) + N2 (g)

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 TESTS FOR NITROGEN (I) OXIDE

Because of its ability to re-light a glowing splint and to allow various other substances to burn in it, the
gas can be confused with oxygen. The two can be distinguished by the following properties:

Property oxygen Nitrogen (I) Oxide

Smell No smell Sweet smell
Solubility in water Insoluble in cold water Soluble in cold water
Reaction with N2O Forms brown fumes of NO2 No reaction
Reaction with hot copper Forms black copper (II) oxide Forms copper (II) oxide and
only nitrogen gas

USES OF NITROGEN (I) OXIDE

•
Was used as a mild an aesthetic during minor surgical operations when used with
oxygen. But patients recovering from such surgery laugh hysterically hence
commonly called laughing gas.
• Is used in rocket motors as an oxidizer.
• Is used in internal combustion engine of racing cars to cause engine to burn more fuel
by providing more oxygen for powerful combustion for more energy.
• Is used as a food additive in which as an inert gas is used to displace oxygen to inhibit
bacteria growth when packaging of snacks.
• Used to produce flames for analytical work.
2. NITROGEN (II) OXIDE (NITROGEN MONOXIDE)

Is prepared by the action moderately conc HNO3 (1 volume of conc nitric (V) acid + 1 volume of water
or 1:1 or 50% nitric (V) acid)
3Cu (s) + 8HNO3 (aq) 3Cu (NO3)2 (aq) + 2NO (g) + 4H2O (l)

A vigorous reaction occurs and Nitrogen (II) Oxide is formed however the brown fumes of nitrogen (IV)
oxide are also produced due to presence of oxygen in the apparatus.

Nitrogen (IV) oxides however dissolves in water the trough leaving nitrogen (II) oxide.
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Physical properties of NO

a. Colorless
b. Slightly denser than air.
c. Is slightly soluble in water.
d. Forms a neutral solution.

NB its smell is unknown because it quickly gets oxidized to nitrogen (IV) oxide when exposed to air.

Chemical properties of NO

a. Reaction with burning substances.

It does not burn or support combustion. However, it decomposes to nitrogen and oxygen at
temperature above 1000 ºC
2NO (g) 1000 ºC N2(g) + O2 (g)

The oxygen produced will support the combustion of hot burning substances. The substances are
oxidized.
2Mg (s) + 2NO (g) 2MgO (s) + N2 (g)

P4 (s) + 10NO (g) 2 P2O5(s) + 5N2 (g)

2Cu(s) + 2NO (g) 2CuO(s) + N2 (g)

The heat energy produced by a burning splint is so weak that it cannot decompose NO and thus it is
extinguished.
b. Reaction with atmospheric oxygen.
Nitrogen (II) oxide is readily oxidized by oxygen to form nitrogen (IV) oxide
NO (g) + O2 (g) 2NO2 (g)
(Colorless) (Brown fumes)
NO is the only gas that exhibits this property and is used as a test for NO gas
c. Reaction with iron (II) sulphate solution.
It dissolves in cold iron (II) sulphate turning it from a pale green solution to dark brown solution, iron
(II) sulphate – nitrogen (II) oxide complex, FeSO4 •NO. (nitroso-iron (II) sulphate)
FeSO4 (aq) + NO(g) FeSO4 •NO (aq)
This is the confirmatory test for NO gas

USES OF NITROGEN (II) OXIDE

• Is used in manufacture of nitric (V) acid

• Is given to premature babies. Inhaling the gas mixed with oxygen reduces complications
related to premature babies like breathing problems.
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 3. NITROGEN (IV) OXIDE (NITROGEN DIOXIDE)

Is prepared by action of concentrated nitric (V) acid on copper metal.

Cu (s) + 4HNO3 (l) Cu(NO3)2 (aq) + 2NO2 (g) + 2H2O(l)
The gas is collected by downward delivery (Upward displacement of air) because it is denser than air.

But if a purer nitrogen (IV) oxide is required, nitrates of metals below sodium are thermally
decomposed.
Lead (II) nitrate is the most preferred because:
It crystallizes without water of crystallization which would otherwise interfere with the preparation.
It is non-deliquescent unlike most nitrates.
2Pb (NO3)2 (s) Heating 2PbO(s) + 4NO2 (g) + O2 (g)
The two gases are separated by a freezing mixture of ice + salt. Nitrogen (IV) oxide is condenses to form
a pale-yellow solution called dinitrogen tetra oxide, N2O4 which is a molecular dimer of nitrogen (IV)
oxide.
2NO2 (g) Cooling N2O4 (l)
The two exist as an equilibrium mixture
NO2 (g) N2O4 (l)
(Red brown) (Pale yellow)

When heated, N2O4 dissociates to form NO2.

N2O4 (l) NO2 (g)
This is thermal dissociation reaction.
Oxygen is then collected by overwater method (Downward displacement of water)

Physical properties of NO2

• Is dark brown gas in color

• Has a pungent irritating smell and highly poisonous.
• Is denser than air and thus collected by downward delivery.
• Is easily liquefied on cooling (b.p 22ºC)
• Is soluble in water.
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Chemical properties of NO2

a. Reaction with water

It dissolves in water to form a pale yellow solution which is a mixture of nitric (III) acid and
nitric (V) acid

2NO2 (g) + H2O(l) HNO3 (aq) + HNO2 (aq)

The oxygen in the air the oxidizes nitric (III) acid to nitric (V) acid.

2HNO2 (aq) + O2 (g) 2HNO3 (aq)

b. Reaction with alkalis.

Nitrogen (IV) oxide neutralizes alkalis forming a mixture of nitrates and nitrites.

2NO2 (g) + 2NaOH(aq) NaNO3 (aq) + NaNO3 (aq) + H2O(l)

c. Reaction with hot burning metals/non-metals.

Magnesium and phosphorus continue to burn in nitrogen (IV) oxide because the heat energy
released is able to decompose the gas liberating oxygen which supports combustion of the hot
elements.

4Mg(s) + 2NO2 (g) 4MgO(s) + N2 (g)

2P4 (s) + 10NO2 (g) 4P2O5 (g) + N2 (g)

Uses of nitrogen (IV) Oxide

• Used in manufacture of nitric (v) acid

• As an intermediate in manufacture of explosives, nylon and plastics. i.e. is used as a
nitrating agent in manufacturing of organic compounds with nitrogen
• Is used as an oxidizing agent for rocket fuels and in lead chamber during manufacture of
sulphuric (VI) acid.
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 AMMONIA

Ammonia is a gas at room temperature. It is a compound of nitrogen and hydrogen i.e it is a hydride of
nitrogen or a nitride of hydrogen. A molecule of ammonia has a structure in which a lone pair of
electrons is present.

LAB PRERATION OF AMMONIA

In the laboratory, Ammonia is prepared by heating a mixture of any ammonium salt and alkali. The
commonly used reagents are ammonium chloride and calcium hydroxide. . Ammonia is a more volatile
base and is displaced by a less volatile base, e.g., NaOH, KOH and Ca(OH)2.

2NH4Cl(s) + Ca(OH)2 (s) CaCl2 (s) + 2NH3 (g) + 2H2O (l)

The flask containing the mixture is set in a slanting position to prevent water which condenses on
the cooler parts of the apparatus, from running back into the flask and causing it to crack .
On heating the mixture, ammonia gas is evolved. Once the gas jar is full, the moist red litmus paper
turns blue. Ammonia gas is less dense than air hence collected by upward delivery. The gas is also
highly soluble in water and cannot be collected overwater.
Ammonia gas cannot be dried using drying agents like concentrated Sulphuric (VI) acid and
anhydrous calcium chloride because it reacts with the two
e.g
With concentrated sulphuric (VI) acid, ammonium sulphate salt is formed.
2NH3 (g) + H2SO4 (l) (NH4)2SO4 (s)
With anhydrous calcium chloride, tetreammine calcium chloride is formed, which is a complex
compound.
CaCl2 (s) + 4NH3 (g) CaCl2 •4NH3 (s)
Therefore, Calcium oxide (Quick lime) is the best drying agent for Ammonia gas.
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 Physical properties of ammonia gas.
• Colourless gas with a characteristic choking pungent smell.
• Less dense than air
• Very soluble in water. This could be demonstrated by Fountain Experiment.
• Boils at -33.4ºC and melt at -77.7ºC
• Can easily be liquefied at high pressure.
Chemical properties of ammonia.
a. Ammonia turns a moist red litmus paper to blue.
This shows that the gas is alkaline when dissolved in water.
This is the confirmatory test for ammonia gas
b. Reaction with hydrogen chloride gas
When a glass rod dipped in concentrated hydrochloric acid is brought to the mouth of a gas jar full of
ammonia, the two react to form ammonium chloride fumes.
NH3 (g) + HCl(g) NH4Cl(g)
c. Reaction with water.
Ammonia gas dissolves in water to form an alkaline solution. Ammonium ions and hydroxyl ions are
generated.

NH3 (g) + Water NH3 (aq)

(Ammonium solution)
NH3(g) + H2O(l) NH+4 (aq) + OH-(aq)
The hydroxyl/hydroxide ions make the solution alkaline. When dissolving ammonia gas in water, a
funnel is inverted over water to prevent “sucking back of water” by providing a large surface area for
absorption of ammonia.
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Ammonia is very soluble in water; one volume of water dissolves about 750 volumes of the gas at room
temperature and pressure.

d. Reaction of aqueous ammonia with cations.

Place about 2cm3 of solutions containing ions of calcium, magnesium, aluminium, zinc, iron, lead and
copper ion separate test-tubes. To each solution add aqueous ammonia drop by drop. Shake the mixture
after each drop. Continue adding aqueous ammonia until it is in excess. Record your observations in
table below.

Metal ions in solution Observations on addition of ammonia

Few drops of ammonia Excess drops of ammonia

Ca2+ White precipitate White precipitate persists;

Mg2+ White precipitate Precipitate persists;

Al3+ White precipitate Precipitate persists;

Zn2+ White precipitate Forms a white Precipitate which

dissolves in excess ammonia

Fe2+ Pale green precipitate Precipitate persists; slowly turns red-

brown on exposure to air;

Fe3+ Red-brown precipitate Precipitate persists;

Pb2+ White precipitate Precipitate persists;

Cu2+ Pale blue precipitate Precipitate dissolves forming a deep

blue solution;

Discussion
When ammonia solution is added to a salt solution, hydroxide ions are brought into contact with metal
ions and metal hydroxides are formed. If the metal hydroxide is highly insoluble, then it is precipitated.
If the metal hydroxide is slightly soluble, like calcium hydroxide, then a precipitate is not observed
because ammonia solution is a very weak base and cannot precipitate such hydroxide.
Ionic equations representing precipitation of insoluble metal hydroxides include:

1. Mg2+(aq) from MgCl2;

MgCl2(aq) + 2NH4OH(aq) Mg(OH)2(s) + 2NH4Cl(aq)

Ionically:
Mg2+(aq) + 2OH-(aq) Mg(OH)2(s)
(White ppt)
2. Fe2+ from Fe(NO3)2;
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Fe(NO3)2(aq) + 2NH4OH(aq) Fe(OH)2(s) + 2NH4NO3(aq)

Ionically:
Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)
(Pale green ppt)
3. Fe3+ from FeCl3;

Ionically:
Fe3+(aq) + 3OH-(aq) Fe(OH)3(s)
(Red brown ppt)
Note:
Zn2+(aq) and Cu2+(aq) dissolve in excess ammonia solution forming complex ions.

4. Zinc ions and ammonia solution.

➢ With little ammonia:

ZnCl2(aq) + 2NH4OH(aq) Zn(OH)2(s) + 2NH4Cl(aq)

Ionically:
Zn2+(aq) + 2OH-(aq) Zn(OH)2(s)
(White ppt.)
➢ In excess ammonia:
- The white precipitate of Zn(OH)2(s) dissolves in excess ammonia to form a colourless solution; proof that
solution has Zn2+ ions;
- The colourless solution is a complex salt of tetra-amine zinc (II) ions.
Equation:
Zn(OH)2(s) + 4NH3(aq) [Zn(NH3)4]2+(aq) + 2OH-(aq)
(White ppt.) (Colourless solution-tetra amine zinc (II) ions)
5. Copper (II) ions.

➢ With little ammonia:

- A pale blue precipitate is formed.

Ionically:
Cu2+(aq) + 2OH-(aq) Cu(OH)2(s)
(Pale blue ppt.)

➢ In excess ammonia:
- The pale blue precipitate of Cu(OH)2(s) dissolves in excess ammonia to form a deep blue solution; proof that
solution has Cu2+ ions;
- The deep blue solution is a complex salt of tetra-amine copper (II) ions.
Equation:
Cu(OH)2(s) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 2OH-(aq)
(Pale blue ppt.) (Deep blue solution-tetra amine copper (II) ions)
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 e. Reaction of ammonia with oxygen
Under normal conditions ammonia does not burnt in air. However it burns in oxygen with a green –
yellow flame forming nitrogen and steam.
4NH3 (g) + 3O2(g) 2N2 (g) + 6H2O (g)

The set up below could be used to react the two gases

4NH3 (g) + 3O2(g) 2N2 (g) + 6H2O (g)

Ammonia can also react with air or oxygen in presence of a catalyst; Platinum wire.
The set-up is as shown below.

This is known as catalytic oxidation of ammonia

When hot platinum at a temperature of about 500ºC comes in contact with ammonia, the coil glows. The
reaction between ammonia and oxygen takes place on the surface of the platinum coil that is a catalyst.
A lot of heat is produced during the reaction which enables the platinum to continue glowing.
Ammonia is oxidized to nitrogen (II) oxide.
4NH3 (g) + O2 (g) Platinum catalyst 4NO (g) + 6H2O (g)

Red brown fumes are observed because the nitrogen (II) oxide produced is quickly oxidized to nitrogen
(IV) oxide.
2NO (g) + O2 (g) 2NO2 (g)
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NB Reaction between ammonia and oxygen may explode when ignited so care must be taken
during ignition.
Catalytic oxidation of ammonia is the basis of manufacture of nitric (V) acid.

f. Reaction of ammonia with hot copper (II) oxide.

Ammonia is a reducing agent and will reduce oxides of metals low in the reactivity series to form their
metals.
For example when ammonia is passed over heated copper (II) oxide turnings, the black solid starts to
glow red and gradually changes to brown powder; copper metal. Ammonia is in turn oxidized to
produce nitrogen gas and water. Nitrogen gas is collected over water and water is collected as colourless
liquid droplets in a U-tube. The ice-cold water is used to condense the liquid vapour.

The equations for the reactions include:

CuO(s) + 2NH3 (g) 3Cu(s) + N2 (g) + 3H2O(l)
(Black) (Brown solid)
Lead (II) oxide could also be reduced by ammonia gas.
PbO (s) + NH3 (g) Pb(s) + N2 (g) + 3H2O (l)
(Yellow –cold (Grey)
Orange –hot)

LARGE SCALE MANUFACTURE OF AMMONIA (HABER PROCESS)

The raw materials for the formation of ammonia are:

i. Nitrogen gas
ii. Hydrogen gas
Nitrogen gas is obtained by fractional distillation of liquid air.
Hydrogen gas is obtained as a by – product of cracking crude oils

(iii). Conditions
➢ High pressures
- The process is favored by high pressures and thus a pressure of approximately 200 to 300 atmospheres
is used.
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Reason:
- The volume of gaseous reactants from equation is higher than volume of gaseous products. Thus,
increased pressure shifts the equilibrium to the right; favoring the production of more ammonia.
➢ Low temperatures
- Low temperatures favor production of ammonia;
Reason:
- The reaction is exothermic (releases heat to the surrounding) hence lower temperature will favor the
forward reaction (shift the equilibrium to the right), producing more ammonia.

➢ Catalyst
- The low temperatures make the reaction slow and therefore a catalyst is used to increase the rate of
reaction
- The catalyst used is finely divided iron catalyst

Operation of Haber process

Step 1: Purification
The two gases are mixed in the ratio of 1:3 and passed through purifiers to remove impurities which
would otherwise poison the catalyst.
The impurities removed are:
i. Carbon (IV) oxide
ii. Sulphur (IV) oxide
iii. Dust particles
Step 2: Compression
The mixture is then compressed to pressure of about 200 to 500 atmospheres and then passed into
catalytic chamber; where the mixture is passed over finely divided iron catalyst. The temperature is
about 400○C and 500○C. The reaction is highly exothermic. Around 15% of the gases are converted to
ammonia.
N2 (g) + 3H2 (g) 2NH3 (g) + Heat
Reason for compression
➢ To increase chances of molecules reacting;
➢ To increase rate of collision of the reacting particles.
Ammonia formed is then condensed out as a liquid from the gaseous mixture and stored in cylinders.
Unreacted nitrogen and hydrogen are recycled to raise the yield of ammonia.
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The yield of ammonia is high at higher pressures and low temperature. However it is expensive to
maintain higher pressure. At low temperatures the reaction is slow. To reduce the production cost
optimum conditions of 500°C, 200 atmospheres and iron catalyst are employed.
The optimum conditions for obtaining a high yield of ammonia are:

i. Moderate temperature of about 500○C. since the reaction is exothermic, very high
temperatures will reduce the yield.
ii. A pressure of 200atmospheres; too high pressure means pipes have to be too thick
which is costly.
iii. An iron catalyst.

Uses of ammonia

• Manufacture of nitrogenous fertilizers.

• Manufacture of nitric (V) acid by catalytic oxidation
• Manufacture of sodium carbonate in the Solvay process.
• Used as mild household cleaner to remove oily and greasy dirt.
• Manufacture of hydrazine that is used as rocket fuel.
• As a refrigerant in large cold storage but is replaced by gases known as ‘freons’
• Is used in laundry work to soften hard water and neutralize acidic stains.

NITRIC (V) ACID

Nitric Acid is prepared in the lab by reacting concentrated Sulphuric (VI) acid with a Nitrate like
Potassium Nitrate. Potassium Nitrate or Sodium Nitrate is preferred because:
i. They are volatile and are readily displaced from nitrates by the less volatile concentrated
Sulphuric (VI) acid.
ii. They are less hygroscopic and can be found as dry solids.
The mixture is heated and fumes of brown nitric (V) acid are produced. The fumes are condensed and
collected in a water- cooled receiver as a yellow liquid.
KNO3 (s) + H2SO4 (l) KHSO4 (s) + HNO3 (aq)

The apparatus used is all glass because nitric (V) acid attacks rubber, cork connections and other organic
matters. The pure acid is colourless but the yellow colouration is due to the presence of nitrogen (IV)
oxide formed by the thermal decomposition of the hot acid.
20
 c 4HNO3 (aq) 4NO2 (g) + 2H2O (l) + O2 (g)

The yellow colour could be removed by blowing air through the acid. KHSO4 is formed instead of the
normal salt K2SO4 because the reaction requires high temperature to achieve that which cannot be
sustained in such glass apparatus.

INDUSTRIAL MANUFACTURE OF NITRIC (V) ACID (OSTWALD PROCESS)

The OSTWALDS PROCESS majorly relies on catalytic oxidation of ammonia.
The raw materials are:
i. Ammonia
ii. Air
iii. Water

The mixture of ammonia and air is passed through purifiers to remove dust particles and other impurities
which would otherwise ‘poison’ the catalyst. The mixture is then compressed to a pressure of 9
atmospheres and then passed on the catalytic chamber via heat exchanger. The mixture is at a
temperature of about 230○C. In the catalytic chamber, the temperature is raised to 900○C. The catalyst
used is platinum-rhodium.
The ammonia combines with oxygen to form nitrogen (II) oxide. The reaction is highly exothermic.
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
The hot gaseous products from the catalytic chamber are cooled in the heat exchanger. Nitrogen (II)
oxide is mixed with more air and is oxidized to nitrogen (IV) oxide.
2NO (g) + O2 (g) 2NO2 (g)
This reaction is carried out at a temperature of below 45○C to ensure a high yield of nitrogen (IV) oxide.
The mixture of nitrogen (IV) oxide, air and nitrogen (II) oxide is passed up the absorption tower against
a downward flow of hot water. Nitrogen (IV) oxide and water combine to form nitric (V) acid and nitric
(III) acid (Nitrous acid)
2NO2 (g) + H2O (l) HNO3 (aq) + HNO2 (aq)
(Nitric (v) acid (Nitric (III) acid)

The nitric (III) acid is oxidized to form nitric (V) acid

2HNO2 (aq) + O2 (g) HNO3 (aq)
The mixture resulted is 65% nitric (V) acid and 35% water. The acid is concentrated by careful
distillation of the solution over phosphorus (V) oxide or concentrated sulphuric (VI) acid; a dehydrating
21
agent. Concentrated nitric (V) acid is a colourless fuming liquid with a boiling point of 83ºC.
Commercial nitric (V) acid is 68% pure and has a density of 1.42g/cm3
ASSIGNMENT
WRITE NOTES OF REACTIONS OF DILUTE NITRIC (V) ACID
REACTION OF CONCENTRATED NITRIC (V) ACID.
a. Reaction with iron (II) sulphate.
Concentrated nitric (V) acid is a very powerful oxidizing agent. It oxidizes acidified pale green iron (II)
sulphate to yellow iron (III) sulphate. The acid itself is reduced to nitrogen (II) oxide which is quickly
oxidized to red – brown nitrogen (IV) oxide.
6FeSO4 (aq) + 3H2SO4 (l) + 2HNO3 (l) 3Fe (SO4)3 (aq) + 2NO (g) + 4H2O (l)
b. Reaction with sulphur.
Hot concentrated nitric (V) acid oxidizes sulphur to sulphur (VI) acid while itself is reduced to nitrogen
(IV) oxide.
S(s) + 6HNO3 (aq) H2SO4 (aq) + 6NO2 (g) + 2H2O(l)
c. Reaction with copper metal
Copper is oxidized to copper (II) nitrate as the acid is reduced to water and nitrogen (IV) oxide.
Cu(s) + 8HNO3 (aq) 3Cu(NO3)2 (aq) + 2NO2 (g) + 4H2O(l)
USES OF NITRIC (V) ACID
Manufacture of nitrogenous fertilizers e.g. ammonium nitrate
Is an oxidizing agent during production of artificial fibres like nylon and terylene.
Used in refining of precious metals like gold. A mixture of concentrated nitric (V) acid and hydrochloric
acid in volume ratio 1:3 is known as ‘royal water (Aqua regia)’ and it dissolves metals like gold and
platinum.
Manufacture of dyes and drugs.
Manufacture of explosives like TNT (Trinitrotoluene), ammonium nitrate
NITRATES

Are salts derived from nitric (V) acid.

