SECOND TERM NOTE FOR SS2

[2024 – 2025] ACADEMIC SESSION.

JESUIT MEMORIAL COLLEGE
PORT HARCOURT.

NAME:
………………………………………………….....

SUBJECT:
………………….....................................................

CLASS:
……………………………………………………

IDENTIFICATION NUMBER:
…………………………………………………….
Study to show thyself approved unto God, a
workman that needeth not to be ashamed,
rightly dividing the word of truth. 2 Timothy 2:
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1
OXYGEN AS AN ELEMENT
Oxygen is the most abundant element on earth and occurs in nature in both the free and
combined state, as free oxygen constitutes about 21% by volume of atmospheric air. It is the
first element in group VI of the periodic table and was discovered by Scheele in 1772 and
Priestley in 1774. It accounts for 55% by mass of the earth’s crust, the oceans and the air in
its combined form. It is present in trioxosilicates (IV) and oxides of both metals and non –
metals, which make up the rocks and clays.

Water, one of the most abundant compounds on earth is made up of 88% oxygen by mass.

BONDING CAPACITY OF OXYGEN

Oxygen atom has six electrons at its outermost shell (valence electrons) and can attain the
stable octet electronic configuration by:

1. Accepting two electrons from electropositive elements like metals to form the
negative oxide ion, O2- (i.e. formation of ionic compounds), e.g
Ca2+ + O2- → CaO
2. Entering into covalent bond formation with non – metals by covalently sharing two
out of its outer electrons. E.g
H–C=O

OH

It also forms single covalent bonds with two hydrogen atoms to give water molecules,

O–H

In oxygen molecule, a double covalent bond joins the two oxygen atoms, O = O.

Oxygen forms a wide variety of ionic and covalent compounds and it is the only element of
group VI which forms multiple bonds with itself.

2
LABORATORY PREPARATION OF OXYGEN
Oxygen is usually prepared in the laboratory by;

1. Thermal decomposition of potassium trioxochlorate (V) and

hydrogen peroxide

2. Oxidation of hydrogen peroxide

3
Other methods includes reaction of sodium peroxide with water, thermal decomposition of
oxides of metals such as: mercury, silver and lead. E.g

Heat

2HgO(s) → 2Hg(l) + O2(g)

Heat

2Ag2O(s) → 4Ag(s) + O2(g)

Heat

PbO2(s) → Pb(s) + O2(g)

2Na2O2(s) + 2H2O(l) → 4NaOH(aq) + O2(g)

4
From trioxochlorate (V):
Potassium trioxochlorate (V) on heating at a temperature of 368oC, decomposes to release all
its oxygen. The presence of manganese (IV) oxide, which acts as a catalyst makes the
reaction to occur at a lower temperature and at a much faster rate.

MnO2

2KClO3(s) → 2KCl(s) + 3O2(g)

Heat

The oxygen gas produced is collected over water, and if required dry, it is passed through
anhydrous calcium chloride or concentrated tetraoxosulphate (VI) acid and then collected
over mercury.

From hydrogen peroxide:

Hydrogen peroxide decomposes readily to liberate oxygen without any heating, in the
presence Of manganese (IV) oxide. This is called catalytic decomposition of hydrogen
peroxide.

MnO2

2H2O2(g) → 2H2O(l) + O2(g)

Hydrogen peroxide also reacts with acidified potassium tetraoxomanganate (VII) solution in
cold to produce oxygen. This is an oxidation – reduction reaction, in which the
tetraoxomanganate (VII) is the oxidizing agent and the hydrogen peroxide, the reducing
agent.

5H2O2(aq) + 2KMnO4(aq) + 3H2SO4(aq) → K2SO4(aq) + 2MnSO4(aq) + 8H2O(l) + 5O2(g)

This method is safe and requires no heating.

INDUSTRIAL PREPARATION OF OXYGEN

Oxygen is prepared industrially by electrolysis of water where cheap electricity is available
or by fractional distillation of liquid air. This method involves two stages, namely: the
liquefaction of atmospheric air and the fractional distillation of the liquefied air.

5
*Liquefaction of air:
Liquefied air is obtained by filtering air and passing it through caustic soda to remove dust
particles and carbon (IV) oxide. Air is compressed to a high pressure of about 200atm, to
give out a lot of heat. The compressed air is then cooled and allowed to escape rapidly
through a minute jet into an expansion chamber.

This process is repeated until all the gaseous air become liquid at -200oC.