Test for nitrates
Carry out the following tests and record you observations.
Test Observation
1. Place one spatulaful of sodium nitrate
into a clean test tube. Add 2cm3 of
distilled water and shake the mixture.
Add 1 cm3 of freshly prepared iron (II)
sulphate and shake. Add concentrated
sulphuric (VI) acid slowly and carefully
along the wall of the test tube as shown
2. Place a spatulaful of sodium nitrate in a
dry test tube. Add a few drops of
concentrated sulphuric (VI) acid. Warm
the mixture and add a few pieces of
copper turnings
22

Diagrams KLB Pg 173

Discussion
When concentrated sulphuric (VI) acid is added to the mixture of sodium nitrate and iron(II) Sulphate,
the acid sinks to the bottom because it is denser than the solution. The reaction produces heat. A brown
ring is formed at the junction of the two layers. The brown ring is due to the formation of iron (II)
sulphate – nitrogen (II) oxide complex (Nitroso-iron (II) sulphate); FeSO4 • NO.
All nitrates give the same result; hence this reaction is referred to as Brown ring test for nitrates. This
is the confirmatory test for nitrates.
When sodium nitrate is mixed with concentrated sulphuric (VI) acid and the mixture warmed in
presence of copper turnings, brown fumes of nitrogen (IV) oxide are produced. The reaction takes place
in two stages:
NaNO3 (s) + H2SO4 (l) NaHSO4 (aq) + HNO3 (l)
Cu(s) + 4HNO3 (l) Cu(NO3)2 (aq) + 2H2O(l) + 2NO2 (g)
ASSIGNMENT
Write notes on:
Pollutions effects of nitrogen compounds in the atmosphere and reduction of the pollution.
PAPER 3
SUMMARY AND USEFUL INFORMATION ON QUALITATIVE ANALYSIS:
1. FLAME TEST

Cation Flame

K blue lilac

Na Golden Yellow

Ca red flame

Mg bright white

Fe orange

Cu green flame
23
COLOURS OF SUBSTANCES IN SOLIDS AND SOLUTIONS IN WATER.
COLOUR
SOLID AQUESOUS SOLUTION IDENTITY
(IF SOLUBLE)
1. White Colourless Compound of K+; Na+, Ca2+; Mg2+; Al3+; Zn2+; Pb2+; NH4+
2. Yellow Insoluble Zinc oxide, ZnO (turns white on cooling); Lead oxide, PbO
(remains yellow on cooling, red when hot)
Yellow Potassium or sodium chromate;
3. Blue Blue Copper (II) compound, Cu2+
4. Pale green Pale green (almost colourless) Iron (II) compounds,Fe2+
Green
Green Nickel (II) compound, Ni2+; Chromium (II) compounds, Cr3+;
(Sometimes copper (II) compound, Cu2+)
5. Brown Brown (sometimes yellow) Iron (III) compounds, Fe3+;

Insoluble Lead (IV) oxide, PbO2

6. Pink Pink (almost colourless) Manganese (II) compounds, Mn2+;
Insoluble Copper metal as element (sometimes brown but will turn black on
heating in air)
7. Orange Insoluble Red lead, Pb3O4 (could also be mercury (II) oxide, HgO)
8. Black Purple Manganate (VII) ions (MnO-) as in KMnO4;
Brown Iodine (element)-purple vapour
Insoluble Manganese (IV) oxide, MnO2
Copper (II) oxide, CuO
Carbon powder (element)
Various metal powders (elements)

Reactions of cations with common laboratory reagents and solubilities of some salts in water

CATION SOLUBLE INSUOLUBLE REACTION WITH REACTION WITH

COMPOUNDS (IN COMPOUNDS (IN AQUEOUS SODIUM AQUEOUS AMMONIA
WATER) WATER) HYDROXIDE SOLUTION
Na+ All None No reaction No reaction
K+ All None No reaction No reaction
Ca2+ Cl-; NO3-; CO32-; O2-; SO42-; OH- White precipitate insoluble White precipitate insoluble
; in excess in excess, on standing;
Al3+ Cl-; NO3-; SO42- O2-; OH-; White precipitate soluble White precipitate insoluble
in excess in excess
Pb2+ NO3-; ethanoate; All others; White precipitate soluble White precipitate insoluble
in excess in excess
Zn2+ Cl-; NO3-; SO42- CO32-; O2-; SO42-; OH- White precipitate soluble White precipitate soluble
; in excess in excess
Fe2+ Cl-; NO3-; SO42- CO32-; O2-; OH-; (Dark) pale green (Dark) pale green
precipitate insoluble in precipitate insoluble in
excess excess
Fe3+ Cl-; NO3-; SO42- CO32-; O2-; OH-; (Red) brown precipitate (Red) brown precipitate
insoluble in excess insoluble in excess
Cu2+ Cl-; NO3-; SO42- CO32-; O2-; OH-; Pale blue precipitate Pale blue precipitate
insoluble in excess soluble in excess forming
a deep blue solution
NH4+ All None; Ammonias gas on Not applicable.
warming
24
Qualitative analysis for common anions.

SO42-(aq) Cl-(aq) NO3-(aq) CO32-(aq)

TEST Add Ba2+(aq) ions Add Ag+(aq) from Add FeSO4(aq); Add dilute HNO3(aq); bubble
from Ba(NO3)2(aq); AgNO3(aq). Tilt the tube and gas through lime water;
acidify with dilute Acidify with dilute carefully add 1-2
HNO3(aq) HNO3 cm3 of
Alternatively; concentrated
Add Pb2+ from H2SO4(aq)
Pb(NO3)2 and warm
OBSERVATION The formation of a The formation of a The formation of a Evolution of a colourless gas
white precipitate white precipitate brown ring shows that forma a white precipitate
shows presence of shows presence of the presence of with lime water, turns moist
SO42- ion; Cl- ion; NO3- ions blue litmus paper red; and
Formation of a white extinguishes a glowing splint
precipitate that shows presence of CO32- ions
dissolves on
warming shown
presence of Cl-(aq)
ions
EXPLANATION Only BaSO4 and Only AgCl and Concentrated All CO32- or HCO3- will
BaCO3 can be formed AgCO3 can be H2SO4 forms liberate carbon (IV) oxide with
as white precipitates. formed as white nitrogen (II) oxide dilute acids
BaCO3 is soluble in precipitates. with NO3-(aq) and
dilute acids and so AgCO3 is soluble in this forms brown
BaSO4 will remain on dilute acids but AgCl ring complex
adding dilute nitric is not; (FeSO4.NO) with
acid - PbCl2 is the only FeSO4;
white precipitate that
dissolves on
warming

Checklist:
1. Why is it not possible to use dilute sulphuric acid in the test for SO42- ions;
2. Why is it not possible to use dilute hydrochloric acid in the test for chloride ions?
3. Why is it best to use dilute nitric acid instead of the other two mineral acids in the test for CO32- ions?
4. How would you distinguish two white solids, Na2CO3 and NaHCO3?

What to look for when a substance is heated.

1. Sublimation White solids on cool, parts of a test tube indicates NH4+

compounds;
Purple vapour condensing to black solid indicates iodine
crystals;
2. Water vapour (condensed) Colourless droplets on cool parts of the test tube indicate
water of crystallization or HCO3- (see below)
3. Carbon (IV) oxide CO32- of Zn2+; Pb2+; Fe2+; Fe3+; Cu2+;
4. Carbon (IV) oxide and water vapour (condensed) HCO3-
5. Nitrogen (IV) oxide NO3- of Cu2+; Al3+; Zn2+; Pb2+; Fe2+; Fe3+
6. Oxygen NO3- or BaO2; MnO2; PbO2;
25
26
 [PREVIEW]

CHAPTER 5

By the end of the chapter, the learner should be able to:

(a). Name the sources of sulphur.
(b) Describe the extraction of sulphur.
(c) Describe the preparation of the allotropes of sulphur.
(d) State the properties and uses of sulphur.
(e) Name and describe the preparation of the oxides of sulphur.
(f) State the properties and uses of the oxides of sulphur.
(g) Describe the contact process for the manufacture of sulphuric acid.
(h) Describe the properties and state the uses of sulphuric acid.
(i) Describe the preparation and state the properties of hydrogen
sulphide.
(j) Explain pollution effects of sulphur containing compounds.

Introduction
Sulphur is a second member of group 6 elements . It has atomic number
16 and electronic configuration of 2.8.6. Sulphur occurs naturally as an
element in deposits in USA,
and Italy. It also occurs in
combined states as sulphides
and sulphates e.g. gypsum,
(CaSO4•2H2O) and copper
pyrites (CuFeS2)
27
 Extraction of Sulphur Deposits
Sulphur is extracted by the Frasch process.
The Frasch Process
The process of extracting Sulphur from its ore is based on low melting point of Sulphur which ranges
between 113ºC and 119ºC. This method is used to mine Sulphur from underground where it exists as
free element. After sinking boreholes to the bottom of Sulphur deposit, 3 concentric pipes are placed
inside the borehole. These pipes have different functions:

a) The outer pipe contains superheated water (160ºC -180ºC) and under pressure of 10 atms. The
high pressure ensures water remains in liquid state even at that temperature. Superheated water is
used to melt Sulphur. Sulphur melts at 113ºC. Molten Sulphur is heavier than the hot water, it
thus floats.
b) Hot compressed air at a pressure of about 15atmos is forced through the innermost pipe with
diameter of 2cm. it aerates the molten Sulphur forming froth and reduces its density. The high
pressure forces the Sulphur-water mixture up through the middle pipe.
c) The middle pipe carries the mixture into tanks where Sulphur solidifies to form yellow solids.
Sulphur obtained this way is about 99.5% pure.
However, Frasch process needs a lot of energy and access to large volumes of water.

ALLOTROPES OF SULPHUR
Sulphur exhibits allotropy. Allotropy
refers to the existence of different forms
of the same element in the same physical
state
Allotropes hence are different forms of
the same element in the same physical
The main allotropes of Sulphur/
Crystalline include;
28
 1. Rhombic Sulphur/ Alpha (α) Sulphur/Octahedral Sulphur

2. Monoclinic Sulphur/Beta (β) Sulphur/Prismatic Sulphur

The two allotropes consist of the S8 structures. They only differ in the way they are packed in the
crystal.
The two allotropes are inter- convertible with changing temperature.

Other forms of Sulphur include/ None Crystalline:

• Plastic Sulphur
Is prepared by heating Sulphur until it boils and the boiling Sulphur poured in beaker of cold water.
Long plastic threads of Sulphur are formed.
• Amorphous Sulphur
Is prepared by saturating distilled water with hydrogen sulphide. The solution is exposed to air and a
powder of Sulphur is formed
2H2S(aq) + O2 (g) 2H2O(l) + 2S(s)
• Colloidal sulphur
Is prepared by reacting dilute HCl with dilute sodium thiosulphite (Na2S2O3)
Na2S2O3 (aq) + 2HCl (aq) 2NaCl (aq) + H2O (l) + SO2 (g) + S(s)
N/B
The differences in the properties of the two main allotropes are shown below;
Rhombic Sulphur Monoclinic Sulphur
Octahedral yellow crystals Prismatic (needle like yellow-
brown crystals ) or hexagonal
prism
Stable below 96ºC. slowly Stable between 96ºC and 119ºC.
changes to monoclinic above 96ºC changes slowly to rhombic below
96ºC
Melting point is 113ºC Melting point is 119ºC
3
Density of 2.1g/cm Density of 1.98g/cm3
29
The two allotropes are soluble in Carbon Disulphide and Methylbenzene. They are all insoluble in
water.

Effect Of Heat On Sulphur

Temperature 96 ºC is known as transition temperature. This is the temperature at which one allotrope
changes to another.

When Sulphur is heated, at a temperature of 113ºC, yellow Sulphur melts to clear pale yellow liquid
which flows easily. This liquid consists of S8 rings.

On further heating, at about 150ºC, it becomes red-brown and very viscous. The red – brown flows
slowly. It remains like syrup and a test tube may be inverted without sulphur getting poured. This is
because the S8 ring is broken and formation of a long chains which twist together and do not flow over
one another.

Above 160ºC the liquid darkens further and becomes almost black. Its viscosity reduces. This is because
the long chains are broken to shorter and less entwined chains.

At 444 ºC, sulphur boils to form brown vapours consisting of S8, S6 and S2 which easily form yellow
sublimate (flowers of sulphur) on cold surface.

Physical properties of Sulphur.

• Is a yellow non-metallic element, brittle, crystalline Solid.

• It has a faint characteristic smell, but no taste.
• Sulphur is insoluble in water
• Sulphur is highly soluble in Carbon (IV) Sulphide and methylbenzene. It is sparingly soluble in
alcohol and ether.
• It has a boiling point of about 114ºC.
• Occurs in a number of allotropic forms; two of which are crystalline, rhombic and monoclinic.
30
Chemical properties of sulphur.

a. Sulphur burns in air or oxygen with a blue flame to form Sulphur (IV) oxide.
S(s) + O2 (g) SO2 (g)
In excess oxygen, Sulphur (VI) oxide is formed.
2S(s) + 3O2 (g) 2 SO3 (g)
b. Sulphur combines with some element to form Sulphides. E.g. when iron is mixed with Sulphur
and heated strongly, an exothermic reaction occurs in which iron (II) Sulphide is formed. Once
the reaction starts, the mixture continues to glow because the heat evolved is able to sustain the
reaction.
Fe(s) + S(s) FeS(s)
(Black)

Hot powdered copper also reacts with sulphur to form copper (I) sulphide.
Cu(s) + S(s) Cu2S(s)
(Black)
Sulphur also combines with some non-metals, at high temperature, such as carbon and hydrogen
to form non-metallic sulphides.
C(s) + S(s) CS2 (s)
H2 (g) + S(s) H2S(g)
These two products are highly poisonous.
c. Sulphur is oxidized by hot concentrated Sulphuric (VI) acid to Sulphur (IV) oxide.
S(s) + H2SO4 (l) 3SO2 (g) + 2H2O(l)
Sulphur is oxidized by hot concentrated nitric (V) acid to form sulphuric (VI) acid. The presence
of sulphate ions (SO42-) is tested by adding solution of barium chloride or barium nitrate.
Formation of a white precipitate (Barium sulphate) shows that the solution has sulphate ions.
S(s) +6 HNO3 (aq) H2SO4 (aq) + 6NO2 (g) + 2H2O (l)

N/B
Dilute acids have no effect on Sulphur. Sulphur is only oxidized by hot concentrated acids; nitric
and Sulphuric (VI) acid. Concentrated hydrochloric acid is not an oxidizing agent and thus does
not react with Sulphur.
Uses of Sulphur
• In manufacture of sulphuric (VI) acid
• As a fungicide to kill fungi that cause diseases and sulpha-drugs.
• Making sulphur dyes which are used for dyeing cotton
• Used in vulcanization of rubber (Hardening). Sulphur is heated together with rubber
making rubber tough, harder and less sensitive to temperature
• In manufacture of bleaching agent (Calcium hydrogen sulphite) used to bleach wood pulp
in paper industry.
• Making of important chemicals like carbon (IV) sulphide.
• Manufacture of gunpowder, fireworks and matches
31
Oxides Of Sulphur
Sulphur form majorly two oxides ,
• Sulphur (IV) oxide SO2
• Sulphur (VI) oxide SO3

SULPHUR (IV) OXIDE

It is prepared in the lab by the following ways:
a. Reacting copper with hot concentrated Sulphuric (VI) acid.
The mixture is heated the solution to become hot, the gas is evolved.
Cu(s) + H2SO4 (l) CuSO4 (aq) + 2H2O (l) + SO2 (g)
There is no reaction when the solution is not hot.

The gas produced is passed through concentrated sulphuric (VI) acid to dry it and collected by
downward delivery because it is denser than air.

b. From Sodium Sulphite

Is prepared by action of dilute hydrochloric acid on sodium Sulphite.

Na2SO3 (s) + 2HCl (aq) 2NaCl (aq) + 2SO2 (g) + H2O (l)

Heat is not necessary, but if the reaction is slow, heat may be supplied.

Nitric (V) acid is not used because it. is a strong oxidizing agent which can oxidize the Sulphite to
Sulphate
32
The gas jar is confirmed to be full when the orange potassium chromate (VI) paper turns green.

N/B

- These experiments should be carried in a fume chamber because sulphur (IV) oxide is poisonous.
- To prepare a solution of sulphur (IV) oxide in water, the gas is not dried and is directly bubbled
into water using an inverted funnel to prevent sucking back.
- Nitric (V) acid should not be used.
Reason:
- It is a strong oxidizing agent and cannot therefore reduce the metal sulphites.
- Instead it will oxidize the SO2 produced to sulphuric (VI) acid
Equation:
2HNO3(aq) + SO2(g) 2NO2(g) + H2SO4(l)
Other ways of preparing sulphur (IV) oxide include:

i. Heating sulphur in air

S(s) + O2 (g) SO2 (g)
ii. (c). Roasting sulphur in air
S(s) + O2(g) SO2(g)
iii. Burning of sulphides in air
4FeS2(s) + 11O2 (g) 2Fe2O3 (s) +8SO2 (g)

Preparation of sulphur (IV) oxide solution.

33
(ii). Procedure
- Gas is directly passed into water using an inverted funnel; to prevent “sucking back” by increasing
surface area for dissolution.
Physical properties of Sulphur (IV) oxide

• It is a Colourless gas
• It has an irritating choking smell
• It is easily liquefied at low pressure (3atmos)
• It is 2.5 denser than air
• Is highly soluble in water forming acidic solution
• Has a boiling point of -10ºC and melting point of -72.7ºC

Chemical properties of Sulphur (IV) oxide

A. It Is A Strong Reducing Agent.

An aqueous solution of sulphur (IV) oxide, sulphurous acid is strong reducing agent. The sulphite
radical, SO32-, acts as a supplier of electrons; the overall reaction results into formation of sulphate ions.
Equations:
H2SO3(aq) 2H+(aq) + SO32-(aq) then;
SO32-(aq) + H2O(l) SO42-(aq) + 2H+(aq) + 2e-

i. Reduction of acidified potassium manganate (VII).

When Sulphur (IV) oxide solution is added to acidified potassium manganate (VII) solution. Purple solution
changes to colorless.
This is because purple manganate (VII) ions are reduced to colourless manganate (II) ions, while H2SO3
(sulphurous (IV) acid) is Oxidized to sulphate ions and water.

Equation:
2KMnO4(aq) + 5SO2(g) + 2H2O K2SO4(aq) + 2MnSO4(aq)+ H2SO4(aq)
Ionically;
2MnO-4(aq) + 5SO32-(aq) + 6H+(aq) 2Mn2+(aq) + 5SO42-(aq) + 3H2O(l)
ii. Reduction of potassium chromate (IV) solution

When Sulphur (IV) oxide solution is added to acidified potassium chromate (VI) solution. Acidified potassium
chromate (VI) solution change from orange to green.
Equation
K2Cr2O7(aq) + 3SO2(aq) + H2SO4(aq) K2SO4(aq) + H2O(l) + Cr2(SO4)3(aq)
(Orange) (Green)
Ionically: Oxidation

Cr2O72-(aq) + 3SO32-(aq) + 8H+(aq) 2Cr3+(aq) + 3SO42-(aq)

Reduction
34
N/B
the above equations (reduction of Acidified potassium chromate (VI) solution & acidified
potassium manganate (VII) solution) are the usual chemical tests for Sulphur (IV) oxide.
- Sample experiment
Procedure 1
To 2 cm3 of Sulphur (IV) oxide solution, 2 cm3 of dilute H2SO4 was added, followed by an equivalent volume of
potassium chromate (VI) solution.