*Fractional distillation of liquid air:

The liquid air which is mainly a mixture of nitrogen and oxygen is then passed into a
fractionating column. On distillation, nitrogen which is more volatile boils out first at a lower
boiling point of – 196oC and is collected as liquid nitrogen. Oxygen boils out at a
temperature of – 183oC and is collected as liquid oxygen. The liquid oxygen is compressed
and stored in strong steel cylinders under a pressure of about 100atm.

PHYSICAL PROPERTIES OF OXYGEN.

1. Pure oxygen is a colourless, odourless and tasteless

2. It is neutral to litmus paper

3. It is slightly soluble in water. This dissolved oxygen is of vital importance to aquatic life

4. Gaseous oxygen liquefies at – 183oC solidifies at – 225oC.

5. It has about the same density as that of air.

CHEMICAL PROPERTIES OF OXYGEN

1(a).Oxygen gas supports combustion of many substances. Metals,

except mercury, silver and gold, react with oxygen to form basic oxides.

4Na(s) + O2(g) → 2Na2O(s)

4K(s) + O2(g) → 2K2O(s)

2Ca(s) + O2(g) → 2CaO(s)

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The oxides of very reactive metals like potassium, sodium and calcium dissolves in water to
form alkalis.

2K2O(s) + 2H2O → 4KOH

Na2O(s) + 2H2O → 4NaOH

CaO(s) + H2O → Ca(OH)2

1(b).When sodium and potassium are heated in a plentiful supply of oxygen, higher
oxides [Na2O2 and K2O2] are formed instead of the basic oxide.

4Na(s) + 2O2(g) → 2Na2O2

4K(s) + 2O2(g) → 2K2O2

3. Non – metals such as sulphur, carbon and phosphorous burn in oxygen to form acidic
oxides. The acidic oxides are also known as acid anhydride because they dissolve in
water to form acids.
+H2O

S(s) + O2(g) → SO2(g) → H2SO3(aq)

+6H2O

P4(s) + 3O2(g) → P4O6 → 4H3PO3(aq)

+6H2O

P4(s) + 5O2(g) → P4O10 → 4H3PO4(aq)

+H2O

C(s) + O2(g) → CO2(g) → H2CO3(aq)

4. Most hydrocarbons burn in oxygen to produce carbon (IV) oxide and water.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

7
 5. The oxygen we breathe in oxidises the carbohydrate we eat to release energy.
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l) + Energy

Reaction of oxygen with elements and compounds are examples of oxidation reactions. An
oxidation reaction in which heat and light are produced is called combustion.

TEST FOR OXYGEN

Oxygen rekindles a glowing splinter. Dinitrogen (I) oxide, N2O, also behaves similarly.

DIFFERENCES BETWEEN OXYGEN AND DINITROGEN (1)

OXIDE

PROPERTY OXYGEN DINITROGEN (I) OXIDE

(i)Odour Odourless Pleasant odour
(ii) Solubility in water Slightly soluble Fairly soluble
(iii) Reaction with nitrogen Produces reddish brown No reaction
(II) oxide fumes of nitrogen (IV) oxide
(iv) Reaction with heated No residual gas Residual gas N2
copper

USES OF OXYGEN
(i) It is used as an aid to breathing where the natural supply of oxygen is insufficient.
E.g in high altitude flights, mountaineering and diving operations.
(ii) It is used for resuscitating fainting patient, adding breathing in some lung diseases
and when anaesthetics are administered to patient.
(iii) It is used in oxy – ethyne and oxy – hydrogen flames for cutting and welding
metals.
(iv) It is used in steel industry for the removal of carbon, sulphur and phosphorous.
(v) Oxygen is used in the manufacture of important chemical compounds like
tetraoxosulphate (VI) acid, trioxonitrate (V) acid, ethanoic acid etc

8
OXIDES
Oxides are binary compounds formed when elements combine with oxygen. Binary
compounds are compounds containing two elements only. Oxides are classified into the
following groups, namely: acidic oxides, basic oxides, amphoteric oxides, neutral oxides and
higher oxides.

1. Acidic Oxides:
These are oxides of non – metals. They are formed when non – metals reacts with oxygen.
E.g

C(s) + O2(g) → CO2

S(s) + O2(g) → SO2

As acidic oxides, they react with alkalis to form salt and water only.