Procedure 2
To about 2 cm3 of Sulphur (IV) oxide solution, 2 cm3 of dilute H2SO4 was added, followed by an equal volume of
potassium manganate (VII) solution.
Observation
1. The acidified potassium chromate (VI) solution changes from orange to green
2. Purple solution changes to Colorless

Inference /Conclusion

SO32- ions Present

iii. Reduction of Iron (III) ions to Iron (II) ions (Fe3+ to Fe2+)
When Sulphur (IV) oxide gas bubbled through heated Iron (III) chloride solution, the brown solution turned
green. This is because Aqueous sulfur (IV) oxide reduces to Fe3+ in FeCl3, which is brown to green Fe2+ in
FeCl2(aq).
Ionic Equation
2Fe3+(aq) + SO32-(aq) + H2O(l) Fe2+(aq) + SO42-(aq) + H+(aq)
Sample experiment
About 3 cm3 of Iron (III) chloride solution is heated in a test tube, and sulfur (IV) oxide gas is bubbled
into it.
Observation
The brown solution turns green.

iii. Reduction of bromine water

When sulfur (IV) oxide solution is added to acidified bromine water. The brown color changes to
colorless. In addition to barium chloride, a white precipitate is formed due to the formation of insoluble
barium sulfate.
Equation
Br2(aq) + SO2(g) + 2H2O(l) 2HBr(aq) + H2SO4(aq)

Ironically: Oxidation

Br2(aq) + H2O(l) + SO32-(aq) 2HBr(aq) + SO42-(aq)

(Red-brown) (Colourless)
Reduction
35
In addition to barium chloride
Equation:
Ba2+(aq) + SO42-(aq) BaSO4(s)

Sample experiment
Procedure
Bromine water (red-brown) is added to a solution of sulfur (IV) oxide followed by HCl and BaCl2
solution.
Observation

In addition to barium chloride, a white precipitate is formed

Conclusion/ Inference
SO42- present
N/B
- This test confirms the presence of SO42- since a white precipitate insoluble in dilute hydrochloric acid
is formed.
- CO32-(aq) and SO32- also forms a white precipitate with BaCl2(aq) but the white precipitates dissolve in
dilute HCl(aq)

(v). Reduction of hydrogen peroxide

Procedure
- To 2 cm3 of aqueous sulphur (IV) oxide, an equal volume of hydrogen peroxide is added followed by 1
cm3 of HCl, then a few drops BaCl2 solution.

Observation and explanations:

- Bubbles of a colourless gas; that relights a glowing splint.
- Hydrogen peroxide is reduced to water; while the sulphite ion in aqueous sulphur (IV) oxide
(H2SO3(aq)) is oxidized to SO42-(aq)

EQUATION
H2O2(l) +SO32-(aq) H2O(l) + SO42-(aq)
- On addition of BaCl2, a white precipitate insoluble in dilute HCl.
- This confirms presence of sulphate ions.

Equation:
Ba2+(aq) + SO42-(aq) BaSO4(s)

(vi). Reduction of concentrated nitric (V) acid

Procedure
- Sulphur (IV) oxide is bubbled through (into) a solution of concentrated nitric (v) acid.
Observation
- Brown fumes (of NO2) are liberated.
36
Explanation
- Sulphur (IV) oxide reduces nitric (V) acid to nitrogen (IV) oxide (brown) while it is itself oxidized by
HNO3 to form H2SO4.
- Thus, while SO2 is the reducing agent; HNO3 is the oxidizing agent.

Equation:
2HNO3(l) + SO2(g) 2NO2(g) + H2SO4(aq)
(Brown fumes)
(vii). Reaction with atmospheric oxygen in light.

PROCEDURE:
- About 2 cm3 of Sulphur (IV) oxide solution is left in a test tube in light for 24 hours, dilute HCl is then
added, followed by barium chloride.

OBSERVATIONS AND EXPLANATIONS:

- Atmospheric oxygen in light oxidizes sulphite ion (SO32-) into sulphate (SO42-)

EQUATION:
2SO32-(aq) + O2(g) 2SO42-(aq)
- On adding barium chloride, a white precipitate insoluble in dilute HCl results; confirming presence of
sulphate ion.
Equation:
Ba2+(aq) + SO42-(aq) BaSO4(s)
(White ppt)
B. Sulphur (IV) Oxide As Oxidizing Agent
- It reacts as an oxidizing agent with reducing agents more powerful than itself.
Examples

(a). Reaction with hydrogen sulphide

Procedure
- A test tube of dry hydrogen sulphide gas is inverted into a gas jar full of moist sulphur (IV) oxide, and
the gases allowed to mix.
Observation
- Yellow deposits of sulphur is produced.
Examples:
Oxidation

2H2S(g) + SO2(g) 2H2O(l) + 3S(s)

Reduction
Explanations:
37
- H2S is a stronger reducing agent than sulfur (IV) oxide.
- Thus, sulfur (IV) oxide acts as an oxidizing agent supplying oxygen to the hydrogen sulfide.

NOTE
- Dry gases do not react, and for this reaction to occur, the gases must be moist, or at least one of
them must be moist.
(b). Reaction with burning magnesium
Procedure
- Burning magnesium is lowered into a gas jar full of sulphur (IV) oxide.
Observation
- White fumes of magnesium oxide and yellow specks of sulphur.
Equation

2Mg(s) + SO2(g) 2MgO(s) + S(s)

C. Sulphur (IV) Oxide As Bleaching Agent.

Procedure
- Coloured flower petals are placed in a test-tube full of sulphur (IV) oxide.
Observation
- The coloured (blue or red) petals are bleached (turned colorless);
Explanations:
- In presence of water, sulphur (IV) oxide acts as a bleaching agent. It bleaches by reduction (removal
of oxygen form the dye)
- It first combines with water forming the sulphurous acid; which then reduces the dye to form a
colourless product.
Equations:
SO2(g) + H2O(l) H2SO3(aq)

H2SO3(aq) 2H+(aq) + SO32-(aq)

Then;
SO32-(aq) + [O] SO42-(aq)
From dye
General equation
SO2(g) + H2O(l) + [Dye + (O)] Dye + H2SO4(aq)
Coloured Colourless
Note
- The original color may be restored by oxidation or prolonged exposure to air. This explains why old
newspapers, which were originally bleached white by sulfur (IV) oxide, turn brown with time.
38
- Chlorine bleaches by oxidation; hence, its oxidation is permanent. SO2 is, however preferred because
it is milder in action.

D. Reaction with sodium hydroxide (alkalis)

Procedure
- A gas jar full of sulfur (IV) oxide is inverted over sodium hydroxide solution in a trough and shaken.
Observations
- Solution seen rises in the jar.
Explanation
- Sulphur (IV) oxide is acidic and hence easily absorbed by alkaline solutions such as sodium hydroxide
solution.
- Sodium sulfite and sodium hydrogen sulfites are formed depending on amount of sulphur oxide.
Equations
➢ With limited sulphur (IV) oxide:
2NaOH(aq) + SO2(g) Na2SO3(aq) + H2O(l)

➢ With excess sulphur (IV) oxide:

NaOH(aq) + SO2(g) NaHSO3(aq)

E. Reaction With Chlorine:

-Sulphur (IV) oxide reacts with moist chlorine to form an acidic mixture of sulphuric (VI) acid
and hydrochloric acid.
Equation:
SO2(g) + SO2(g) H2O(l) H2SO4(aq) + 2HCl(aq)
Explanation:
- Sulphur (IV) oxide serves as the reducing agent reducing chlorine into hydrochloric acid;
- Chlorine acts as the oxidizing agent; oxidizing the sulphur (IV) oxide into sulphuric (VI) acid

Tests For Sulphur (Iv) Oxide

1. Characteristic pungent smell.
2. Bleaches flower petals.
3. Decolourises purple potassium manganate (VII)
4. Turns filter paper soaked in acidified orange potassium dichromate (VI) solution to green

Sulphur (IV) oxide as a pollutant

- It is industrial waste in some chemical processes.
- The emission to the air it dissolves forming sulphurous acid.

Equation:
SO2(g) + H2O(l) H2SO3(aq)
39
- Sulphurous acid is readily oxidized to sulphuric (VI) acid; which attacks stonework and metal
structures causing them to corrode.
- If breathed in, SO2 causes lung damage.
Uses of sulphur (VI) oxide
- Industrial manufacture of sulphuric (VI) acid.
- Fumigation in green houses for purposes of pest and disease control.
- Preservative in jam and fruit juices.
- Bleaching agent for wool, straw, paper pulp etc.
Sulphuric (VI) Acid
Industrial Manufacture Of Sulphuric (VI) Acid: The Contact Process
-Sulphur.
- Water
- Oxygen (air)
- Concentrated Sulphuric (VI) Acid.

Step 1: Production of Sulphur (IV) Oxide

Sulphur (IV) oxide is obtained by burning the metal ores of sulphides or elemental sulphur in air.
Equation:
S(s) + O2(g) SO2(g)
- Obtaining sulphur (IV) oxide form pyrites is cheaper than form sulphur. However, flowers of sulphur form
pyrites is impure and contains dust; which involves extra expenses and time in purification.
Step 2: Purification and drying
- The Sulphur (IV) oxide and excess air are passed through a series of driers and purifiers.
- Purifiers remove dust particles, which would otherwise poison the catalyst used in this process by
taking up the catalytic surface thus impairing the catalytic efficiency.
- Purification (removal of dust) is by electrostatic precipitation.
- Are dried through concentrated sulphuric acid then passed through heat exchanger.
Step 3: Heat exchanger reactions
- The pure dry SO2 and excess air mixture are passed into heat exchanger reactions.
40
Reason:

- To lower their temperatures since reaction in the proceeding chamber (catalytic chamber) are
exothermic hence requiring lower temperatures.

Step 4: Catalytic chamber

- Dry dust-free SO2 is mixed with clean excess air, heated and passed into a catalytic chamber
containing vanadium (V) oxide catalyst.
Equation V2O5
2SO2(g) + O2(g) 2SO3(g) + Heat
o
450 C
- The product is sulphur (VI) oxide, SO3.
- Formation of sulphur (VI) oxide is accompanied by evolution of heat (exothermic reaction) and a
reduction in volume.

For maximum yield of SO3, the following conditions must be met

1. Temperature
- The forward reaction is exothermic hence the yield can be favourable in low temperatures.
2. Pressure
- High pressures favour production of more sulphur (VI) oxide.
Reasons
- The volume of gaseous reactants is higher than volume of gaseous products.
- Since reaction involves reduction in volume, theoretically pressure used should be as high as is
economically convenient.
3. Catalyst
- A catalyst neither takes part in a reaction nor increases the yield.
- It merely speeds up the reaction i.e. reduces the time taken to react at equilibrium of 450oC.
- Main catalyst is vanadium (V) oxide (V2O5).
Reasons:
- It is not easily poisoned by dust particles.
- It is cheaper and readily available.
Note:
- The highest yield of sulphur (VI) oxide is obtained at optimum conditions of 4500C and
pressure 2-3 atmospheres in presence of vanadium (V) oxide or platinised asbestos.
Step 5: Heat exchanger reactions
- Hot SO3 gas from catalytic chamber is again passed through heat exchanger for cooling after which the
cooled gas is taken into an absorption chamber.
Step 6: Absorption chamber
- The SO3 is not dissolved (passed) into water directly.
Reason
- It dissolves in water exothermically with a loud, hissing sound giving off corrosive vapour resulting
into harmful sulphuric acid “sprays” or mist all around.
41
- The SO3 is dissolved in conc. H2SO4 forming oleum (pyrosulphuric acid/ fuming sulphuric acid).
Equation:
SO3(g) + H2SO4(l) H2S2O7(l)
- Resultant “Oleum” is then channeled into a dilution chamber.
Step 7: Dilution chamber.
- Oleum is diluted with correct amounts of water to form concentrated sulphuric acid.
Equation:
H2S2O7(l) + H2O(l) 2H2SO4(aq)

Pollution control in contact process

- Main source of pollution is sulphur (IV) oxide.
- In catalyst chamber, SO2 reacts with oxygen forming SO3.
Equation: V2O5
2SO2(g) + O2(g) 2SO3(g) + Heat
o
450 C
- This is a reversible reaction and upto 98% conversion is possible and excess (unreacted) SO2 warmed
and released into atmosphere via long chimneys.
- However, SO2 being a pollutant, little or none should be released into atmosphere.
- This is done by scrubbing the gas.
- This involves neutralizing the chimney gas by a solution of Calcium hydroxide forming a salt (calcium
sulphite) and water.
Equation:
Ca(OH)2(aq) + SO2(g) CaSO3(aq) + H2O(l)
Note:
- In certain cases, filters are also installed to remove any traces of acid spray or mist form the exhaust
gases.
- The unreacted gases (SO2 and SO3) may also be recycled within the process.
Properties of concentrated sulphuric (VI) acid
Physical properties
1. - Colourless, odourless, oily liquid.
2. - Very dense; with density 1.84 gcm-3.
3. - Soluble in water and gives out considerable heat when a solution is formed.
4. - It is hygroscopic – absorbs atmospheric moisture to become wet.
Chemical properties

A. It is a dehydrating agent.
(a). Action on blue hydrated copper (II) sulphate (CuSO4.5H2O) crystals.
(i). Procedure
- A few crystals of hydrated CuSO4.5H2O were put in a test tube and enough concentrated sulphuric (VI)
acid added, to cover them completely.
42
(ii). Observation:
- Blue copper (II) sulphate pentahydrate crystals turn to white powder of anhydrous CuSO4.
Equation
Conc. H2SO4
CuSO4.5H2O(s) CuSO4(s) + 5H2O(l)
(Blue crystals) (White crystals)
Explanations:
- Conc.H2SO4 has a very strong affinity for water and hence removes water of crystallization from
crystals hence dehydrating them.

(b). Action on white sugar (C12H22O11)

(i). Procedure:
- A tablespoonful of sugar is put in an evaporating dish form a beaker and adequate volume of conc.
H2SO4 is added.
(ii). Observations:
- Sugar turns form brown then yellow and finally to a charred black mass of carbon.
- A spongy black mass of charcoal (carbon) rises almost filling the dish.
- Steam is also give off and dish becomes very hot since reaction is exothermic.
Equation Conc.
H2SO4
C12H22O11(s) 12C(s) + 11H2O(l)
(White crystals) (Black solid)
Explanation
- The acid removed from the sugar elements of water (hydrogen and oxygen, ratio 2:1) to form water,
leaving behind a black charred mass of carbon.

(c). Action on oxalic acid (ethanedioic acid (H2C2O4)

- Conc. H2SO dehydrates oxalic acid on heating to a mixture of carbon (II) oxide and carbon (IV) oxide.

Equation
Conc. H2SO4
H2C2O4(s) CO(g) + CO2(g) + H2O(l)
Note:
- Conc. H2SO4 acid gives severe skin burns because it removes water and elements of water from skin
tissue.
- Should the acid spill on skin, it is washed immediately with plenty of water followed with a solution
of sodium hydrogen carbonate.
- Holes appear where the acid spills on clothes for same reason.

(d). Action on alcohols (alkanols)

- Conc. sulphuric (VI) acid dehydrates alcohols to corresponding alkenes.
Example: dehydration of ethanol to ethene
43
Equation:
Conc. H2SO4

CH3CH2OH(s) C2H4(g) + H2O(l)

(Ethanol) (Ethene)

(e). Action on methanoic acid.

- Conc. sulphuric (VI) acid dehydrates methanoic acid to form CO.
Equation:
Conc. H2SO4
HCOOH(s) CO(g) + H2O(l)

B. Further reactions of conc. H2SO4 as an oxidizing agent.

- Hot concentrated Sulphuric acts as an oxidizing agent in which cases it is reduced to sulphur (IV)
oxide and water.

Examples:
(a). Reaction with metals.
➢ Copper
Cu(s) + 2H2SO4(l) CuSO4(aq) + SO2(g) + 2H2O(l)
Note: the copper (II) sulphate formed is white since the conc. H2SO4 further dehydrates the hydrated
CuSO4.
➢ Zinc
Zn(s) + 2H2SO4(l) ZnSO4(aq) + SO2(g) + 2H2O(l)
(Hot acid)
Zn(s) + H2SO4(l) ZnSO4(aq) + H2(g)
(Cold acid)
➢ Lead
Pb(s) + 2H2SO4(l) PbSO4(aq) + SO2(g) + 2H2O(l)
(Hot; conc.) (Insoluble)

C. Reaction with non-metals.

- Concentrated sulphuric acid oxidizes non-metals such as sulphur and carbon to their respective
oxides.
Equations:
➢ With carbon
C(s) + 2H2SO4(l) CO2(g) + 2SO2(g) + 2H2O(l)
➢ With Sulphur
S(s) + 2H2SO4(l) 3SO2(aq) + 2H2O(l)

8. It is a less volatile acid; and displaces more volatile acids (refer to lab preparation of HNO3)

Uses of Sulphuric (VI) acid

44
 • Manufacture of fertilizers.
• Processing of metal ores.
• Manufacture of detergents.
• Manufacture of plastics.
• Manufacture of dyes and paints.
• Manufacture of lead and accumulators.
• Manufacture of polymers.
• Manufacture of petroleum (petroleum refinery).
• Drying agent in industrial processes.
Assignment Write notes on pollution

Hydrogen sulphide gas

- It is a colourless gas with a characteristic “rotten egg” smell; and is usually given out by rotting
cabbage and eggs.

Laboratory preparation

(i). Apparatus:
Dil HCl
Dil. HCl

H2S(g)
Iron (II)
sulphide

Anhydrous Dry H2S gas

Or Warm water

Iron (II)
Calcium chloride sulphide
(ii). Procedure:
- Dilute hydrochloric acid is poured into Iron (II) sulphide in a round-bottomed flask.
- Resultant gas is passed through U-tube with anhydrous calcium chloride to dry the gas.
- This can also be done with phosphorous (V) oxide.

Equation:
FeS(s) + 2HCl(aq) H2S(g) + FeCl2(aq)

Ionically:
S2-(aq) + H+(aq) H2S(g)

(iii). Collection of gas

- When dry, the gas is collected by downward delivery because it is denser than air.
- When wet is collected over warm water because it is more soluble in cold water.
➢ Hydrogen sulphide test.
45
- When a strip of filter paper soaked in aqueous lead (II) ethanoate is put in hydrogen sulphide, the
paper turns black or dark brown.

Reason:
- Due to the formation of lead (II) sulphide which is black.

Equation
H2S(g) + (CH2COOH)2Pb(aq) PbS(s) + 2CH3COOH(aq)
Properties Of Hydrogen Sulphide Gas
Physical properties
1. Colourless and very poisonous gas (similar to hydrogen cyanide)
2. Has a repulsive smell (similar to that of rotten eggs or decaying cabbages)
3. Soluble in water giving a weak acid (only slightly ionized)

Equation:
H2S(g) + H2O(l) H2S(aq)

Then:
H2S(aq) H+(aq) + HS-(aq) 2H+(aq) + S2-(aq)
- The acid is dibasic hence forms hydrogen sulphides.
Equation:
2NaOH(aq) + H2S(g) NaHS(aq) + 2H2O(l)
Note:
- Potassium hydroxide reacts similarly like sodium hydroxide.
Chemical properties
4. Combustion
- Burns in a blue flame in a limited supply of oxygen (air) forming a yellow deposit of sulphur and
steam.
Equation:
2H2S(g) + O2(g) 2SO2(s) + 2H2O(g)
- In plentiful supply (excess) of Oxygen (air) it burns with a blue flame forming SO2 and steam.
Equation
2H2S(g) +3O2(g) 2S(s) + 2H2O(g)
5. It is a reducing agent
- It supplies electrons which are accepted by the oxidizing agent and forms sulphur.
Ionically:
H2S(aq) + 2H+(aq) + S2-(aq)

Then
S2-(aq) S(s) + 2e-(aq)
H2S(aq) + [O] S(s) + H2O(l); in terms of addition of oxygen.
46
EXAMPLES
(i). With acidified K2Cr2O7 solution (potassium dichromate VI)

Equation:
Reduction:

Cr2O72-(aq) + 3H2S(g) + 8H+(aq) 2Cr3+(aq) + 7H2O(l) + 3S(s)

(Orange) (Green)
Oxidation
Observation: The orange solution turns green and H2S oxidized to yellow sulphur.
(ii). Potassium manganate (VII) (KMnO4)
Equation:
Reduction:

2MnO4-(aq) + 5H2S(g) + 6H+(aq) 2Mn2+(aq) + 8H2O(l) + 5S(s)

(Purple) (Colourless)
Oxidation
Observation:
- The Purple solution turns colourless
- Manganate (VII) ions are reduced to manganate (II) ions; H2S oxidized to yellow sulphur
(iii). Action on Iron (III) chloride ions
Equation:
FeCl3(aq) + H2S(g) 2FeCl2(aq) + 2HCl(aq) + S(s)
Ionically:
Reduction:

Fe3+(aq) + S2-(g) Fe2+(aq) + 3S(s)

(Brown) (Pale green)
Oxidation
Observation:
- The brown solution turns pale green;
- The Fe3+(aq) are reduced to Fe2+(aq); while the S2-(aq) are oxidized to yellow sulphur.
(iv). Action with Conc. HNO3
Equation:
2HNO3(aq) + H2S(g) 2H2O(aq) + 2NO2(aq) + S(s) + Heat
Ionically:
Reduction:

2H+(aq) + 2NO3-(aq) + H+(aq) + S2-(aq) 2H2O(l) + 2NO2(g) + S(s) + Heat

(Colourless solution) (Brown) (Yellow)
Oxidation
47
Observation:
- Evolution of brown fumes; and deposits of a yellow solid;
- HNO3(aq) is reduced to brown NO2(g); while S2-(aq) are oxidized to yellow sulphur;
Note: The solution also contains H2SO4 produced by the reaction:
Reduction

2HNO3(aq) + H2S(g) H2SO4(aq) + 8NO2(aq) + 4H2O(l) ;

Oxidation
(v). Action of air on H2S
- The gas is dissolved in distilled water in a beaker and exposed to air; after a few days, a white disposal
is formed.
Equation:
H2S(g) + O2(g) 2H2O(l) + 2S(s)
(vi). Action with concentrated sulphuric (VI) acid.
Equation
Reduction

H2SO4(aq) + 3H2S(g) 4S(s) + 4H2O(l)

Oxidation
(vii). Action with halogen elements
➢ Red-brown bromine water
- Red-brown bromine water is reduced forming colourless hydrogen bromide (Hydrobromic acid) and
yellow deposits (suspension) of sulphur.
Equation:
Reduction

Br2(aq) + H2S(g) 2HBr(aq) + S(s)

(Red-brown) (Colourless) (Yellow suspension)
Oxidation
(viii). Action with hydrogen peroxide.
Equation:
Reduction

H2O2(aq) + H2S(g) 2H2O(l) + S(s)

(Red-brown) (Colourless) (Yellow suspension)
Oxidation
PREPARATION OF METALLIC SULPHIDES
- Hydrogen sulphide reacts with metal ions in solution to form precipitates of metal sulphides; majority
48

of which are black in colour.