CO2(g) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)

SO3(g) + 2KOH(aq) → K2SO4(aq) + H2O(l)

Nitrogen (IV) oxide forms two salts with sodium hydroxide, since it is a mixed anhydride.

2NO2(aq) + 2NaOH(aq) → NaNO3(aq) + NaNO2(aq) + H2O(l)

2. Basic Oxides:
These are oxides of metals. They are oxides formed when a metal reacts with oxygen. E.g

4Na(s) + O2(g) → 2Na2O(s)

2Ca(s) + O2(g) → 2CaO(s)

They react with acids to form salt and water.

Na2O(s) + 2HCl(aq) → 2NaCl(aq) + H2O(l)

CaO(s) + 2HNO3(aq) → Ca(NO3)2(aq) + H2O(l)

3. Amphoteric Oxides:
They are oxides of metals which can behave both as basic oxides and as acidic oxides, i.e
they can react with both acids and alkali to form salts and water only.

9
With acids, amphoteric oxides behave as bases, forming a salt and water.

ZnO(s) + H2SO4(aq) → ZnSO4(aq) + H2O(l)

With alkalis, they behave like acids and exhibit acidic properties by forming complex salts

ZnO(s) + 2NaOH(aq) + H2O(l) → Na2Zn(OH)4(aq)

Sodium tetrahydroxozincate (II)

Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)

Sodium tetrahydroxoalluminate (III)

Amphoteric oxides include the oxides of aluminium, zinc, lead and tin.

4. Neutral Oxides:
These are oxides which show neither acidic nor basic properties. They are neutral to litmus
paper and include: carbon (II) oxide, CO, dinitrogen (I) oxide, N2O and water, H2O.

5. Higher Oxides:
These are oxides containing higher proportion of oxygen than the ordinary oxides. Higher
oxides are classified into three groups, namely the peroxides, the dioxides and the mixed
oxides.

COMPOUNDS OF OXYGEN

HYDROGEN PEROXIDE (H2O2)

This is the second major hydride of oxygen apart from water. Various compounds of oxygen
ranges in chemistry, including the ozone (O3). In nature, ozone occurs in traces in snow and
dew.

LABORATORY PREPARATION OF HYDROGEN PEROXIDE

10
Hydrogen peroxide is prepared by the action of a cold dilute acid on a certain metallic
peroxide. Usually barium peroxide and dilute tetraoxosulphate (VI) acid are used because the
barium tetraoxosulphate (VI) produced is insoluble and can be separated easily by filtration.
BaO2(s) + H2SO4(aq) → BaSO4(aq) + H2O2(l)

The temperature of the reaction must be kept low in order to minimize the decomposition of
hydrogen peroxide.

INDUSTRIAL PREPARATION OF HYDROGEN PEROXIDE

Hydrogen peroxide is produced industrially by the oxidation of propan – 2 – ol with oxygen
under pressure.
(CH3)2CHOH(l) + O2(g) → (CH3)2C = O(l) + H2O2(l)

PHYSICAL PROPERTIES OF HYDROGEN PEROXIDE

1. Pure hydrogen peroxide is a pale blue syrupy liquid
2. It dissolves in water to give a very weak acidic solution
3. It boils with decomposition at 150oc and freezes at about -0.9oC

CHEMICAL PROPERTIES OF HYDROGEN PEROXIDE

1. Decomposition: Hydrogen peroxide decomposes when exposed to air to form
water and oxygen.
2H2O2(l) → 2H2O(l) + O2(g)
The decomposition reaction is exothermic and accelerated by heating, addition of
alkalis or introduction of finely divided platinum or manganese (IV) oxide as catalyst.
Propan – 1, 2, 3 – triol and mineral acids retard the decomposition of hydrogen
peroxide. They are usually added to commercial hydrogen peroxide to minimize its
decomposition.

2. As an oxidizing agent: Hydrogen peroxide is a strong oxidizing agent

because it can donate oxygen or accept electrons. During the process the hydrogen
peroxide is reduced to water.
Donate oxygen: H2O2(l) → H2O(l) + [O]
Accept electrons: H2O2(l) + 2H+(aq) + 2e- → 2H2O(l)
(a) For example, it oxidizes lead (II) sulphide to lead (II) tetraoxosulphate (VI) and
itself reduced to water
PbS(s) + 4H2O2(l) → PbSO4(s) + 4H2O(l)
(b) With potassium iodide: Hydrogen peroxide reacts with potassium iodide solution
acidified with dilute tetraoxosulphate (VI) acid to liberate iodine. The
tetraoxosulphate (VI) acid first reacts with the iodide to form iodic acid, HI,
which is then oxidised by the peroxide to liberate iodine. The hydrogen peroxide
oxidizes by accepting electrons from the iodide ion and itself is reduced to water.
2KI(aq) + H2SO4(aq) + H2O2(aq) → K2SO4(aq) + 2H2O(l) + I2(aq)

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 Ionically
2I-(aq) + 2H+(aq) + H2O2(aq) → 2H2O(l) + I2(aq)

3. As a reducing agent: Hydrogen peroxide behaves as a reducing agent when it

reacts with a more powerful oxidizing agent. Hydrogen peroxide behaves as a
reducing agent because it can accept oxygen or donate electrons. During the process,
the hydrogen peroxide itself is converted to gaseous oxygen.
Accept oxygen: H2O2(l) + [O] → H2O(l) + O2(g)
Donate electrons: H2O2(l) → 2H+(aq) + 2e- O2(g)
(i) With tetraoxomanganate (VII): Hydrogen peroxide reduces
acidified tetraoxomanganate (VII) to manganese (II) ion. During the
process, the purple tetraoxomanganate (VII) ion changes to a pale pink
manganese (II) ion.
2KMnO4(aq) + 3H2SO4(aq) + 5H2O2(aq) → K2SO4(aq) + 2MnSO4(aq) + 8H2O(l) +
5O2(g)
(ii) With chlorine and silver oxide: Hydrogen peroxide reduces
chlorine to hydrochloric acid and silver oxide to the metal.
Cl2(g) + H2O2(l) → 2HCl(aq) + O2(l)
Ag2O(s) + H2O2(l) → 2Ag(s) + H2O(l) + O2(l)

NOTE: Hydrogen peroxide exhibits oxidizing properties by donating

oxygen or accepting electrons and reducing properties by accepting
oxygen or donating electrons.

USES OF HYDROGEN PEROXIDE

1. Hydrogen peroxide is used as an antiseptic
2. It is used for water purification
3. It is also used as a bleaching agent for delicate materials such as silk, wood, wood
pulp and human hair that could be damaged by chlorine or sulphur (IV) oxide. It
bleaches by oxidation.
4. It is used in making of compounds like sodium dioxochlorate (III) and some organic
peroxides
5. Liquid hydrogen peroxide provides oxygen for the burning of fuel in space rockets
and diesel oil in the engines of submarines
6. It is used in the treatment of blackened white lead (II) paint to restore the white
colour.

NOTE: White lead (II) paints containing lead (II) trioxocarbonate (IV) blackens when
exposed to atmospheric hydrogen sulphide because the lead (II) compounds present are
converted to lead (II) sulphide. Treatment with hydrogen peroxide oxidises the lead (II)
sulphide to lead (II) tetraoxosulphate (VI), thus restoring the white colour.
PbS(s) + 4H2O2(l) → PbSO4(s) + 4H2O(l)

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OZONE (TRIOXYGEN)
Ozone is an unstable triatomic molecule of oxygen. J. Soret, in 1866 demonstrated that ozone
was an allotrope of oxygen, formed from atmospheric oxygen by lightning flashes. Small
fractions of ozone are also formed around electrical machinery when they are in operation.
Ozone exists in a layer at a height of about 25km above earth surface.

Ozone, or trioxygen, is an inorganic molecule with the chemic al formula O3.

It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is
much less stable than the diatomic allotrope O2 breaking down in the lower atmosphere to O2
or dioxygen. Ozone is formed from dioxygen by the action of ultra-violet light and also
atmospheric electrical discharges, and is present in very low concentrations throughout the
Earth’s atmosphere (stratosphere). Its concentration is highest in the ozone layer region of the
atmosphere, which absorbs most of the Sun's ultraviolet (UV) radiation.

PREPARATION OF OZONE
Ozone is prepared from oxygen by the use of silent electrical discharge. Dry oxygen is
passed through the space between the glass tubes. Each tube is coated with tin – foil which is
connected to the terminals of an induction coil. Silent electrical discharge is preferred
because sparking would generate heat, which decomposes the ozone. An ozonizer is used for
ozonizing oxygen.

3O2(g) → 2O3(g)

The ozonized oxygen should not be allowed to come into contact with rubber because it is
attacked by ozone.