(i). Procedure
- The gas is bubbled through solutions of the following salts: Pb (NO3)2, CuSO4, FeSO4 etc.
(ii). Observations and equations
➢ Lead ions:
Pb(NO3)2(aq) + H2S(aq) PbS(s) + 2HNO3(aq)
(Colourless) (Black)
Ionically:
Pb2+(aq) + S2-(aq) PbS(s)
➢ Copper (II) ions:
CuSO4(aq) + H2S(aq) CuS(s) + H2SO4(aq)
(Blue) (Black)
Ionically:
Cu2+(aq) + S2-(aq) CuS(s)
➢ Iron (II) ions:
FeSO4(aq) + H2S(aq) FeS(s) + H2SO4(aq)
(Pal green) (Black)
Ionically:
Fe2+(aq) + S2-(aq) FeS(s)
➢ Zinc ions:
Zn(NO3)2(aq) + H2S(aq) ZnS(s) + 2HNO3(aq)
(Colourless) (Black)
Ionically:
Zn2+(aq) + S2-(aq) ZnS(s)
Note:
- Most metal sulphides are insoluble in water except those of sodium, potassium and ammonium.
Sulphites
- Are compounds of the sulphite radical (SO32-) and a metallic or ammonium cation
Effects of heat
- They decompose on heating, forming SO2;
Example:
Heat
CuSO3(s) CuO(s) + SO2(g)
Test for sulphites
(I). PROCEDURE
- To 2cm3 of the test solution, ad 2 cm3 of BaCl2 or Ba (NO3)2; i.e. addition of barium ions.
- To the mixture add 2 cm3 of dilute HCl or HNO3.

(ii). Observation
- A white precipitate (BaSO3) is formed which dissolves on addition of acid.
- Production of a colourless gas that turns filter paper soaked in acidified orange potassium dichromate
(VI) to green.
(III). EXPLANATIONS
- Only BaSO3; BaCO3 and BaSO4 form white precipitates;
49
- The precipitates of BaSO3 and BaCO3 dissolve on addition of dilute acids; unlike BaSO4;
- BaSO3 produces SO2(g) as it dissolves on addition of a dilute acid; SO2 turns orange acidified
potassium dichromate (VI) to green;
- BaCO3 of the other hand dissolves in dilute acids producing CO2; which has no effect on K2Cr2O7; but
forms a white precipitate in lime water;
➢ On addition of Ba2+:
Ba2+(aq) + SO32-(aq) BaSO3(s)
(White precipitate)
➢ On addition of dilute HCl(aq):
BaSO3(s) + 2HCl(aq) BaCl2(aq) + SO2(g) + H2O(l)
(White precipitate) (Colourless)
Ionically:
BaSO3(s) + 2H+(aq) Ba2+(aq) + SO2(g) + H2O(l)
SULPHATES
- Are compounds of the sulphate radical (SO42-) and a metallic or ammonium cation.
Effects of heat.
- Decompose on heating and liberate SO2 and SO3 or SO3 alone;
- However quite a number of sulphates do not decompose on heating; and thus require very strong
heating in order to decompose.
Examples:
Heat
2FeSO4(s) Fe2O3(s) + SO2(g) + SO3(g)
(Pale green) (Brown) (Colourless gases)
Heat
CuSO4(s) CuO(s) + SO3(g)
(Blue) (Black) (Colourless)
ACTION OF ACIDS
TEST FOR SULPHATES
- To about 2 cm3 of the test solution, 2 cm3 of BaCl2 or Ba (NO3)2 solution is added.
- To the mixture, 2 cm3 of dilute HCl or HNO3 is added.
OBSERVATION
- A white precipitate is formed when Ba (NO3)2 is added; which is insoluble in excess acid.
Explanations.
- Only BaSO3; BaCO3 and BaSO4 form white precipitates;
- The precipitates of BaSO3 and BaCO3 dissolve on addition of dilute acids; unlike BaSO4;
- Thus the white precipitate insoluble in dilute HCl or HNO3 could only be a sulphate; in this case
barium sulphate.
➢ On addition of Ba2+:
Ba2+(aq) + SO42-(aq) BaSO4(s)
(white precipitate)
➢ On addition of dilute acid:
BaSO4(s) + 2HCl(aq) BaSO4(s) + 2HCl(aq); i.e. no effect;
Assignment (Write on pollution by Sulphur compounds)
50
 [PREVIEW]

CHLORINE AND ITS

COMPOUNDS.

By the end of this Chapter, the learner should be able to:

(a) Describe and explain the laboratory preparation, properties and uses
of chlorine gas.
(b) Describe and explain the laboratory preparation, properties and uses
of hydrogen chloride gas.
(c) Explain the effect of a solvent on the properties of hydrogen
chloride.
(d) Describe the industrial manufacture of hydrochloric acid.
(e) Explain the environmental pollution caused by chlorine and chlorine
containing compounds.

Introduction:
- Chlorine is a molecular non-metallic element made up of
diatomic molecules.
Its electron arrangement is 2.8.7 and it belongs to the halogen
family. Chlorine is a chemical
element; it has symbol Cl and
atomic number 17.

The second-lightest of the

halogens, it appears between
fluorine and bromine in the
periodic table and its
properties are mostly intermediate between them. Chlorine is
a yellow-green gas at room temperature. It is an extremely
reactive element and a strong oxidizing agent:
51
Preparation of chlorine.
Note: It is usually prepared by oxidation of concentrated hydrochloric acid by removal of hydrogen.
Equation:
2HCl(aq) + [O] Cl2(g) + H2O(l)
- The [O] is from a substance containing oxygen.
(a). Preparation of chlorine from MnO2 and HCl.
(i). Apparatus:

(ii). Conditions:
- Heating;
- Presence of an oxidizing agent; in this case it is manganese (IV) oxide.
(iii). Procedure:
- Hydrochloric acid is reacted with manganese (IV) oxide (dropwise);
Equation:
MnO2(s) + 4HCl(aq) Heat MnCl2(aq) + 2H2O(l) + Cl2(g)
(iv). Explanation:
- Manganese (IV) oxide oxidizes hydrochloric acid by removing hydrogen resulting into chlorine.
- The manganese (IV) oxide is reduced to water and manganese chloride.
- The resultant chlorine gas is passed through a bottle containing water.
Reason:
- To remove hydrogen chloride fumes (gas) which is very soluble in water.
- Next it is passed through concentrated sulphuric acid or anhydrous calcium chloride; to dry the gas.
(v). Collection:
(a). Wet chlorine is collected over brine (saturated sodium chloride solution) or hot water.
Reason:
- It does not dissolve in brine and is less soluble in water
(b). Dry chlorine is collected by downward delivery (upward displacement of air)
Reason:
- It is denser than air (2.5 times).
Note:
- Chlorine may also be dried by adding calcium chloride to the jar of chlorine.
(c). The first bottle must contain water and the second concentrated sulphuric acid.
Reason:
- If the gas is first passed through concentrated sulphuric acid in the first bottle then to the water; it will
52

be made wet again.

Properties of chlorine gas.
1. Colour and smell.
Caution: Chlorine is very poisonous.
- It is a green-yellow gas with an irritating pungent smell that attacks the nose and the lungs.
- It is 2.5 times denser than air, hence can be collected by downward delivery.
2. Solubility in water.
- It is fairly soluble in water forming green-yellow chlorine water.
Equation:
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
- Chlorine water is composed of two acids; chloric (I) acid (hypochlorous acid) and hydrochloric acid.
3. Action on litmus paper.
- Moist chlorine turns litmus paper red then bleaches it.
- Dry chlorine turns damp blue litmus paper red then bleaches it.
- Moist chlorine bleaches red litmus paper; dry chlorine bleaches damp red litmus paper.
- Dry chlorine has no effect on dry litmus paper.
Reasons:
(i). In presence of moisture chlorine forms chlorine water which is acidic and hence turns blue litmus
paper red.
(ii). Hypochlorous acid in the chlorine water is an oxidizing agent; thus adds oxygen (oxidizes) to the
colour of most dyes; hence bleaching it.

Equations:
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

Acidic solution
Then:
Dye + HOCl(aq) HCl(aq) + {Dye + [O]}
Coloured Colourless
4. Bleaching action.
- Moist chlorine bleaches dyes but not printers ink which is made of carbon.
- The colour change is due to oxidation by hypochlorous acid.
Equations:
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

Acidic solution
Then:
Dye + HOCl(aq) HCl(aq) + {Dye + [O]}
Coloured Colourless
5. Action on a burning splint.
- The gas put out a glowing splint. It does not burn.
6. Action on hot metals.
53
(a). Preparation of iron (III) chloride.
(i). Apparatus.

(ii). Precaution.
- Experiment should be done in a fume cupboard or in the open.
Reason:
- Chlorine gas is poisonous and will thus be harmful to the human body.
(iii). Procedure:
- Dry chlorine gas is passed over iron wool as per the diagram.
(iv). Conditions.
➢ Chlorine gas has to be dry (done by the anhydrous calcium chloride in the U-tube)
Reason:
To prevent hydration hence oxidation of iron (which will then form Fe2O3.5H2O) hence preventing
reaction between iron and chlorine.
➢ Iron metal must be hot; and this is done by heating.

Reason:
To provide activation energy i.e. the minimum kinetic energy which the reactants must have to form
products.
➢ Anhydrous calcium chloride.
- In the U-tube; to dry the chlorine gas.
- In the thistle funnel; to prevent atmospheric water vapour (moisture) from getting into the apparatus
and hence reacting with iron (III) chloride.
(v). Observations:
- Iron metal glows red-hot.
- Red brown fumes (FeCl3(g)) are formed in the combustion tube.
- A black solid (FeCl3(s)) is collected in the flask.
Note:
- Iron (III) chloride cannot be easily collected in the combustion tube.
Reason:
- It sublimes when heated and hence the hotter combustion tube causes it to sublime and its vapour is
collected on the cooler parts of the flask.
(vi). Reaction equation.
2Fe(s) + 3Cl2(g) 2FeCl3(g)
54
(vii). Conclusion.
- Iron (III) chloride sublimes on heating; the black solid changes to red-brown fumes on heating.
Equation:
FeCl3(s) FeCl3(g)
(black) (Red-brown)
(b). Aluminium chloride.
2Al(s) + 3Cl2(g) 2FeCl2(s)
2Al(s) + 3Cl2(g) Al2Cl6(s)
Note:
- Aluminium chloride also sublimes on heating.
Equation:
AlCl3(s) AlCl3(g)
(White) (White)
(c). Reaction with burning magnesium.
(i). Procedure:
- Burning magnesium is lowered into a gar jar of chlorine gas.
(ii). Observations:
- The magnesium continues to burn with a bright blinding flame;
- Formation of white fumes (MgCl2); which cools into a white powder.
(iii). Equation:
Mg(s) + Cl2(g) MgCl2(s)
- Generally, chlorine reacts with most metals when hot top form corresponding chlorides.

Note:
Where a metal forms two chlorides when it reacts with chlorine, the higher chloride is usually formed.
Reason:
The higher chloride is stable. This explains why reactions of chlorine with iron results into iron (III)
chloride and not iron (II) chloride.
7. Reaction with non-metals.
- It reacts with hot metals; forming covalent molecular compounds.
(a). Reaction with phosphorus.
(i). Procedure:
- A piece of warm phosphorus is lowered into a gas jar of chlorine.
(ii). Observations:
- Phosphorus begins to smoulder and then ignites spontaneously.
- Evolution of white fumes (PCl3 and PCl5)
(iv). Explanation.
- Chlorine reacts with warm dry phosphorus to form white fumes of phosphorus (III) and (V) chlorides.
Equations:
P4(s) + 6Cl2(g) 4PCl3(s)
(With limited chlorine)
55
P4(s) + 10Cl2(g) 4PCl5(s)
(With excess chlorine)
(b). Reaction with hydrogen.
(i). Conditions:
- Heating or presence of light; since chlorine and hydrogen do not react with each other at room
temperature.
(ii). Precaution
- The experiment is performed in a fume chamber (cupboard); since the reaction is explosive;
(iii). Procedure:
- Chlorine gas is mixed with hydrogen gas and the mixture heated or exposed to direct light; then
aqueous ammonia brought near the mouth of the jar.
(iv). Observations:
- White fumes at the mouth of the jar.
(v). Explanations:
- Chlorine reacts explosively with hydrogen to form hydrogen chloride gas.
Equation:
Cl2(g) + H2(g) Heat/ Light 2HCl(g).
- The hydrogen chloride gas diffuses upwards and reacts with ammonia at the mouth of the test tube to
form white fumes of ammonium chloride; NH4Cl.
Equation:
HCl(g) + NH3(g) NH4Cl(g)
White fumes.

8. Chlorine as an oxidizing agent.

- Chlorine is a strong oxidizing agent and oxidizes many ions, by readily accepting electrons.
- During the process, chlorine itself undergoes reduction.
(a). Reaction with hydrogen sulphide gas.
(i). Procedure:
- A gas jar full of chlorine gas is inverted into another containing hydrogen sulphide gas.
(ii). Apparatus:

(iii). Observations:
- Yellow deposits (of sulphur)
56
- Misty fumes (hydrogen chloride gas)
(iv). Explanations:
- Chlorine oxidizes hydrogen sulphide gas to sulphur solid, while itself is reduced to hydrogen chloride
gas.
Equation: Oxidation

Cl2(g) + H2S(g) 2HCl(g) + S(s)

Reduction

(v). Conditions:
- At least one of the gases must be moist; they do not react with each other in absence of moisture.
Note:
- In absence of moisture both gases are still in molecular form and hence cannot react; water facilitates
their ionization hence ability to react.
- If aqueous hydrogen sulphide is used, then sulphur forms as a yellow suspension on the acidic
solution.

Equations:
Stoichiometric:
Cl2(g) + H2S(aq) 2HCl(aq) + S(s)
Ionic:
Cl2(g) + S2-(g) 2Cl-(g) + S(s)
(b). Reaction with sodium sulphite.
Procedure:
- Chlorine gas is bubbled through sodium sulphate in a beaker.
- Resulting solution is then divided into two portions.
- To the first portion, drops of dilute nitric acid are added followed by few drops of barium nitrate
solution.
- To the second portion, few drops of lead (II) nitrate are added and the mixture warmed then cooled.
(ii). Observations:
1st portion: White precipitate formed indicating presence of SO42-;
Explanations:
- The white precipitate indicate presence of SO42-; the precipitate is barium sulphate Ba(SO4)2;
- Chlorine oxidizes SO32- in Na2SO3 to SO42- while itself is reduced to chloride ions;
Equations:
H2O(l) + Cl2(g) + Na2SO3(aq) Na2SO4(aq) + 2HCl(aq)
Ionically:
Cl2(g) + SO32-(aq) + H2O(l) SO42-(aq) + 2H+(aq) + 2Cl-(aq)
- On adding barium nitrate (Ba(NO3)2); the Ba2+ ions react with the SO42- to form insoluble BaSO4; the
white precipitate.
57
Ionically;
Ba2+(aq) + SO42-(aq) BaSO4(s)
(White precipitate)
Note:
- The solution is first acidified (with HNO3) before addition of Ba(NO3)2 to prevent precipitation of
BaSO3(s) and BaCO3(s).
2nd portion:
Observation:
- Formation of a white precipitate on addition of Pb(NO3)2 solution.
- On warming the white precipitate dissolves then recrystalizes back on cooling.
Explanations:
- The white precipitate shows presence of either Cl-; SO32- or SO42-
- However the fact that it dissolves on warming confirms the presence of Cl-(aq) and not SO32-(aq) and
SO32-(aq)
Equation:
Pb2+(aq) + Cl-(aq) PbCl2(s)
(White precipitate soluble on warming)
(c). Reaction with ammonia.
(i). Procedure:
Chlorine gas is bubbled through aqueous ammonia.
(ii). Observations:
- Evolution of white fumes.
(iii). Explanation.
- Chlorine gas oxidizes ammonia to nitrogen, while is itself reduced to white fumes of ammonium
chloride.
Equation: Reduction

8NH3(g) + 3Cl2(g) 6NH4Cl(g) + N2(s)

Oxidation

(d). Displacement reactions with other halogens.