PHYSICAL PROPERTIES OF OZONE

1. Ozone is a pale blue gas at ordinary temperature and pressure
2. It has a characteristic smell like that of a dilute chlorine
3. It is poisonous at concentration above 100 parts per million
4. Pure ozone can be obtained as blue liquid by cooling ozonized oxygen to 112oC.
5. Ozone is slightly soluble in water but dissolves in turpentine

CHEMICAL PROPERTIES OF OZONE

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 1. Ozone has similar chemical properties with oxygen except that it is more reactive. It
decomposes into ordinary oxygen on heating.
2O3(g) → 3O2(g)
2. Ozone is a more powerful oxidizing agent than oxygen. It oxidises lead (II) sulphide
and hydrogen sulphide to tetraoxosulphate (VI) acid.
PbS(s) + 4O3(g) → 4O2(g) + PbSO4(aq)
H2S(g) + 4O3(g) → 4O2(g) + H2SO4(aq)
It also oxidises sulphur (IV) oxide to sulphur (VI) oxide.
SO2(g) + O3(g) → O2(g) + SO3(g)
Oxygen is formed as a bye product in these reactions.
3. Ozone liberates iodine from potassium iodide in acidic solution.
KI(aq) + H2SO4(aq) + O3(g) → I2(aq) + O2(g) + K2SO4(aq) + H2O(l)

UOF OZONE
1. Ozone is a good bleaching agent
2. It is used as a disinfectant in water and sewage purification
3. It is used for ventilating areas which get very little fresh air
4. It is used in air conditioning plants

ALLOTROPY OF OXYGEN AND OZONE

Oxygen and ozone are allotropes. Allotropy is the ability of an element to exist in more than
one form in the same physical state.

DIFFERENCES BETWEEN OZONE AND OXYGEN

Oxygen (O2) Ozone (O3)

1. Insoluble in turpentine 1. Absorbed by turpentine
2. No effect on rubber 2. Attacks rubber
3. Has no effect on potassium iodide 3. Liberates iodine from potassium
solution iodide solution
4. Oxidizing agent 4. Powerful oxidizing agent
5. Heat has no effect 5. Heat converts ozone into oxygen
2O3(g) → 3O2(g)

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 6. No effect on mercury at room 6. Makes mercury wet glass
temperature

OZONE LAYER DEPLETION

Ozone, a pale blue gas with pungent smell, is harmless in small concentrations. If the
concentration rises above 120ppm, it can cause respiratory problems and headache.

FORMATION OF OZONE LAYER

In the lower atmosphere (troposphere), ozone is formed in many instances

1. The reaction between nitrogen oxides and hydrocarbon in sunlight

2. Passing a stream of oxygen through an electric discharge
3. Electric spark in car engines and electrical appliances (photocopiers)
4. Lightning: In the stratosphere (between 20 – 50km above the earth’s surface) ozone is
formed from atmospheric oxygen when ultra violet (u.v) radiation of the light energy
is absorbed. When ozone absorbs u.v light, on the other hand, it undergoes photo
dissociation giving molecular oxygen and atomic oxygen. This reaction is responsible
for the screening effect of ozone, which is very important for living organisms on
earth. The ozone screens off 99% of the dangerous u.v radiation from the sun. Thus,
depletion of the ozone layer will invariably result in excess u.v radiation reaching the
earth. This will lead to an increase in the incidence of skin cancer, eye cataract and a
disastrous decrease in crop yields.
u.v light
O3(g) → O2(g) + O(g)

CHLOROFLUORO CARBONS (CFCs)

CFCs makes up a family of organic compounds containing chlorine (Cl2), fluorine (F2) and
carbon (C). They are used for a number of purposes because of their low toxicity, non –
flammability and unreactive nature.

15
HALOGENS
Halogens are family of group VII elements in the periodic table which includes the following
as members, fluorine, chlorine, bromine, iodine and astatine. Each halogen atom has seven
valence electrons which accounts for the similarity in their chemical properties. They are
very reactive non – metal with distinguishing colour and some having distinct colour. They
are not free in nature, but combined with metals to form compounds because they are very
reactive. Fluorine is the most reactive element among the halogens. Astatine which is
radioactive has been made artificially and does not occur in nature.

ELECTRONIC CONFIGURATION AND PROPERTIES OF

HALOGENS
Identical electronic configuration of seven valence electrons is responsible for the similar
properties found in all the halogens. Electronic configuration of the halogens is one electon
short of the noble gas structure, and the chemistry of the group is dominated by the tendency
to complete octet arrangement or structure either by;
- Gaining an electron, usually from the metals of group 1 and group 11 to form a
univalent negative ion, e.g F-, Cl-,Br-
or
- Sharing a pair of electrons in a single covalent bond with another atom having a fairly
similar electronegative value as in gaseous chlorine, Cl – Cl, and hydrogen chloride.
H – Cl.

ELECTRONIC CONFIGURATIONS OF SOME HALOGENS

Flourine 2, 7
Chlorine 2, 8, 7
Bromine 2, 8, 18, 7
Iodine 2, 8, 18, 18, 7

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GENERAL PROPERTIES OF THE HALOGENS
The general properties of the halogens are as follows:
1. They are all composed of covalent molecules containing two atoms, X2, (i.e diatomic
molecules) where X is a halogen. This accounts for their low melting and boiling
points and their solubility in covalent non – polar liquids.
2. At room temperature, fluorine and chlorine are gases, bromine is a liquid and iodine
is a solid. The boiling points increases with increase in atomic mass.
3. Halogens are coloured with typical penetrating odours. The colours deepen down the
group. Fluorine is pale yellow, chlorine is yellow, bromine is red and iodine is violet.
4. All halogens dissolve to some extent in water, fluorine reacts vigorously and
completely with water to give oxygen and hydrogen fluoride.
5. Halogens are very reactive elements. The reactivity decreases down the group.
6. All halogens are strong oxidizing agents. Fluorine oxidizes water to peroxide,
chlorine reacts slowly with water to give oxochlorate (1) acid, HOCl. The oxochlorate
(1) acid decomposes to give hydrochloric acid and oxygen.
2HOCl(aq) → 2HCl(aq) + O2(g)
7. All halogens combine readily with most metals and non – metals to form ionic and
covalent compounds respectively. These compounds contain halide ion, X- in which
they have oxidation state of -1.
2Na(s)+ X2(g) → 2NaX(s)
2P(s)+ 3X2(g) → 2PX3(s)
8. Halogens combine with hydrogen to form gaseous covalent compounds of formula
HX, where X is a halogen. The halide ion has an oxidation state of -1.
9. Halogens react with silver to form AgX. The silver halides [AgCl, AgBr, AgI] with
the exception of the fluoride [AgF] are insoluble in water. This can be used as a test
for halides.
Ag++ Cl- → AgCl [White precipitate]
Ag+ + Br- → AgBr [Pale yellow precipitate]
Ag++ I-→ AgI [Bright yellow precipitate]
The reactivity series of the halogens such as volatility, solubility, electronegativity, oxidizing
ability and tendency to enter into chemical combination decreases down the group. This
makes fluorine the most powerful electronegative and oxidizing agent among the halogens,

17
and iodine the least. This is because of the increased complexity of the atoms from fluorine
to iodine.

FLUORINE
Fluorine is the first member and the most reactive of the halogen family. It does not occur
free in nature because of its reactivity. It is found mainly in minerals like cryolite [NaF. AlF 3]
and Fluospar [CaF2]

PREPARATION OF FLUORINE
Fluorine is prepared by the electrolysis of potassium fluoride solution in anhydrous hydrogen
fluoride. Carbon is used as an anode in order to resist attack by the fluorine produced and
steel vessel is used as the cathode. Water MUSTnot be present because it reacts with the
fluorine produced.

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INDUSTRIAL PREPARATION OF CHLORINE.

PROPERTIES OF FLUORINE
1. Fluorine is a poisonous yellow gas with an irritating smell.
2. It has a boiling point of -188oC
3. It is the most reactive element found on earth. Most metals catch fire in fluorine.
Even inactive metals like gold and platinum are attacked when heated in a stream of
fluorine gas.
4. It combines directly with all other non – metals except nitrogen, helium, neon,
oxygen and argon to form fluorides like PF5 and SF6.
5. Fluorine has a great affinity for hydrogen. It reacts explosively with hhydrogen or
hydrogen containing compound to form hydrogen fluoride.
H2(g) + F2(g) → 2HF(l)
2NH3(g) + 3F2(g) → 6HF(l) + N2(g)
CH4(g) + 4F2(g) → 4HF(l) + CF4(g)
The hydrogen fluoride produced is a fuming colourless liquid, with a very low boiling
point of [19.5oC] which is higher than the boiling point of hydrogen chloride [-84oC]
because the hydrogen fluoride molecules are linked together by hydrogen bonding.