(i). Procedure:
- Chlorine is bubbled through aqueous solutions of fluoride, bromide and iodide ions contained in
separate test tubes.
(ii). Observations and explanations:
➢ With fluoride ions.
- No observable change or no reaction; because chlorine is a weaker oxidizing agent than fluorine.
➢ With bromide ions:
- If potassium bromide was used, the colourless solution turns red-brown.
58
Reason:
- Chlorine has a higher tendency to gain electrons than bromine.
- It readily oxidizes bromide ions (in KBr) to form potassium chloride and bromine which immediately
dissolves to make the solution red-brown.
Equation: Reduction

2KBr(aq) + Cl2(g) 2KCl(aq) + Br2(l)

Oxidation Red brown

Ionically;
2Br-(aq) + Cl2(g) 2Cl-(aq) + Br2(l)
With iodide ions.
- Using potassium iodide the colourless solution would turn black.
Reason:
- Chlorine has a higher tendency to gain electrons that iodine.
- It readily oxidizes the I- (in KI) to form iodine and potassium chloride.
- Iodine solid in the resulting solution makes it black.
Equation: Reduction

2KI(aq) + Cl2(g) 2KCl(aq) + I2(l) (black)

Oxidation

Ionically;
2I-(aq) + Cl2(g) 2l-(aq) + Br2(l)
9. Reaction with alkalis.
(a). Reaction with sodium hydroxide solution.
(i). Procedure:
- Bubble chlorine slowly through cold dilute sodium hydroxide solution.
- Dip litmus paper.
(ii). Observation:
- Litmus paper is bleached; the product has the colour and smell of chlorine.
(iii). Explanation:
- Chlorine dissolves in sodium hydroxide to form a pale yellow solution of sodium chlorate (I) or
sodium hypochlorite (NaClO);
- The sodium chlorate (I) bleaches dyes by oxidation.
Equation:
Cl2(g)+ 2NaOH(l) NaCl(aq) + NaClO(aq) + H2O(l)

Pale yellow solution

59
Bleaching action of NaClO:
- The NaClO donates oxygen to the dye making it colourless; and thus it bleaches by oxidation.
Equation:
Dye + NaClO(aq) NaCl(aq) + {Dye + [O]}
Coloured Colourless
Note:
With hot concentrated sodium hydroxide, the chlorine forms sodium chlorate (III); NaClO3.
Equation:
3Cl2(g)+ 6NaOH(l) 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
(b). Reaction with potassium hydroxide
- Follows the trend of sodium.
(c). Reaction with slaked lime {Ca(OH)2(s)}
Equation:
Cl2(g)+ Ca(OH)2(l) CaOCl2(aq) + 3H2O(l)
Calcium chlorate I
Note:
Bleaching powder, CaOCl2 always smells of strongly of chlorine because it reacts with carbon (IV)
oxide present in the atmosphere to form chlorine.
Equation:
CaOCl2(s) + CO2(g) CaCO3(s) + Cl2(g)
10. Effects of chlorine gas on:
(a). A burning candle.
(i). Procedure:
- A burning candle is lowered into a gas jar of chlorine.
(ii). Observations:
- It burns with a small, red and sooty flame.
(iii). Explanations:
- Wax (in candles) consists of mainly hydrocarbons.
- The hydrogen of the hydrocarbon reacts with chlorine forming hydrogen chloride while leaving behind
carbon.
(b). warm turpentine.
(i). Procedure:
- A little turpentine is warmed in a dish and a filter paper soaked (dipped) in it.
- The filter paper is then dropped into a gas jar of chlorine.
(ii). Observation:
- There is a red flash accompanied by a violent action whilst a black cloud of solid particles form.
(iii). Conclusion:
- Black cloud of slid is carbon.
- Turpentine (a hydrocarbon) consists of hydrogen and carbon combined together.
- The chlorine combines with hydrogen and leaves the black carbon behind.
60
Equation:
C10H16(l) + 8Cl2(g) 16HCl(g) + 10C(s)
11. Effects of sunlight on chlorine water.
(i). Procedure:
- Chlorine water is made by dissolving the gas in water.
- A long tube filled with chlorine water is inverted over a beaker containing water.
- It is then exposed to sunlight (bright light) as shown below.
(ii). Apparatus:

(iii). Observations:
- After sometime a gas collects in the tube and on applying a glowing splint, the splint is rekindles
showing that the gas collected is oxygen.
(iv). Explanation:
- Chlorine water has two components.
Equation:
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
- The HOCl being unstable will dissolve on exposure to sunlight, giving out oxygen.
Equation:
2HOCl(aq) 2HCl(aq) + O2(g) (slow reaction)
Overall reaction:
2H2O(l) + 2Cl2(g) 4HCl(aq) + O2(g)

Industrial manufacture of chlorine (the mercury cathode cell)

The electrolysis of brine
(i). Apparatus.
61
(ii). Electrolyte.
- Brine, concentrated sodium chloride solution, NaCl
(iii). Electrodes.
Anode: carbon (graphite)
Cathode: Flowing mercury;
(iv). Ions present:
NaCl(aq) Na+(aq) + Cl-(aq)
H2O(l) H+(aq) + OH-(aq)

(v). Reactions:
Anode:
- Cl- and OH- migrate to the anode.
- Because of high concentration of Cl-(aq), they are discharged in preference to OH- ions.
Equation:
2Cl-(aq) Cl2(g) + 2e-
(Green-yellow)
Cathode:
- H+(aq) and Na+(aq) migrate to the cathode.
- Because the cathode is made of mercury, Na+(aq) is discharged in preference to H+(aq) ions;
Equation:
2Na+(aq) + 2e- 2Na(s)
Note:
- Sodium formed at the cathode dissolves in the flowing mercury cathode to form sodium amalgam
(Na/Hg).
- Sodium amalgam is reacted with water to form sodium hydroxide and hydrogen.
- Mercury (in the sodium amalgam) remains unreacted.
Equation:
2Na/Hg(l) + 2H2O(l) 2NaOH(aq) + H2(g) + 2Hg(l)
- The unreacted mercury is recycled.
(vi). Products:
- Chlorine gas at the anode.
- Hydrogen and sodium hydroxide at the cathode.

Uses of chlorine gas and its compounds.

1. Manufacture of hydrochloric acid.
2. Used in form of bleaching powder in textile and paper industries.
3. For sterilization of water for both domestic and industrial use and in swimming pools.
4. Used in sewage treatment e.g. NaOClO3 solution used in latrines.
5. Manufacture of plastics (polyvinyl chloride; PVC)
6. Manufacture of germicides, pesticides and fungicides e.g. DDT and some CFCs.
7. CFCs are used to manufacture aerosol propellants.
62
8. Manufacture of solvents such as trichloromethane and some chlorofluorocarbons (CFCs).
9. CFCs are commonly freons are used as refrigerants in fridges and air condition units due to their
low boiling points.
10. Manufacture of chloroform, an aesthetic.
Hydrogen chloride gas.
Laboratory preparation of hydrogen chloride gas.
(i). Apparatus:

(ii). Procedure:
- Concentrated sulphuric acid is reacted with sodium chloride, and the mixture heated gently.
- Resultant gas is passed through conc. Sulphuric (VI) acid; to dry the gas.
(iii). Equation:
H2SO4(l) + NaCl(aq) NaHSO4(s) + HCl(g)
Ionically;
H+(aq) + Cl-(aq) HCl(g)
Note:
- The reaction can proceed in the cold, but on large scale HCl(g) is produced by the same reaction but
the heating is continued to re hot.
Properties of hydrogen chloride gas.
1. Colourless gas with a strong irritating pungent smell.
2. Slightly denser than air (1¼ times). This makes it possible to collect the gas by downward delivery.
3. Very soluble in water; and fumes strongly in moist air forming hydrochloric acid deposits.
Diagram:

- The aqueous solution is known as hydrochloric acid.

- It is almost completely ionized (a strong acid) in aqueous solution.
63
Equation:
HCl(aq) H+(aq) + Cl-(aq)
- This solution has the usual acidic properties:
Examples:
(i). turns blue litmus red.
(ii). Liberates hydrogen gas with certain metals e.g. zinc, Magnesium, iron etc.
Note:
Hydrochloric acid does not react with metals below hydrogen in the reactivity series.
Equations:
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
Fe(s) + 2HCl(aq) FeCl2(aq) + H2(g)
(iii). Neutralizes bases to form salt and water.
Examples:
HCl(aq) + NaOH(aq) NaCl(aq) +H2O(l)
2HCl(aq) + CuO(s) CuCl2(aq) + H2O(l)
(iv). Liberates carbon (IV) oxide from carbonates and hydrogen carbonates.
Examples:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
ZnCO3(s) + 2HCl(aq) ZnCl2(aq) + H2O(l) + CO2(g)
NaHCO3(s) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
Note:
As the hydrogen chloride gas very soluble in water, the solution must be prepared using a funnel
arrangement; to prevent sucking back and increase the surface area for the dissolution of the gas;
Diagram: dissolution of hydrogen chloride gas

4. Dry hydrogen chloride is NOT particularly reactive at ordinary temperatures, although very reactive
metals burn in it to form the chloride and hydrogen gas.
Equation:
2Na(s) + 2HCl(aq) 2NaCl(s) + H2(g)
Metals above hydrogen in the reactivity series react with hydrogen chloride gas when heated.
Note:
If reacted with some metals it forms 2 chlorides e.g. iron where iron (II) and iron (III) chlorides exist.
5. Hydrogen chloride gas forms white fumes of ammonium chloride when reacted with ammonia gas;
64
Equation:
NH3(g) + HCl(g) NH4Cl(s)
Note: This is the chemical test for hydrogen chloride gas.
6. Hydrogen chloride is decomposed by oxidizing agents, giving off chlorine.
Examples:
PbO2(s) + 4HCl(g) PbCl2(s) + 2H2O(l) + Cl2(g)
MnO2(s) + 4HCl(g) MnCl2(s) + 2H2O(l) + Cl2(g)
Diagram: reacting hydrogen chloride with an oxidizing agent.

Test For Chlorides.

Test 1: Using silver ions:
Procedure:
- To the test solution, add silver ions from silver nitrate.
- Acidify with dilute nitric acid.
(ii). Observations and inference:
- Formation of a white precipitate shows presence of Cl-(aq)
(iii). Explanations:
- Only silver carbonate and silver chloride can be formed as white precipitates.
- Silver carbonate is soluble in dilute nitric acid but silver chloride is not.
Equations:
- Using Cl- from NaCl as the test solution;
NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s)
White ppt.
Ionically;
Ag+(aq) + Cl-(aq) Ag(s)
White ppt.
Note:
- This precipitate dissolves in excess ammonia.
- The white precipitate of silver chloride turns violet when exposed to light.
Test 2: Using lead ions
(i) Procedure:
- To the test solution, add lead ions from lead (II) nitrate, then warm
(ii). Observations and inference:
65
- Formation of a white precipitate that dissolves on warming shows presence of Cl-(aq)
(iii). Explanations:
- Only lead carbonate, lead sulphate, lead sulphite and lead chloride can be formed as white precipitates.
- Only lead chloride dissolves on warming; unlike the rest which are insoluble even on warming.
Equations:
Using Cl- from NaCl as the test solution;
2NaCl(aq) + Pb(NO3)2(aq) 2NaNO3(aq) + PbCl2(s)
White ppt.
Ionically;
Pb2+(aq) + Cl-(aq) PbCl2(s)
White ppt.
Hydrochloric Acid.
Large scale manufacture of hydrochloric acid.
(i). Diagram:

(ii). Raw materials:

- Hydrogen obtained as a byproduct of petroleum industry; electrolysis of brine or from water by Bosch
process;
- Chlorine obtained from the electrolysis of brine or as fused calcium chloride.
(iii). Procedure:
- A small sample of hydrogen gas is allowed through a jet and burnt in excess chlorine gas to avoid
explosion.
Equation:
H2(g) + Cl2(g) 2HCl(g)
Precaution: A mixture of equal volumes of hydrogen and chlorine explodes when put in sunlight. To
control the reaction, a small amount of hydrogen gas is allowed to burn in excess chlorine through a jet.
- The hydrogen chloride gas formed is dissolved in water over glass beads.
- The glass beads increase the surface area over which absorption takes place.
- Commercial hydrochloric acid is about 35% pure.
- Hydrochloric acid is transported in steel tanks lined inside with rubber.
- If the acid comes into contact with exposed parts of metal or with rust, it forms iron (III) chloride that
makes the acid appear yellow.
66
Pollution in an industry manufacturing hydrochloric acid.
(i). Chlorine is poisonous.
(ii). Mixture of hydrogen and oxygen in air is explosive when ignited.
Uses of hydrochloric acid.
1. Sewage treatment.
2. Treatment of water (chlorination) at the waterworks.
3. Removing rust from metal e.g. descaling iron before it is galvanized or and other metals before they
are electroplated.
4. Making dyes, drugs and photographic materials like silver chloride on photographic films.

Environmental Pollution By Chlorine And Its Compounds.

1. Chlorine may dissolve in rain and fall as acid rain, which has adverse effects on plants and animals,
buildings and soil nutrients.
2. CFCs are non-biodegradable. Over time, they diffuse into the atmosphere breaking down to free
chlorine and fluorine atoms. These atoms deplete the ozone layer. Chlorine is thus one of the
greenhouse gases.
3. PVCs are non-biodegradable.
4. DDT is a pesticide containing chlorine and has a long life span, affecting plants and animal life.
Note: DDT is banned in Kenya; NEMA advises increased use of pyrethroids in mosquito control.

67
68
 GAS LAWS [PREVIEW]

By the end of this Chapter, the learner should be able to:

(a) State Boyle’s and Charles’s laws.

(b) Describe experiments to illustrate Boyle’s and Charles’ laws.
(c) State and use the combined gas law to solve numerical problems.
(d) State Graham’s law of diffusion and relate the rate of diffusion to
relative molecular mass of a gas.
(e) Explain diffusion in terms of kinetic theory of matter.

Introduction To Gas Law

Matter is made up of small particle in accordance to Kinetic Theory of
matter and these particles are always in constant random motion.
Naturally, there are basically three states of matter: Solid, Liquid and
gas. However, gases are always affected by physical conditions.
These physical conditions include:
(i) Temperature
(ii) Pressure
(iii) Volume
To explain the behaviour of gases, it is important to understand the
interrelationship between pressure, volume and temperature of a fixed
mass of a gas. Therefore, this chapter will focus on the properties of
matter in the gaseous state.

Additionally, unlike Solids

and Liquids, the forces of
attraction between gas
molecules are very weak, this
allows gas particles to be in
continuous random motion
because they possess kinetic energy. For this reason, gases spread to
occupy any available space.
69
Boundary conditions
In this topic we shall study , the gas law by considering the effect of change in physical conditions of
gases in a closed system. (Fixed mass of gas). i.e restricting our argument on fixed mass of gas.
The effect of physical conditions of temperature, volume and pressure was investigated and expressed in both
Boyles and Charles laws.

1. BOYLES LAW
Boyle’s law deals with the relationship between pressure and volume of a fixed mass of a gas when
temperature is kept constant.

Boyle’s law: The volume of a fixed

mass of a gas is inversely proportional
to its pressure at constant temperature

Boyle’s law implies that if temperature

is hold constant for a fixed mass of gas,
as the pressure increases, the volume will
decrease. i.e doubling the pressure cause
the volume to be halved. This can be
represented diagrammatically as
Mathematical representation of the Boyles Law

Volume α 1 (Fixed /constant T)

Pressure
PV = Constant
Graphical Representation of Boyles Law
1. Graphically therefore a plot of volume(V) against pressure (P) produces a curve.

2. And a plot of volume(V) against inverse/reciprocal of pressure (1/p) produces a straight line
70
For two gases then
P1 V1 = P2 V2
P1 = Pressure of gas 1
V1 = Volume of gas 1
P2 = Pressure of gas 2
V2 = Volume of gas 2

2. CHARLES’ LAW
Charles’ Law deals with the relationship between the volume of a fixed mass of a gas with its
temperature at constant pressure.
The heat energy increases the kinetic energy of the gas molecules. This leads to increased rate of collisions with
the walls of the container causing an increase in the gas
pressure.

The relationship between temperature and volume of a

fixed mass of gas is summarized by Charle’s Law.

Charles’s Law: The volume of a given mass of a gas is

directly proportional to its absolute temperature, its
pressure being kept constant.

This law implies that the volume of a fixed mass of a gas

increases in the same proportion, as the absolute temperature provided its pressure remains constant.

N/B. Absolute temperature is the lowest temperature at which a gas can exist. This temperature is called
absolute zero.( -273 0C)
71
From Charles law , an increase in temperature of a gas cause an increase in volume. i.e doubling the
temperature cause the volume to be doubled.
V α T (Fixed /constant P)
For two gases then
V1/V2 = T1/T2
Combined Gas Law
The combined gas law deals with the variation in the volume of a fixed mass of a gas with respect to
changes in temperature and pressure. The mathematical expression of Charles’s Law, V α T can be
combined with that of Boyle’s law V α 1/P to obtain the expression:

Therefore, PV α T
Hence, PV/ T = Constant
If a fixed mass of a gas of volume V1 exerts a pressure P1 at absolute temperature T1 , the expression
may be written as:
P1V1 / T1 = Constant
Suppose the same mass of gas has a volume, V2, and exerts a pressure, P2, at absolute temperature, T2,
then the expression becomes:
P2V2 / T2 = Constant

Therefore, P1V1 / T1 = P2V2 / T2

This is an important equation. It enables the volume of a gas to be obtained under any conditions of
temperature and pressure provided its volume under some other conditions of temperature and pressure
is known. It is called the ideal gas equation.
Standard Conditions
Both temperature and pressure changes in a gas can cause the volume to change. For this reason, volumes of gases
are always compared under the same conditions of temperature and pressure.
There are two conditions considered when comparing volumes of gases:
• Standard temperature and pressure (s.t.p). The s.t.p conditions refer to a temperature of 273K
(00C)and a pressure of 760 mmHg (1 atmosphere).
• Room temperature and pressure (r.t.p). This refers to a temperature of 298 K (250C) and a pressure of
760 mmHg. It should be seen that from the standard conditions, all computations of temperature should
be expressed in Kelvin.

Application
1. Inflating tyres, balls and balloons appropriately depending on the prevailing temperature conditions.
2. Designing of aerosol cans and tear-gas canisters which contain a gas compressed under pressure to act
as a propellant of liquid contents in the cans.
3. Regulation of pressure in an aircraft for comfortable in-flight environment at high altitude.
72
Diffusion and the Graham’s Law
Fluids refers to both gases and liquids. The migration of fluids from one point to another is based on
1. concentration difference of the molecules
2. Pressure difference
Therefore, Diffusion is the process by which
particles spread out from a region of high
concentration to regions of low concentration.
In this section of the chapter we shall examines
diffusion in liquids and gases and the factors
affecting diffusion in gases.

Rate of diffusion of gas / Rate of movement of gas

Rate of diffusion refers to the volume of gas that
passes through a given section per unit time. The
continuous random motion of gases differs from gas
to the other .
R = V/t
The rate of diffusion of a gas depends on its density. i.e. The higher the rate of diffusion, the less dense
the gas. Consequently, the density of a gas depends on its molar mass/relative molecular mass. i.e. The
higher the density the higher the molar mass/relative atomic mass and thus the lower the rate of
diffusion.
For example
1. Carbon (IV)oxide(CO2) has a molar mass of 44g. Nitrogen(N2)has a molar mass of 28g. (N2)is
thus lighter/less dense than Carbon (IV)oxide(CO2). N2 diffuses faster than CO2.
2. Ammonia(NH3) has a molar mass of 17g. Hydrogen chloride gas has a molar mass of 36.5g.
Both gases on contact react to form white fumes of ammonium chloride .When a glass/cotton
wool dipped in ammonia and another glass/cotton wool dipped in hydrochloric acid are placed at
opposite ends of a glass tube, both gases diffuse towards each other. A white disk appears near to
glass/cotton wool dipped in hydrochloric acid. This is because hydrogen chloride is
heavier/denser than Ammonia and thus its rate of diffusion is lower .

100 cm

Graham studied this behavior and came up with a law thus the rate of diffusion of a gas is in accordance
to Grahams law of diffusion.
73
Graham’s Law: Under the same conditions of temperature and pressure, the rate of diffusion of a gas
is inversely proportional to the square root of its density.

The mathematical expression of Graham’s Law is:

Class Trial exercise

1. It takes 30 seconds for 100cm3 of carbon(IV)oxide to diffuse across a porous plate. How long
will it take 150cm3 of nitrogen(IV)oxide to diffuse across the same plate under the same
conditions of temperature and pressure. (C=12.0,N=14.0=16.0)
2. How long would 200cm3 of Hydrogen chloride take to diffuse through a porous plug if
carbon(IV)oxide takes 200seconds to diffuse through.
3. Oxygen gas takes 250 seconds to diffuse through a porous diaphragm. Calculate the molar mass
of gas Z which takes 227 second to diffuse.
4. 25cm3 of carbon(II)oxide diffuses across a porous plate in 25seconds. How long will it take
75cm3 of Carbon(IV)oxide to diffuse across the same plate under the same conditions of
temperature and pressure. (C=12.0,0=16.0)
5. Equal volumes of carbon(II) oxide and carbon(IV) oxide are allowed to diffuse through the same
medium. Calculate the relative rate of diffusion of carbon(II) oxide. (C = 12.0, Oxygen = 16.0)
6. If it takes 20 seconds for 200 cm3 of oxygen gas to diffuse across a porous plug. How long will
it take an equal volume of sulphur(IV) oxide to diffuse across the same plug? (O = 16.0, S =
32.0).
7. Determine the molecular mass of the gas Y which diffuses times slower than Oxygen. 0 = 16.0
8. If it takes 30 seconds for 100 cm3 of carbon(IV) oxide to diffuse across a porous plate. How long
will it take 150 cm3 of nitrogen(IV) oxide to diffuse across the same plate under similar
conditions? (C = 12.0, N = 14.0, O = 16.0).
74
75
ORGANIC CHEMISTRY
[PREVIEW]
The branch of chemist

that study compounds

whose molecules

contain carbon

constitutes is known

as organic chemistry.

This term arose from

the eighteenth-century

belief that organic

compounds could be
Introduction
formed only by living
Organic Chemistry refers to the chemistry of hydrogen carbon chain
compounds. (that is, organic)in this
- It is the study of carbon compounds except the oxides of carbon i.e.
chapter, functional
CO, CO2 and Carbonates.
groups will be
ORGANIC CHEMISTRY I: THE HYDROCARBONS
introduced and its
Definitions
Hydrocarbons important properties to
Are compounds of hydrogen and carbon only; and are the simplest
organic chemistry.
organic compounds.
(A). MAIN GROUPS OF HYDROCARBONS
Are classified on the basis of the type of bonds found within the carbon Since certain types of
atoms. reactions have their
➢ Alkanes: Are hydrocarbons in which carbon atoms are linked by
single covalent bonds. own unique
➢ Alkenes: Carbon atoms are held by at least one double bond.
➢ Alkynes: Have at least one triple bond between any two carbon characteristics these
atoms.
molecules will grouped
Properties of carbon that allow it to be studied in hydrocarbons.
- Ability to form Tetravalency (i.e it has four valence electrons together based on
used in bonding)
- Ability to undergo cationization (i.e ability to form bonds to functional groups for
itself) reactions that share a
76

common theme.
(B). Saturated And Unsaturated Hydrocarbons
i . Saturated Hydrocarbons
- Are hydrocarbons which the carbon atoms are bonded to the maximum number of other atoms
possible.
- hydrocarbons which don’ react and hence cannot decolourise both Bromine water and acidified
potassium manganate (VII).
- They are compounds in which each carbon atom has only single covalent bonds, throughout the
structure.
ii. Unsaturated Hydrocarbons
- Are hydrocarbons which contain at least one double or bond, between any two adjacent carbon atoms.
- The carbon atoms do not have maximum covalency.
- They can decolourise both bromine water and acidified potassium manganate (VII).
Examples: All alkenes and Alkynes.

(C). Homologous Series

- Refers to a group of organic compounds that have the same general formula, whose consecutive
members differ by a similar unit, and usually have similar chemical properties.

Characteristics Of A Homologous Series.

(i). Can be represented by a general formula;
(ii). Have similar chemical properties
(iii). They show a steady gradation of physical properties
(iv). Can usually be prepared by similar methods.
(D). Structural and molecular formula
✓ Molecular formulae
- Simply shows the number and type of elements (atoms) in the compound.
✓ Structural formula
Shows how the different atoms in the molecules (of a compound) are bonded or joined together.
Example: 1
Methane
Molecular formula CH4;
Structural formula

(E). Isomerism
- Is the existence of two or more compounds that have similar molecular formulae but different
structural formula.
- Such compounds are called isomers, i.e compounds with the same molecular formula but different
structural formula.
(F). Functional groups
- A functional group is a part of a compound which has a characteristic set of properties.
1. Alkanes the functional group is the single bond
2. Alkenes the double bond
77

3. Alkynes the triple bond

 1. ALKANES
Alkanes are the simplest hydrocarbons
with the general formula; CnH2n + 2 where
n = number of Carbon atoms in the
molecule.

(a). General formula

- The Alkanes have a general formula
CnH2n+2 where n is the number of carbon
atoms in the molecule.
Example
For compound with only
- 1 carbon atom, formula = CH4
- 2 carbon atoms; the formula = C2H6
- 3 carbon atoms; the formula = C3H8

(b). Homologous series

- The Alkanes differ from each other by a
–CH2-.
- Thus methane, CH4 differs from ethane,
C2H6 by –CH2-, and ethane in turn differs
from propane C3H8 by –CH2.
- They therefore form a homologous series of -CH2

(c). Functional groups

- A functional group of alkanes is C

(d). Structure
- In all Alkanes the distribution of bonds around each carbon atom is tetrahedral. (four bonds)
(e) Isomerism
Alkanes undergo structural isomerism
Occurs when a substituent group is attached or altered to one of the carbon atoms in the largest chain
containing the double bond.
Sources of Alkanes
There are 3 known natural sources of alkanes:
(i). Natural gas: this consists of mainly of methane;
(ii). Crude oil:
- Consists of a mixture of many Alkanes
- It can be separated into its components by fractional
distillation.
Reason:
- The different components have different boiling points.
(iii). Biogas: This contains about 60-75% of methane
gas/marshy gas.
(iv) Cracking of Alkanes
Cracking refers to the breaking of large alkane molecules into
smaller Alkanes, alkenes and often hydrogen. Cracking usually occurs under elevated temperatures of about 400-
700oC
78
 Nomenclature
Alkanes follow an IUPAC system of naming that is used conventionally all over the world
The first four alkanes in the homologous series is named using the Latin names and adding suffix -ane.
The fifth hydrocarbon onward uses the roman numbers with a suffix -ane
Molecular Fomular Number of Carbon Name

CH4 1 Methane
CH3CH3 2 Ethane
CH3CH2CH3 3 Propane
CH3CH2CH2CH3 4 Butane
CH3CH2CH2CH2CH3 5 Pentane
CH3CH2CH2CH2CH2CH3 6 Hexane
CH3CH2CH2CH2CH2CH2CH3 7 Heptane
CH3CH2CH2CH2CH2CH2CH2CH3 8 Octane
CH3CH2CH2CH2CH2CH2CH2CH2CH3 9 Nonane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 10 Decane

HOW TO Name an Alkane Using the IUPAC System .

Step [1] Find the parent carbon chain and add the suffix.
Find the longest continuous carbon chain, and name the molecule by using the parent name for that number of
carbons, given in Table 4.1. To the name of the parent, add the suffix -ane for an alkane. Each functional group
has its own characteristic suffix.

• Finding the longest chain is just a matter of trial and error. Place your pencil on one end of the chain, go
to the other end without picking it up, and count carbons. Repeat this procedure until you have found the
chain with the largest number of carbons.
• It does not matter if the chain is straight or has bends. All of the following representations are equivalent.
79
• If there are two chains of equal length, pick the chain with more substituents. In the following example, two
different chains in the same alkane contain 7 C’s, but the compound on the left has two alkyl groups attached to
its long chain, whereas the compound to the right has only one.

Step [2] Number the atoms in the carbon chain.

• Number the longest chain to give the first substituent the lower number.

• If the first substituent is the same distance from both ends, number the chain to give the second
substituent the lower number. Always look for the first point of difference in numbering from each end of
the longest chain.

80
 • When numbering a carbon chain results in the same numbers from either end of the chain, assign the
lower number alphabetically to the first substituent.

Step [3] Name and number the substituents.

• Name the substituents as alkyl groups, and use the numbers from Step 2 to designate their location.

• Every carbon belongs to either the longest chain or a substituent, but not both.
• Each substituent needs its own number.
• If two or more identical substituents are bonded to the longest chain, use prefixes to indicate how many:
di- for two groups, tri- for three groups, tetra- for four groups, and so forth. The preceding molecule has
two methyl substituents, and so its name contains the prefix di- before the word methyl → dimethyl.
• When the substituent groups are a halogen and an alkyl group, the halogen is always placed before the
alkyl group. (i.e the halogen group is given the preference over alkyl group in the longest chain therefore
we assign integers in the longest chain in a way that the halogen receives the lowest integer.)

Step [4] Combine substituent names and numbers + parent + suffix.

• Precede the name of the parent by the names of the substituents.
• Alphabetize the names of the substituents, ignoring all prefixes
• Precede the name of each substituent by the number that indicates its location. There must be one number
for each substituent.
• Separate numbers by commas and separate numbers from letters by hyphens. The name of an alkane is a
single word, with no spaces after hyphens or commas.
81
SAMPLE EXERCISE
1. Give the systematic name for the following alkane:

SOLUTION
Analyze: We are given the condensed structural formula of an alkane and asked to give its name.
Plan : Because the hydrocarbon is an alkane, its name ends in -ane. The name of the parent hydrocarbon is based
on the longest continuous chain of carbon atoms. Branches are alkyl groups, named after the number of C atoms in
the branch and located by counting C atoms along the longest continuous chain.
Solve: The longest continuous chain of C atoms extends from the upper left CH3 group to the lower left CH3 group
and is seven C atoms long:

The parent compound is thus heptane. There are two methyl groups branching off the main chain. Hence, this
compound is a dimethylheptane. To specify the location of the two methyl groups, we must number the C atoms
from the end that gives the lower two numbers to the carbons bearing side chains. This means that we should start
numbering at the upper left carbon. There is a methyl group on C3 and one on C4.

Answer The compound is thus 3,4-dimethylheptane.

2. Write the structural formula for 3-ethyl-2-methylpentane.

SOLUTION
Analyze : We are given the systematic name for a hydrocarbon and asked to write its structural formula.
Plan : Because the name ends in -ane, the compound is an alkane, meaning that all the carbon–carbon bonds are
single bonds. The parent hydrocarbon is pentane, indicating five C atoms (Table 24.2). There are two alkyl groups
specified, an ethyl group (two carbon atoms, C2H5) and a methyl group (one carbon atom, CH3). Counting from
left to right along the five-carbon chain, the name tells us that the ethyl group is attached to C3 and the methyl
group is attached to C2.
Solve: We begin by writing five C atoms attached by single bonds. These represent the backbone of the parent
pentane chain:
C-C-C-C-C
We next place a methyl group on the second C and an ethyl group on the third C of the chain. We then add
hydrogens to all the other C atoms to make four bonds to each carbon:
CH3

H3C-CH2-CH-CH2-CH3

H2C-CH3
82
[Trial question] Give the IUPAC Name of each compound

Preparation of Alkanes In the laboratory

Alkanes are prepared by the reaction between soda lime and an appropriate alkanoate. Soda lime is a
mixture of sodium hydroxide and calcium oxide. An alkanoate is a salt of an organic acid.
In this reaction, calcium oxide acts as a drying agent to dry the deliquescent salt of sodium hydroxide.
A higher alkanoate is reacted with soda lime to yield lower alkane
e.g
Higher Alkanoate Lower Alkane
Sodium Hexanoate Propane
Sodium Pentanoate + Soda lime Butane
Sodium Butanoate Propane
Sodium Propanoate Ethane

A. Preparation of Methane Gas

Equation
CH3COONa + NaOH CH4 + Na2CO3
B. Preparation of Ethane Gas

Equestion
83

CH3CH2COONa + NaOH C2 H6 + Na2CO3

Physical Properties

1. Methane is a non-poisonous, colourless gas. It is slightly soluble in water and hence can be
collected over water. However, it is quite soluble in organic solvents such as ethanol and
tetrachloromethane.
2. Its less dense than air

Chemical Properties
1. Burning
The first four members of alkane are very flammable and burns in excess air // oxygen with a pale blue
non-luminous flame to give carbon (IV) oxide ad water vapour.
Equation:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Note: In a limited supply of air, the flame is luminous. This is due to incomplete combustion of the
methane. A mixture of methane and air explodes violently when ignited if the volume ratio is
approximately 1:10 and this is often the cause of fatal explosions in coal mines

2. Reaction with Bromine water and acidified potassium permanganate

When methane is bubbled through bromine water the red brown colour of bromine persists; and when
bubbled through acidified potassium manganate (VII) solution; the purple colour of the solution
remains.

N/B
This is the chemical test for alkane in the laboratory
Identity/observation
A liquid /solid that burns with a blue flame and on addition of yellow Bromine water or / purple
acidified potassium manganate (VII) , the colour of the solutions remains.
Thus,
It has no effect on either bromine water or acidified potassium permanganate because it is a saturated
hydrocarbon.
3. Substitution Reactions
i. Reaction with Halogens (X)
Alkanes react with halogens in the presence of sunlight because the halogen molecules are supplied with
energy from light necessary to split them into atoms. These free halogen atoms are very reactive hence
they replace the hydrogen atoms in the molecule.
N/B
Condition : There must be a presence of light for the reaction to occur because, in the dark at room
temperature because there is no enough energy to split the halogen molecules into atoms.
Example is the chemical reaction between methane and bromine gas
sunlight
CH4(g) + Br2(g) CH3Br(g) + HBr(g)
N/B
Only one hydrogen atom is removed at a time.
This process can be repeated until all hydrogen atoms in CH4 are replaced.
84
Uses Of Alkanes
1. Gasoline obtained by fractionating petroleum is suitable for
use as automobile fuel.
2. In cracking, the hydrocarbons are mixed with a catalyst to
produce hydrogen
3. Alkanes are also used in manufacture of paints and
computer toners

[Trial Questions]
1. Draw the structure corresponding to each IUPAC name.
a. 3-ethyl-2-methylhexane
b. 2,2,6,6,7-pentamethyloctane
c. 4-butyl-1,1-diethyloctane
d. 2,4,5-trimethylheptane
e. 3-ethyl-1,1-dimethylhexane
2. Draw the structural isomers of all compounds that fit the following Molecular formula.
a. C4H8.
b. C7H16.
c. C6H12.
3. Give the IUPAC name for each compound.

4. Give the structure and IUPAC name for each of the nine isomers having molecular formula
C9H20 that contains seven carbons in the longest chain and two methyl groups as substituents.
85
 Alkenes are unsaturated hydrocarbons that
contain at least one bond and have the general
formula CnH2n.
The first member of the series is ethene C2H4.
because at least two carbon atoms are
necessary for a double bond to be formed.

(a). General formula

Alkenes have a general formula CnH2n where
n is the number of carbon atoms in the
molecule.

Example
For compound with only
- 2 carbon atoms; the formula = C2H4
- 3 carbon atoms; the formula = C3H6

(b). Homologous series

Alkenes differ from each other by a –CH2- therefore, they can be concluded to form a homologous series
of -CH2

(c). Functional groups

- The functional group of alkenes is the double bond . ie (the part of the compound which has a

characteristic set of properties) and it is written

(d). Structure
The simplest alkene is , called ethene. In all Alkanes the distribution of bonds around each carbon atom
is tetrahedral. (four bonds)
(e) Isomerism
Alkanes undergo both
i. Branching isomerism
ii. Positional isomerism
Branching isomerism; in alkenes
Occurs when a substituent group is attached or altered to one of the carbon atoms in the largest chain
containing the double bond

.
86
Positional isomerism; in alkenes
Occur due to alteration of the position of the double bond (functional group).
1
C = 2C - 3C -4C - 5C
1
C - 2C = 3C -4C - 5C
1
C - 2C - 3C = 4C - 5C

Nomenclature
[Step 1] Find the longest chain that contains both carbon atoms of the double bond.

Step [2] Number the carbon chain to give the double bond the lower number, and apply all other
rules of nomenclature.

• Compounds with two double bonds are named as dienes by changing the -ane ending of the
parent alkane to the suffix -adiene. Compounds with three double bonds are named as trienes,
and so forth. Always choose the longest chain that contains both atoms of the double bond
87
Preparation in the laboratory
1. Dehydration of Alcohol by conc Sulphuric (VI) Acid
2. Dehydration Of Alcohol using Aluminium Oxide
In these methords, Alcohol is dehydrated to produce its respective alkene gas
e.g
Alcohol Alkene Produced
Ethanol Ethene
Propanol Propene
Butanol Butene
Pentanol Pentene

1. Preparation of alkene gas through the use of conc Sulphuric (VI) Acid
Condition
Presence of temperature between 160 0C – 180 0C. This is because at a temperature of 140 0C, different
compound called ether is predominantly formed.

When a mixture of ethanol and concentrated sulphuric(VI) acid is heated at temperatures between 160°C
and 180°C, water is removed from ethanol and ethene gas is formed
.
Conc H2SO4
C2H5OH CH2CH2 + H2O
88
The gas produced is passed through sodium hydroxide to remove sulphur(IV) oxide and carbon(IV)
oxide which are formed when concentrated sulphuric acid and ethanol decompose respectively due to
heat.

2. Preparation of alkene gas through the use of conc Sulphuric (VI) Acid
Ethene can also be prepared by dehydration of ethanol using aluminium oxide. In this reaction the
aluminium oxide acts both as a catalyst as well as a dehydrating agent.

Physical Properties

1. Ethene is a colourless and oduorless gas.

2. It is slightly soluble in water hence is collected over water.
The solubility of alkenes decreases with increase in molecular mass. Ethene is very soluble in organic
solvents such as methylbenzene, and tetrachloromethane.
3. Melting and boiling point
The melting point, and boiling points of alkenes generally increase with increase in the number of
carbon atoms due to an increase in inter-molecular forces, hence, high boiling and melting points.

Chemical Properties

a) Burning/combustion
Just like an alkenes and alkanes, ethene burn in air, producing carbon dioxide and large quantities of
heat.
C2H4 (g) + 3O2 (g) → 2CO2 (g) + 2H2O
b) Additional reactions
Is a reaction in which are molecule adds to another to form a single product occur in alkenes due to
presence of a double bond.
1. With oxidizing reagents (addition of Oxygen)
a. Reaction with acidified potassium permanganate.

Procedure: when ethene is bubbled into a test tube containing acidified potassium permanganate or Acidified
potassium permanganate is added to a solution to test for saturation.
89
Observation: The purple colour of the solution disappears.
Explanation: Ethene reduces the potassium permanganate to Manganese (II) ion and water.

Note:
The net effect of the above reaction is the addition of two –OH groups to the double bond forming ethan-1, 2-diol
(ethylene glycol).
In cold countries ethylene glycol is used as an antifreeze in car radiators.
Reaction of alkene with potassium permanganate is slow and requires temperature to increase the rate of reaction
or leaving the solution for some time before taking the observation

b. Reaction with acidified potassium chromate (VI) (K2Cr2O7)

Procedure: when ethene is bubbled into a test tube containing acidified potassium Chromate (VII) or Acidified
potassium Chromate (VII) is added to a solution to test for saturation.

Observation: The purple orange of the solution turns to yellow.

Explanation: Ethene reduces the potassium Chromate (VII) to chromate (III) ions.

2. Halogenations
Halogenation is the addition of halogen atoms across a double bond.
e.g Reaction of ethene and bromine

When ethene is mixed with bromine gas/ water

Observation: The reddish-brown bromine gas is decolored/becomes colourless.
Explanation: This is because bromine is decoloursed due to the addition of Bromine atoms
to the two carbon atoms double bond forming 1.2 dibromethane.
Note:
The above two chemical properties are used to test for the presence of unsaturation in a
compound.
The reaction site is the double bond and hence/all alkenes will react in a similar manner.

3. Addition of Hydrogen Halides( hydrohalogenation)

Hydro-halogenation is the addition of hydrogen and halogen atoms across a double bond.
e.g Reaction of ethene and hydrogen bromide

4. Hydrogenation Ethene with Hydrogen i.e. (Hydrogenation.)

Is commonly termed hydrogenation though just a typical addition reaction. Ethene is reacted with hydrogen,
under special conditions.
Conditions; moderate temperature and pressure.
Nickel catalyst/palladure catalyst.
90
N/b
The above addition it is used industrially in the conversion of various oils into fats e.g. in the preparation
of Margarine.
5. Hydration
Ethene reacts with concentrated Sulphuric acid at room temperature to form ethyl hydrogen sulphate.

Hydration is the addition of water to an alkene to form an alcohol. H2O itself is too weak an acid to
protonate an alkene, but with added H2SO4, H3O+ is formed and addition readily occurs.

6. Self-addition reaction
Alkene molecules have the ability to react with each other to form a larger molecule which has a higher
molecular mass. In this reaction each molecule of ethene is known as a monomer. When many
monomers are joined together, they form a polymer.
Conditions
- High temperatures of about 2000C
- High/elevated pressures of approximately 1000 atmospheres
Polymerization is the process in which several monomers combine to form a polymer.
When ethene molecules join with each other this way, they form a polymer known as polyethene. This
polymerization process can be represented by a general equation;

Uses
1. Manufacture of plastics, through polymerization.
2. Manufacture of ethanol; through hydrolysis reactions
3. Ripening of fruits.

91
 Alkynes contain a carbon–carbon triple
bond. A terminal alkyne has the triple
bond at the end of the carbon chain, so that
a hydrogen atom is directly bonded to a
carbon atom of the triple bond. An internal
alkyne has a carbon atom bonded to each
carbon atom of the triple bond.

(a). General formula

- The Alkynes have a general formula
CnH2n-2 where n is the number of carbon
atoms in the molecule.
Example
For compound with only
- 2 carbon atoms; the formula C2H2
- 3 carbon atoms; the formula C3H4

(b). Homologous series

- The Alkenes differ from each other by a –CH2.
- They therefore form a homologous series of -CH2

(c). Functional groups

- The functional group of alkynes is the double bond . ie (the part of the compound which has a
characteristic set of properties) and it is written as

(d). Structure
- In all Alkynes the distribution of bonds around each carbon atom is tetrahedral. (four bonds)
(e) Isomerism
Alkynes undergo both
i. Branching isomerism
ii. Positional isomerism

Branching isomerism
Occurs when a substituent group is attached or altered to one of the carbon atoms in the largest chain
containing the double bond.
Positional isomerism; in alkenes
92

Occur due to alteration of the position of the double bond.

They also undergo addition reactions because of High unsaturation and may be polymerised like the
alkenes.
Examples

Name Molecular formula

Ethyne C2H2
Propyne C3H4
But-l-yne C4H6
Pent-l-yne C5H8

Nomenclature of alkynes

Gradation in physical properties of Alkynes

Name of Alkyne Formula M.P/0C B.P/0C Density/gcm-3

Ethyne HC CH -8108 -83.6 -
Propyne CH3 CH -103 -23.2 -
Butyne CH3CH2CC CH -122 8.1 -
Pent-l-yne CH3CH2CH2C CH -90 39.3 0.695
Hex-l-yne CH3(CH2)3C CH -132 71 0.716

Preparation and chemical properties of Ethyne.

1. Calcium carbide reacts with water at room temperature to form ethyne and calcium hydroxide.
Conditions
a. Room temperature
93
A layer of sand is placed at the base of the flask because the reaction is highly exothermic. The sand absorbs the
excess heat and therefore prevents the flask from breaking. The flask must be dry before the start of the
experiment to avoid formation of the gas before the set-up is complete.

CaC2 (s) + 2H2O(l) → C2H2 (g) + Ca(OH)2 (aq)

Physical Properties
- Colourless gas, with a sweet smell when pure.
- Insoluble in water and can thus be collected over water.
- Solubility is higher in non- solvents
Chemical properties
1. Combustion
Ethyne burns with a luminous and very sooty flame; due to the high percentage of carbon content, some
of which remains unburnt.
- In excess air, the products are carbon dioxide and water.
In limited air, they undergo incomplete combustion, forming a mixture of carbon and carbon dioxide.

Note: A sooty flame observed when a hydrocarbon burns in air is an indication of unsaturation in the
hydrocarbon.

Addition reactions
During addition reactions of alkynes (Ethyne) the triple bond breaks in stages;

a) Reaction with hydrogen (Hydrogenation)

Note: This reaction occurs under special conditions i.e.
- Presence of a Nickel catalyst
- Temperatures about 2000C

b) Reaction with halogens

i) Reaction with chlorine and Bromine gas
- The red-brown bromine vapour is decoloursed.

Note: In this reaction Cl2 should be diluted with an inert.

Reason: Pure Cl2 reacts explosively with Ethyne, forming carbon and HCl.
c) Reaction with Bromine liquid
When Ethyne reacts with Bromine water, the reddish – brown colour of bromine
water disappears.

Reason: The Bromine adds to the carbon tripple bond leading to the formation of
1,1,2,2-tetrabromoethane.
Ethyne also decolorizes acidified potassium permanganate.

Note: Decolourization of acidified potassium permanganate and bromine water are

tests for unsaturated hydrocarbons (alkanes and alkynes)

d) Reaction with hydrogen halides

Uses of Ethyne
1. Industrial manufacture of compounds like adhesives and plastics
It’s used in the oxy-acetylene flame which is used for welding and cutting metals.
94

2.
 [PREVIEW]
MOLES Even the smallest
samples we deal with in
the laboratory contain
enormous numbers of
atoms, ions, or
molecules. For example,
a teaspoon of water
(about 5 mL) contains
water molecules, a
number so large it almost
defies comprehension.

Chemists therefore have

devised a counting unit
for describing such large
By the end of this topic , the learner should be able to
(a) Define the mole and relate it to relative atomic mass.
numbers of atoms or
molecules. In everyday
(b) Convert mass into moles, and moles to mass.
life we use such familiar
(c) Use data to determine the empirical and molecular formulae of compounds.
counting units as dozen
(d) Define the terms concentration, molarity and dilution of a solution. (e) (12 objects) and gross
Define and prepare molar solutions. (144 objects).
(f) Carry out titrations and solve problems involving molar solutions.
In chemistry the
(g) Write full formulae and ionic equations.
counting unit for
(h) Define molar gas volume and atomicity of gases. numbers of atoms, ions,
(i) State Avogadros’ and Gay Lussac’s laws and carry out related calculations. or molecules in a
(j) Carry out calculations on molar gas volumes both at standard temperature laboratory-size sample is
and pressure and room temperature and pressure. the mole.

One mole is the amount

INTRODUCTION of matter that contains as
In chemistry the counting unit for numbers of atoms, ions, or molecules many objects (atoms,
in a laboratory-size sample is known as the mole. molecules, or whatever
other objects we are
Preview: A dozen is a collective name used to indicate (12) items considering) as the
whether we have a dozen eggs or a dozen elephants. Clearly, however, a number of atoms in
dozen eggs do not have the same mass as a dozen elephants. exactly 12 g of
Similarly, a mole is always the same number (6.023 x 10 23 ), but 1-mol isotopically pure .
samples of different substances have different masses.
95
Compare, for example, 1 mol 12C of and 1 mol of 24Mg . A single atom has a mass of C - 12 amu,
whereas a single atom is twice as massive, Mg - 24 amu (to two significant figures). Because a mole of
anything always contains the same number, a mole of 12C of mass of 12 g must have the same number of
particles as a mole of 24Mg of mass of 24 g. This example illustrates a general rule relating the mass of
an atom to the mass of these atoms.

Moles therefore can be defined as any substance that contain as many particles as contained in 12
grams of carbon 12
Molar Mass
The mass in grams of one mole of a substance (that is, the mass in grams per mole) is called the molar
mass of the substance. The molar mass in grams per mole of any substance is numerically equal to 1 mol
of that element.
I.e ; the molar mass of an element is equal to its RAM
Example
Cl = 35.5g Ca = 40g
Mg = 24g Fe = 56g

Conversion guide of mass to moles and to particles

Cl has RAM of 35.5g 1 mol Cl 6.023 x 1023 atoms
, .
23
Ca has RAM of 40 1 mol Ca 6.023 x 10 atoms
. .
23
Mg has RAM of 24g 1 mol Mg 6.023 x 10 atoms
, .
23
Fe has RAM of 56g 1 mol Fe 6.023 x 10 atoms
Interconversion of Mass to moles and moles to masses moles to particles, mass to
particles and particles to moles , particles to mass

Moles of Elements
A. Mass Moles
1. Calculate how many moles are present in 0.5 grams of Cobalt (Ca = 40)
40g of Ca 1 mole Ca
0.5g of Ca ?
0.5 X 1 = 0.0125 moles
96

40
 2. Calculate the number of moles that are in 0.25g of Magnesium (Mg = 24)
24g of Mg 1 mole Mg
0.25g of Mg ?
0.25 X 1 = 0.0104 moles
24
3. Calculate the number the number of moles present in 0.56g of Iron ( Fe = 56g)

56g of Fe 1 mole Fe
0.56 g of Fe ?

0.56 X 1 = 0.01 moles

56
B. Moles Mass

4. How many grams are present in 0.5 moles of iron (Fe = 56)

56g of Fe 1 mole Fe
? 0.5 moles

0.5 X 56 = 31.36g
1
5. How many grams are present in 0.0025 moles of calcium (Ca = 40)
40 g Mg 1 mole Ca
? 0.0025 moles

0.0025 X 40 = 0.1g
1
6. How many grams are present in 0.25 moles of Magnesium (Mg = 24)

24g of Fe 1 mole Mg
? 0.25 moles

0.25 X 24 = 6g
1
C. Moles Particles / atoms

7. How many atoms are present in 0.5 moles of iron (Fe = 56)
6.023 x 1023 atoms 1 mole
? 0.5 moles

6.023 x 1023 X 0.5 = 3.0115 x 1023

1
8. How many atoms are present in 0.0025 moles of calcium (Ca = 40)
97
6.023 x 1023 atoms 1 mole
? 0.0025 moles

6.023 x 1023 X 0.0025 = 1.50575 x 1022

1

9. How many atoms are present in 0.25 moles of Magnesium (Mg = 24)
6.023 x 1023 atoms 1 mole Mg
? 0.25 moles

6.23 x 1023 X 0.25 = 1.50575 x 1023

1
C. Particles / atoms Moles
23
10. How many moles are present in 1.50575 x 10 atoms of iron (Fe = 56)
6.023 x 1023 atoms 1 mole
1.50575 x 1023

1.50575 x 1023 X 1 =
23
6.023 x 10
11. How many moles are present in 3.0115 x 1023 atoms of calcium (Ca = 40)
6.023 x 1023 atoms 1 mole
3.0115 x 1023
3.0115 x 1023 X 1 =
23
6.023 x 10
12. How many moles are present in 1.2125 x 1023 atoms of Magnesium (Mg = 24)
6.023 x 1023 atoms 1 mole Mg
1.2125 x 1023
1.2125 x 1023 X 1 =
23
6.023 x 10
Moles of molecules
Inter Conversion of Molecules and Moles
Some elements do not exist as atoms but as molecules. For example, a sample of oxygen gas is made up
of oxygen molecules, O2 .
The mass in grams of one mole of a substance (that is, the mass in grams per mole) is called the molar
mass of the substance. The molar mass (sum of mass of element that make up the molecule) in grams
per mole of any molecule is numerically equal to 1 mol
I.e ; the molar mass of a molecule is equal to its RMM
This implies that 1 mole of oxygen molecules has a mass of 32 g. This is because in oxygen atoms there
are two atoms of oxygen in one molecule of oxygen. Therefore, the relative molecular mass of oxygen
molecule is, 16 × 2 = 32. Since each molecule of oxygen has two atoms, then 1 mole of oxygen
molecules would contain 2 × 6.023 × 10 23 = 1.2046 × 10 24 molecules of oxygen.
98
Moles of Compounds
The mass in grams of one mole of a substance (that is, the mass in grams per mole) is called the molar
mass of the substance. The molar mass in grams per mole of any substance is numerically equal to its
formula weight in atomic mass units. For NaCl, for example, the formula weight is 58.5 amu and the
molar mass is 58.5 g.
I.e ; the molar mass of a compound is equal to its RFM

NaOH (23 + 16 + 1) 40g 1 mole 6.023 × 10 23

Na2CO3 (23x2 + 12 + 16x3) 106g 1 mole 6.023 × 10 23

MgSO4 (24 + 32 + 16x4) 120g 1 mole 6.023 × 10 23

Note : a mole is always the same number (6.023 x 10 23 ), but 1-mol samples of different substances
have different masses

Worked examples
1. Calculate how many moles are present in 0.5 grams of sodium hydroxide (Na = 23 O= 16
H=1)
RFM = (23 + 16 + 1) = 40 g
40g of 1 mole
0.5g of ?
0.5 X 1 = 0.0125 moles
40
2. Calculate the number of moles that are in 0.25g of Sodium Carbonate (Na = 23, O= 16, C= 12)
RFM = ( 23x2 + 12 + 16x3) = 106 g
106 g 1 mole
0.25g ?
0.25 X 1 = 0.002358 moles
106
3. Calculate the number the number of moles present in 0.56g of Magnesium Sulphate ( Mg = 24, O =
16 , S = 32)
RFM = ( 24 + 32 + 16x4)
120 1 mole
0.56 g ?

0.56 X 1 = 0.0046667 moles

120
B. Moles Mass
1. How many grams are present in 0.5 moles of Sodium Carbonate (Na = 23, O= 16, C= 12)
RFM = ( 23x2 + 12 + 16x3) = 106 g
106 1 mole Fe
99

? 0.5 moles
0.5 X 106 = 53 g
1
4. How many grams are present in 0.0025 moles of Magnesium Sulphate ( Mg = 24, O = 16 , S =
32)
RFM = ( 24 + 32 + 16x4)
120 g 1 mole
? 0.0025 moles

0.0025 X 120 = 0.3 g

1
1. How many grams are present in 0.25 moles of Sodium Hydroxide (Na = 23 O= 16 H=1)
RFM = (23 + 16 + 1) = 40 g
40 g 1 mole
? 0.25 moles

0.25 X 40 = 10 g
1
Trial questions
1. 0.25g of Sodium Hydroxide reacted with dilute hydrochloric acid for a neutralization reaction .
calculate the number of moles of sodium that reacted completely with dilute acid.
2. 20 cm3 of dilute hydrochloric Acid reacts completely with 0.05 moles of Sodium Carbonate.
Calculate the amount of sodium carbonate in grams required to be added to the acid for complete
reaction
EMPERICAL AND MOLECULAR FOMULAR
Empirical Formula
The empirical formula for a substance tells us the relative number of atoms of each element in the
substance. The empirical formula H2O shows that water contains two H atoms for each O atom. This
ratio also applies on the molar level: 1 mol of H2O contains 2 mol of H atoms and 1 mol of O atoms.
Conversely, the ratio of the numbers of moles of all elements in a compound gives the subscripts in the
compound’s empirical formula. Thus, the mole concept provides a way of calculating empirical
formulas.
How to calculate
Ascorbic acid (vitamin C) contains 40.92% C, 4.58% H, and 54.50% O by mass. What is the empirical
formula of ascorbic
Analyze: We are to determine the empirical formula of a compound from the mass percentages of its
elements.
Plan: The strategy for determining the empirical formula involves the three steps given
Solve
1. For simplicity, we assume we have exactly 100 g of material
2. We calculate the number of moles of each element:
3. We determine the simplest whole-number ratio of moles by dividing each number of moles by
100

the smallest number of moles:

 N/B The ratio for H is too far from 1 to
attribute the difference to experimental
1
error; in fact, it is quite close to 13 .
This suggests we should multiply the
ratios by 3 to obtain whole numbers:

Trial question

1. A 5.325-g sample of methyl benzoate, a compound used in the manufacture of perfumes,

contains 3.758 g of carbon, 0.316 g of hydrogen, and 1.251 g of oxygen. What is the empirical
formula of this substance?
2. A compound weighing 42 grams was found to contain 12 grams magnesium, 6 grams carbon and
the rest oxygen. Determine the empirical formula of the compound. (Mg = 24.0, C = 12.0, O =
16.0).
3. A sample of a hydrocarbon of mass 51.2 g was analyzed and found to contain 12.8 grams
hydrogen. If the formula of the hydrocarbon is Cx Hy . Find the values of x and y. (C = 12.0, H =
1.0).
4. The empirical formula of an organic compound is C1H2 O1 . If the empirical formula mass of
the compound is 30. Find the percentage composition of the elements in the compound (C =
12.0, H = 1.0, O =16.0).
5. A 9.6-gram piece of clean magnesium burned completely in 6.4 grams of pure oxygen, and the
product was allowed to cool to room temperature and pressure r.t.p. Determine the reaction mole
ratio, and hence the formula of the oxide. (Mg = 24.0, O = 16.0).
6. A sample of anhydrous copper(II) sulphate on analysis was found to contain 6.4 grams of
copper, 3.2 grams sulphur and 6.4 grams oxygen. Determine its empirical formula. (Cu = 64.0, S
= 32.0, O = 16.0).
7. In an experiment 3.10 grams of a compound of carbon, hydrogen and oxygen produced 4.4
grams of carbon(IV) oxide and 2.7g of water on complete combustion. Determine the empirical
formula of the compound. (C = 12.0, O = 16.0, H = 1.0).
101
Molecular Formula

We can obtain a molecular formula for any compound from its empirical formula if we know either the
molecular weight or the molar mass of the compound. The subscripts in the molecular formula of a
substance are always whole-number multiples of the subscripts in its empirical formula. This multiple
can be found by dividing the molecular weight by the empirical formula weight:
(Mass of empirical formula)n = Molecular mass,
Worked example
A compound of carbon, hydrogen and oxygen contains 54.55% carbon, 9.0% hydrogen, and 36.6%
oxygen. If its relative molecular mass is 88, what is its molecular formula? (C = 12, O = 16, H = 1).
Solution

(C2H4O)n = 88

44n = 88 n=2

Molecular formula = C4H8O2

Trial questions
1. An organic compound has a relative formula mass of 90 grams. A 7.5 grams sample contains 3
grams carbon, 0.5 grams hydrogen, and 4.0 grams oxygen. Determine its molecular formula. (C
= 12.0, H = 1.0, O = 16.0)
2. A chloride of sulphur was found to have a relative molecular mass of 135 g. A 5.4 grams sample
of the chloride was also found to contain 2.84 grams of chlorine. Determine the molecular
formula of the chloride. (C1 = 35.5, S = 32.0)
3. A hydrated salt of copper has the formula CuSO4 . nH2O. About 25 grams of the salt was heated
until all the water evaporated. If the mass of the anhydrous salt is 16.0 grams. Find the value of
n. (Cu = 64.0, S = 32.0, O = 16.0, H = 1.0)
4. On complete combustion of one mole of a certain alkane, two moles of carbon (IV) oxide and
three moles of water were produced. Determine the relative molecular mass of the alkane. (C =
12.0, H = 1.0)
5. If 7.36 grams of a compound decomposed to produce 6.93 grams of oxygen, and the rest
102

hydrogen. If the molecular mass of the compound is 34 grams. Determine the molecular formula
 Moles of volumes
Molar Solution
A molar solution is a solution that contains one mole of a solute in one litre of the solution.

How can a molar solution be prepared in the lab

From the definition a molar solution is a solution that contains one mole of a solute in one litre of the
solution.
Therefore to prepare a molar solution;
i. Weigh amount of solute equal to the molar mass
ii. Add it in a beaker and add distilled water and stir to dissolve the solute
iii. Tranfer the solution to (1000cm3) 1 litre volumetric Flask
iv. Wrinse the beaker with distilled water and add it to the 1 litre volumetric flask
v. Top up the solution with ditilled water to the litre mark

1. Worked Problem
How can a molar solution of Sodium Carbonate be prepared in the laboratory
Na2CO3
RFM = ( 23x2 + 12 + 16x3) = 106g i.e 106 is the molar mass
i. Weigh 106 grams of sodium carbonate and tranfer it to a beaker
ii. Add 100cm3 of distilled water and stir to dissolve the solute
iii. Tranfer sodium carbonate solution to (1000cm3) 1 litre volumetric Flask
iv. Wrinse the beaker with distilled water and add it to the 1 litre volumetric flask
v. Top up the solution with ditilled water to the litre mark
In this section, the terms concentration, molarity and dilution will be discussed.
Definition od terms
Concentration of a solution
Concentration of a solution is the amount of a solute contained in a given volume of the solution.
The concentration of a solution is always expressed in terms of moles per volume of the solution OR
grams per the volume of the solution
e.g
Consider, 0.25 grams of sodium carbonate dissolved in 150 cm3 of distilled water in a 250cm3 volumetric flask,
and then topped up to the mark by adding enough distilled water.
2. Worked Example
The concentration of the resulting solution can then be expressed as 0.25 grams of
sodium carbonate / 250 cm3 of distilled water.
OR
RFM = ( 23x2 + 12 + 16x3) = 106g
106g 1 mole
0.25g ?
0.25 x 1 = 0.002358 moles
106
103

The concentration of the resulting solution can then be expressed as 0.002358 moles/ 250 cm3
Molarity of a solution
Molarity of a solution is is the amount of a solute contained in 1000cm3 volume of the solution. Molarity
is only given in moles of the solute per litre of solution (moles/100 cm3 ). This is normally expressed as
mol/dm3. Molarity is always denoted by a capital (M)
e.g
0.15 M which implies that 0.15 moles are contained in 1000 cm3 of
solvent
It can also be written as (0.15 mol/dm3 or 0.15 moldm-3 ) which implies
that 0.15 moles are contained in 1000 cm3 of solvent.
This information can be expressed as
0.15 1000cm3
which is then used as a conversion rate.

Trial questions

Concentration
1. Determine the concentration of a solution if 4.0 g of sodium hydroxide were dissolved in 400
cm3 of distilled water then made up to 500 cm3 of solution.
concentration in:
(a) grams.
(b) moles.
Molarity
2. Determine the molarity of a solution containing 10.6 g of sodium carbonate dissolved in: (a) 250
cm3 of distilled water. (b) 500 cm3 of distilled water. (Na = 23, C = 12, O = 16).
3. Calculate the number of moles of sodium carbonate present in 100 cm3 of 2 M Na2CO3
solution.
4. Calculate the mass of sulphuric(VI) acid in 250 cm3 of a solution whose concentration is 0.25
mole dm-3 .
5. Calculate the: (a) Number of moles present in 25 cm3 of a 0.2 M Sodium hydroxide solution. (b)
Mass in grams present in 25 cm3 of a 0.2 M Sodium hydroxide solution. (Na = 23, O = 16, H =
1).
6. Calculate the number of moles of sodium chloride in 500 cm3 of 3 M sodium chloride solution.
7. Calculate the mass of calcium chloride (CaCl2, ) required to make one litre of 0.2 M calcium
chloride solution.
8. When 34.8 grams of potassium sulphate (K2SO4, ) were dissolved in 500cm3 distilled water.
Calculate:
(i) The concentration of potassium sulphate in g/litre.
(ii) The molarity of the solution. (K = 39.0, S = 32.0, O = 16.0)
9. Explain how a 250 cm3 solution of 1.0 M potassium hydroxide solution can be prepared. (K =
104

39, O = 16, H = 1).

 10. Calculate the mass of lead nitrate, Pb(NO3 )2 required to make 500 cm3 of a 0.1 M solution. (Pb
= 207.0, N = 14.0, O = 16.0)
11. Find the mass of nitric acid required to prepare 25 cm3 of a 12.6 g per litre of nitric acid solution.
(O = 16, N = 14, H = 1)
12. In a class of 25 students, each student requires 120 cm3 of 0.2 M potassium hydroxide solution
for a titration experiment. Calculate:
(i) The total volume of potassium hydroxide required for the class. (K = 39, O = 16, H = 1)
(ii) The total mass of potassium hydroxide required to prepare the total volume of solution
for the class.
13. Calculate the molarity of a solution of sulphuric (IV) acid (H2SO4 ) that is obtained by
dissolving 9.8 g of sulphuric(IV) acid in 100 cm3 of solution. (S = 32, O = 16, H = 1)
Dilution of solution
Dilution is a process by which the concentration of a solution is lowered by adding more solvent into the
solution. During dilution, the amount of solute remains the same as the volume of the solution increases.
Solutions of different molarities may be prepared by adding water to equal volumes of solutions of the
same concentration and making up to different volumes.
That it to say, that the molarity of the dilute solution (M2 ) is obtained by multiplying the molarity of the
concentrated solution (M1 ) with the volume of the concentrated solution (VI ), and dividing by the final
volume of the dilute solution (V2 );
This is expressed mathematically as M1V1 = M2V2
Worked example
Calculate the volume of a 5.0 M H2SO4 solution that will be required to make a 1000 cm3 solution of
0.05 M H2SO4
M1V1 = M2V2
5 x Y = 0.05 x 1000
1000 x 0.05 = 10 cm3
5
Trial Questions
1. When 50 cm3 of 2M potassium hydroxide solution was diluted, the final concentration was
0.1M. Calculate the volume of the diluted solution.
2. Calculate the volume of 18 M sulphuric(IV) acid, H2SO4 , that will be required to prepare 3.6
litres of 0.2 M sulphuric(VI) acid.
3. A label on a bottle containing sulphuric(IV) acid has the following information:

Density = 1.836 g/cm3

Percentage purity = 98%
Relative formula Mass = 98
105
 Calculate:
(a) The concentration of the acid.
Mass present in the botlle per littre
1.836g 1 cm3
1000 cm3
1.836 x 1000 = 1836 g/ 1000 cm3
1
Mass of pure sulphuric(IV) acid in a litre
1836 x 98 = 1799.28 g
100
Molarity of pure sulphuric(IV) acid in a litre
Mass in a litre / RFM
1799.28 g = 18.36 M
98
Alternative 2
Density x % purity x 1000
RFM

1.836 x 0.98 x 1000 =18. 36 M

98
(b) The volume of the concentrated sulphuric(VI) acid that should be diluted to produce 2 litres
of 2 M sulphuric(VI) acid.
M1V1 = M2V2
18.36M x V1 = 2 M x 2 litres

2x2 = 0.217865 litres = 218 cm3

18.36
Trial questions
1. About 250 cm3 of a 2 M sodium hydroxide solution is diluted to 2000 cm3 . Calculate the new
concentration.
2. Calculate the volume of 18.4 M sulphuric(VI) acid, H2SO4, that will be required to prepare 500 cm3 of a
2 M sulphuric(VI) acid solution.
3. Calculate the volume of 5.0 M HCl solution that would be required to prepare 400 cm3 of 0.8 M HCl
solution.
4. Calculate the volume of water that is to be added to 20 cm3 of 12.4 M hydrochloric acid, HCl solution to
make 2 M solution.
5. A bottle containing nitric(V) acid has a label with the following information;
• Density = 1.44 g cm–3
• Relative formula Mass = 63
• Percentage purity = 65%
(a) Calculate the concentration of nitric(V) acid, HNO3 , in moles per litre.
106

(b) What will be the concentration of a solution prepared by diluting 20 cm3 of the concentrated
acid to make 250 cm3 of the acid solution.
Stoichiometry of Chemical Equations
A chemical equation in which the reactants and products are in whole number ratios is called a
stoichiometric equation.
Stoichiometry is a quantitative relationship between reactants and products in a chemical reaction.
Consider the chemical equation below, In a balanced chemical equation, the quantities of reactants and
products are in a whole number ratio. For example, in the equation; the reactants and products can be
seen to combine in;
2Mg(s) + O2 (g) 2MgO(s),
The reactants and product are in the mole ratio 2:1:2.
Equally 2 NaOH (aq) + CuSO4 (aq) Cu(OH)2 (s) + Na2SO4 (aq)

Can be said to have combined in a mole ratio of 2 : 1 : 1: 1

Ionic Equation
When a chemical reaction takes place between aqueous ionic compounds, only certain ions combine to
form either a solid, liquid or gas. Ions which do not undergo change in a chemical reaction are called
spectator ions and are usually omitted when writing the ionic equation. There are three possibilities
during ionic changes:
(i) Formation of a precipitate (solid).
(ii) Evolution of a gas.
(iii) Formation of a liquid.
Worked examples
1. Aqueous Sodium hydroxide reacts with aqueous copper(II) sulphate to precipitate copper(II)
hydroxide.
Chemical equation 2 NaOH (aq) + CuSO4 (aq) Cu(OH)2 (s) + Na2SO4 (aq)
+ - 2+
Ionic equations 2 Na (aq) + 2 OH (aq) + Cu (aq) + SO2-4 (aq) Cu(OH)2 (s) + 2 Na+(aq) + SO2-4 (aq)
Net ionic equation Cu 2+ (aq) + 2 OH- (aq) Cu(OH)2 (s)
Ions are combined in a mole ratio of 1: 2: 1

2. Aqueous potassium carbonate reacts with aqueous silver nitrate to precipitate silver carbonate.
Chemical equation K2CO3 (aq) + 2 AgNO3 (aq) Ag2CO3 (s) + 2 KNO3 (aq)
Ionic equations 2 K +(aq) + CO32- (aq) + 2 Ag+(aq) + NO-3 (aq) Ag2CO3 (s) + 2 K+(aq) + NO-3 (aq)
Net ionic equation 2 Ag+ (aq) + CO3-2 (aq) Ag2CO3 (s)
Ions are combined in a mole ratio of 2 : 1: 1

3. Sulphuric acid reacts to neutralize aqueous sodium hydroxide.

Chemical equation 2 NaOH (aq) + H2SO4 (aq) Na2SO4 (aq) + 2 H2O (l)
Ionic equations 2 Na+(aq) + 2 OH- (aq) + 2 H+(aq) + SO2-4 (aq) 2 Na+(aq) + SO2-4 (aq) + 2 H2O (l)
Net ionic equation 2 H+ (aq) + 2 OH- (aq) 2H2O (l)
107

Ions are combined in a mole ratio of 2: 2: 2

Trial questions
1. If 25 cm3 of a 0.1 M Na2CO3 solution neutralised a solution containing 30cm 3 of Sulphuric(VI)
acid
a) calculate the moles of Na2CO3 that reacted with sulphuric (vi) Acid
b) Write the equation for the reaction from this information.
c) Calculate the molarity of sulphuric(IV) acid.
2. 25.0 cm3 of 0.12M potassium hydroxide solution required 30.0cm3 of a solution of a dibasic
acid (H2R) for complete neutralization. The acid contained 3.15g per 500cm3 solution Calculate:
a. The molarity of the acid solution. (1½marks)
b. The relative formula mass of the acid. (1½ marks)
3. In a filtration experiment 25cm3 of a solution of Sodium Hydroxide containing 8g per litre was
required for complete neutralization of 0.245g of a dibasic acid. Calculate the relative molecular
mass of the acid (Na = 23.0, O = 16, H= 1)
4. 6.4g of a mixture of sodium carbonate and sodium chloride was dissolved in water to make
50cm3 solution. 25cm3 of the solution was neutralized by 40cm3 of 0.1M HCl(aq). What is the
percentage of sodium chloride in the solid mixture?

Volumetric Analysis (Paper 3) Titration

Volumetric analysis is a method of quantitative chemical analysis in which the amount of a substance is
determined by measuring volumes of solution.
Procedure; Titration
Two solutions are usually considered. One solution of known concentration and volume is reacted
carefully with another of unknown concentration to determine the reacting volumes. This data is used to
determine the concentration of the said solution.
A solution whose exact concentration is known is called a standard solution.
The apparatus used in volumetric analysis are;
1. Pipettes
2. Burettes.
3. Conical flasks
Precautions before titration
How to use pipette
Before use, the pipette must be rinsed with the solution to be drawn. It is then filled
by sucking the liquid to a few centimeters above the calibration mark.

The solution is then allowed to drain slowly under gravity until the meniscus is at
the same level with the mark. Sucking can be done using the mouth or a pipette
filler.
N/B Pipette fillers must be used especially when solutions are toxic.
108
How to use Burette

A burette is designed to deliver variable volumes of solution as needed during

a titration. Before use, a burette must be rinsed with the solution to be used in
it.

It is then filled carefully beyond the 0.0 mark and the level of the solution is
adjusted until the bottom of the meniscus is at the same level with the
graduation mark.

Recording the values of burette

When recording the burette reading , one must take care of the degree of accuracy of the apparatus; in
this case (the least degree of error the apparatus can measure ).
A burette, is graduated from 0.0 to 50.0 cm3 with unit intervals of 0.1cm3. This indicates that the least
value that can be read from the apparatus is 0.1cm3.
Identify the burette reading in the following burettes

=
= 22.3 cm3 = 20. 2 cm3

The reading on the burette is recorded at the lower meniscus.

NOTE:
The scale of the burette begins from zero at the top and increases downwards to the maximum value.
For example, a reading of 22.2 cm3 on the burette means that the volume of the liquid poured from the
109

burette is 22.2 cm3 and the volume left in the burette is (50 – 22.2) ml, i.e., 27.8 cm3.
Titration
Titration is a quantitative analysis process using solutions.
A solution of known concentration is added gradually to another solution of unknown concentration
until the reaction between the two solutions is complete.
A solution whose exact concentration is known is called a standard solution.

The point at which the reaction is complete is called the end point. An indicator is used to identify the
end point. The point where the indicator turns indicate end point. The volume of the solution that run
out of the burette in every titration experiment is known as a titre.
After the titration the data should be arranged in tabular form as shown

TITRATION 1 2 3
Final Burette Reading
Initial Burette Reading
Titre Volume Used

Technique of filling the table and obtaining average titre

1. The first step is to complete the table with values that have consistent decimal places i.e the titre
should be recorded in one decimal place or depending on the degree of error of the apparatus.
2. While filling , the titre volumes for the three experiments should be consistent and have an
accuracy of ± 0.1 or ± 0.2 cm3
3. The average titre is given by adding the volumes of the consistent titres used divided by number
of experiments done. i.e titre whose values are less or equal to ± 0.2 cm3
110

N/B If the average titre results to decimals, write the decimals in atleast four significant figures
Worked Example 1
You are provided with:
0.1M sodium hydroxide solution A
Hydrochloric acid solution B
You are required to determine the concentration of solution B in moles per litre.
Procedure
Fill the burette with solution B. Pipette 25.0cm3 of solution A into a conical flask. Titrate solution A
with solution B using phenolphthalein indicator to complete the titration table 1

Sample results Titration table 1

Data recorded in the table

TITRATION 1 2 3
Final Burette Reading 23.3 40.8 32.2
Initial Burette Reading 0.0 17.4 9.0
Titre Volume Used 23.3 22.4 22.2
Sample questions
Calculate the average volume of solution B used

22.3 + 22.4 + 22.2 = 22.3 cm3

3

Direct Titration
This is a type of titration that involves the addition of a standard solution to a fixed volume of the
analyte (substance being anlaysed), or vice versa with the sole aim of determining either:
(a) Concentration.
(b) Relative atomic mass of the elements of the sample analyte or,
(c) The percentage composition of the constituent elements.
A good example is a neutralization reaction.
A neutralization reaction is the reaction between an acid and an alkali forms a salt and water only.
In this type of reaction, the acid is often placed in the burette and the base placed in the conical Flask
after pipetting.
111
Worked example
You are provided with:
i. 0.1M sodium hydroxide solution A
ii. Hydrochloric acid solution B
You are required to determine the concentration of solution B in moles per litre.
Procedure
Fill the burette with solution B. Pipette 25.0cm3 of solution A into a conical flask. Titrate solution A
with solution B using phenolphthalein indicator to complete the titration table 1 Sample results Titration
table 1
TITRATION 1 2 3
Final Burette Reading 20.0 20.0 20.0
Initial Burette Reading 0.0 0.0 0.0
Titre Volume Used 20.0 20.0 20.0
1. Calculate the average volume of solution B used
20.0 + 20.0 +20.0 = 20.0cm3
3
2. How many moles of:

i. solution A were present in 25cm3 solution.

1000 cm3 0.1 M
3
25 cm ? 25 x 0.1 = 0.0025 moles
1000

ii. solution B were present in the average Volume

NaOH + HCl NaCl + H2O
Mole ratio 1: 1
Moles of NaOH = 0.0025 moles
1
X 0.0025 moles = 0.0025 moles
1
iii. Solution B moles per litre / concentration of B / molarity of B
20.0 cm3 0.0025 moles
1000 cm 3 ? 0.0025 x 1000 = 0.1 M
20
Back Titration
Back titration is a method of volumetric analysis used to determine the concentration (or amount) of a
reactant. It involves reacting quantities of the substance being analysed with an excess amount of a
suitable reagent whose volume and concentration is known.
The quantity of the excess is then measured through titration. The amount of the reagent that reacted
with the analyte is determined by subtracting the excess amount from the initial.
The data is then used to determine the concentration (or amount) of the analyte.
112
Worked Example
You are provided with:
(i)an impure calcium carbonate labeled M
(ii)Hydrochloric acid labeled solution N
(iii)solution L containing 20g per litre sodium hydroxide.
You are required to determine the concentration of N in moles per litre and the % of calcium carbonate
in mixture M.
Procedure 1
Pipette 25.0cm3 of solution L into a conical flask. Add 2-3 drops of phenolphthalein indicator. Titrate
with dilute hydrochloric acid solution N and record your results in table 1(4mark)
Sample Table 1
TITRATION 1 2 3
Final Burette Reading 6.5 6.5 6.5
Initial Burette Reading 0.0 0.0 0.0
Titre Volume Used 6.5 6.5 6.5
Sample questions
1. Calculate the average volume of solution N used
6.5 + 6.5 + 6.5 = 6.5 cm3
3
2. How many moles of sodium hydroxide are contained in 25cm3 of solution L
40 g 1 mole
20 g ? 20 x 1 = 0.5M
40
3
0.5 M 1000 cm
3
25 cm ? 0.5 x 25 = 0.0125M
1000
3. Calculate:
(i) The number of moles of hydrochloric acid that react with sodium hydroxide in (b)above.
NaOH + HCl NaCl + H2O
Mole ratio NaOH : HCl from stoichiometric equation= 1:1
1
X 0.0125 moles = 0.0125 moles
1
(ii) The molarity of hydrochloric acid solution N.
0.0125 6.5 cm3
? 1000 cm3 1000 x 0.0125 = 1.9231M
6.5
Procedure 2
Place the 4.0 g of M provided into a conical flask and add 25.0cm3 of the dilute hydrochloric acid to it
using a clean pipette. Swirl the contents of the flask vigorously until effervescence stop. Using a 100ml
measuring cylinder add 175cm3 distilled water to make up the solution up to 200cm3.Label this solution
K. Using a clean pipette transfer 25.0cm3 of the solution into a clean conical flask and titrate with
113
solution L from the burette using 2-3 drops of methyl orange indicator. Record your observations in
table 2.
TITRATION 1 2 3
Final Burette Reading 24.5 24.5 24.5
Initial Burette Reading 0.0 0.0 0.0
Titre Volume Used 24.5 24.5 24.5

Sample calculations
1. Calculate the average volume of solution L used
24.5 + 24.5 + 24.5 = 24.5cm3
3
2. How many moles of sodium hydroxide are present in the average volume of solution L used?
1000 cm3 0.5 moles
24.5 24.5 x 0.5 = 0.01225 moles
1000
3. How many moles of hydrochloric acid are present in the original 200cm3 of solution K?
NaOH + HCl NaCl + H2O
Mole ratio NaOH: HCl = 1:1
= 0.01225 moles
3
25 cm 0.01225 moles
3
250 cm
250 x 0.01225 = 0.49 moles
25
4. How many moles of hydrochloric acid were contained in original 25 cm3 solution N used
1.923 M 1000 cm3
25 cm3
25 x 1.923 = 0.04807 moles
1000
5. How many moles of hydrochloric acid were used to react with calcium carbonate present?
0.04807 – 0.01225
= 0.03582 moles
6. Write the equation for the reaction between calcium carbonate and hydrochloric acid.
CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
7. Calculate the number of moles of calcium carbonate that reacted with hydrochloric acid.

From the equation CaCO3(s):2HCl(aq) = 1:2

Moles CaCO3(s) = 1 /2moles HCl

1 /2 X 0.03582 moles
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= 0.01791 moles
 8. Calculate the mass of calcium carbonate in 4.0g of mixture M (Ca=40.0,O = 16.0,C=12.0)
Molar mass CaCO3 = 100g

0.01791 moles x 100g = 1.791g

1.791g
9. (i)Determine the % of calcium carbonate present in the mixture
% CaCO3 = Mass of pure x 100% = 1.791g x 100% = 44.775%
Mass of Impure 4.0

Redox Titration
In redox reactions, both reduction and oxidation take place simultaneously. Titrations involving redox
reactions do not require indicators because the colour of some of the reagents change when their
oxidation states change. Examples of redox titrations involve the use of potassium manganate(VII) and
potassium dichromate(VI). Manganate(VII) ions are purple in colour. When reduced to manganese(II),
the solution becomes colorless.

Worked Example
You are provided with:
✓ Acidified Potassium manganate(VII) solution A
✓ 0.1M of an iron (II) salt solution B
✓ 8.5g of ammonium iron(II)sulphate(VI) crystals (NH4)2SO4FeSO4.xH2O. solid C
You are required to
❖ standardize acidified potassium manganate(VII)
❖ determine the value of x in the formula (NH4)2SO4FeSO4.xH2O.
Procedure 1
Fill the burette with solution A. Pipette 25.0cm3 of solution B into a conical flask. Titrate solution A
with solution B until a pink colour just appears.
Record your results to complete table 1.
Sample results
TITRATION 1 2 3
Final Burette Reading 20.0 20.0 20.0
Initial Burette Reading 0.0 0.0 0.0
Titre Volume Used 20.0 20.0 20.0
Sample worked questions
1. Calculate the average volume of solution A used
20.0 + 20.0 +20.0 = 20.0cm3
3
2. How many moles of:
(i) Solution B were present in 25cm3 solution.
1000 cm3 0.1 M
115

3
25 cm ?
 25 x 0.1 = 0.0025 moles
1000
(ii) Solution A were present in the average volume. Assume one mole of B react with five moles
of B Mole ratio A : B = 1:5
1
X 0.0025 = 0.0005 moles
5
(iii) Solution B in moles per litre.
1000 cm3 ?
3
20 cm 0.0025 moles
0.0025 x 1000 = 0.025 M
3
20 cm
Procedure 2
Place all the solid C into the 250cm3 volumetric flask carefully. Add about 200cm3 of distilled water.
Shake to dissolve. Make up to the 250cm3 of solution by adding more distilled water. Label this solution
C. Pipette 25cm3 of solution C into a conical flask, Titrate solution C with solution A until a permanent
pink colour just appears. Complete table 2.

TITRATION 1 2 3
Final Burette Reading 20.0 20.0 20.0
Initial Burette Reading 0.0 0.0 0.0
Titre Volume Used 20.0 20.0 20.0
Sample worked questions
1. Calculate the average volume of solution A used
20.0+ 20.0 +20.0 = 20.0cm3

2. How many moles of:

(i) Solution A were present in the average titre.
1000 cm3 0.025 M
3
20 cm ?
0.025 x 20 = 0.0005 moles
1000
3
(ii) Solution C in 25cm solution given the equation for the reaction:
MnO4 - (aq) + 8H+ (aq) + 5Fe2+ (aq) Mn2+ (aq) + 5Fe 3+(aq) + 4H2O(l)
Mole ratio MnO4 - (aq): 5Fe2+ (aq) = 1:5
1 x 0.0005 = 0.0001 moles
5
3
(iii) Solution B in 250 cm
25 cm3 0.0001
3
250 cm
0.025 x 20 = 0.0005 moles
116

1000
 3. Calculate the molar mass of solid C and hence the value of x in the chemical formula
(NH4)2SO4FeSO4.xH2O.
(N=14.0, S=32.0, Fe=56.0, H=1.0 O=16.0)
Molar mass = Mass perlitre = 8.5 = 8500 g
-3
Moles per litre 1.0 x 10 moles
(NH4)2SO4FeSO4.xH2O. = 8500
284 + 18x =8500
8500 - 284 = 8216 = 18x = 454.4444
18 18
x = 454 (whole number)
Atomicity and Molar Gas Volume Atomicity

Atomicity
Atomicity is the number of atoms in one molecule of an element.
For example, oxygen (O2 ), hydrogen (H2 ) and nitrogen (N2 ) have two atoms per molecule, thus they
are diatomic. Ozone (O3 ) has three atoms in a molecule and is therefore triatomic. The noble gases are
said to have an atomicity of one (monoatomic) even though they are not molecular.
Molar Gas Volume Atomicity
The volume occupied by one mole of any gas at given temperature and pressure is called the molar gas
volume. Its value at s.t.p is 22.4 dm3/ 22400cm3.
If the volumes are worked out at another temperature and pressure, a different constant value is
obtained. For example, at 25°C, and one atmosphere pressure (r.t.p), the molar gas volume is 24.0 dm3 /
24000 cm3 . The conditions of temperature of 25°C and one atmospheric pressure are called room
temperature and pressure (r.t.p).

The relationship between reacting volumes of gases is summarised by Gay Lussac’s Law:

Gay Lussac’s Law: When gases react, they do so in volumes that bear a simple ratio
to one another and to the volumes of the product if gaseous, temperature and
pressure remaining constant.

It has also been found from experiments that equal volumes of all gases under the same
conditions of temperature and pressure contain an equal number of molecules. This
relationship leads to the Avogadros’ Law:
Avogadros’ Law: “Equal volumes of gases will contain equal number of molecules”.
Avogadro’s law implies that volume ratios of reacting gases can be used interchangeably
with mole ratios when gases react. This means that reacting volumes of gases can be used
to determine the equation of reacting gases provided the volumes are measured under the
117

same conditions of temperature and pressure.

The conversion rate thus is
At stp 1 mole 22400 cm 3
At rtp 1 mole 24000 cm 3

Worked example

118