19
 6. Water is vigorously oxidised by fluorine in a complex reaction which gives mainly
hydrogen fluoride and oxygen, together with traces of hydrogen peroxide and oxygen
difluoride, F2O.
2F(g) + 2H2O(l) → 4HF(l) + O2(g)
7. It can displace all other halogens from aqueous solutions of their compound.
8. It can also react with the most reducing agents and the noble gases like krypton and
xenon.
Xe(g) + 2F2(g) → XeF4(s)
9. Fluorine is the most electronegative element as a result of its small size and electronic
structure. On combination with other elements, it causes them to exhibit their possible
maximum covalency. E.g PF5, SF6, IF7etc

USES OF FLUORINE
1. Sodium fluoride is used for the fluoridation of drinking water while tin (II) fluoride is
used in toothpaste to prevent tooth decay.
2. Hydrogen fluoride and fluorine are used to make uranium hexafluoride, used in
separating the isotopes of chlorine.
3. Fluorine compounds are used as refrigerants, anaesthetic, aerosol – propellant and
insulator.
4. Hydrofluoric acid is used in etching glass and in cleaning steel.
5. Fused cryolite is used asa solvent for bauxite.

CHLORINE
Chlorine is the most important element of all the halogens. It was first discovered by schleele
in 1774, when he heated he heated some concentrated hydrochloric acid with manganese (IV)
oxide. Chlorine does not occur freely in nature, because it is very reactive and is found in the
combined state as chlorides. The most abundant of the chlorides is sodium chloride or
common salt, which is found both in the sea and as salt deposit.

20
LABORATORY PREPARATION OF CHLORINE
Chlorine is prepared in the laboratory by the oxidation of concentrated hydrochloric acid
with a strong oxidizing agent such as manganese (IV) oxide, potassium tetraoxomanganate
(VII) or lead (IV) oxide.

(a)Using manganese (IV) oxide: Heat a mixture of manganese (IV) oxide and
concentrated hydrochloric acid. The acid is oxidised to liberate chlorine.
Heat
MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) + Cl2(g)
The gas is passed through a washed bottle containing water to dissolve any unoxidized
hydrogen chloride gas. Chlorine is dried by passing it through concentrated tetraoxosulphate
(VI) acid, and is collected by upward displacement of air or downward delivery in a fume
cupboard.
Alternatively, adding a solution of concentrated tetraoxosulphate (VI) acid to a mixture of
sodium chloride and manganese (IV) oxide, on heating, the acid reacts with the sodium
chloride to produce hydrogen chloride, which is oxidized by the manganese (IV) oxide to
produce chlorine.
2NaCl(s) + MnO2(s) + 2H2SO4(aq) → Na2SO4(aq) + MnSO4(aq) + 2H2O(l) + Cl2(g)

(b) Using tetraoxomangnate (VII):Potassiumtetraoxomanganate (VII) oxidizes

concentrated hydrochloric acid without heating to liberate chlorine.
2KMnO4(aq) + 16HCl(aq) → 2MnCl2(aq) + KCl(aq) + 8H2O(l) + 5Cl(g)

21
The same apparatus is used as in the first method, but if dry chlorine is not required, the gas
is collected over brine.

INDUSTRIAL PREPRATION OF CHLORINE

Chlorine is manufactured industrially by the electrolysis of:
(i) brine
(ii) the chlorides of molten sodium, magnesium or calcium.
A special designed cell, developed by castner, kellener and solvay is used in the process. The
chlorine gas is then liquefied and stored under pressure I steel cylinders.

22
PHYSICAL PROPERTIES OF CHLORINE
i. Chlorine is a greenish – yellow gas with choking, unpleasant and irritating gas.
ii. It is denser than air.
iii. It is moderately soluble in water.
iv. It can easily be liquefied under pressure.
v. It is a poisonous gas. If inhaled to a small extent, it can damage the mucous lining
of our lung.

BONDING CAPACITY OF CHLORINE

A chlorine atom has seven valence electrons. It is very reactive as it tries to achieve a stable
octet electronic configuration either
i. By gaining an electron, usually from metals of group 1 & 2, to form negative ion,
Cl- as in electrovalent compounds like sodium chloride, NaCl and Calcium
chloride, CaCl2
Or

23
 ii. By sharing a pair of electrons in a single covalent bond with another atom, having
a fairly similar electronegative value, as in gaseous chlorine Cl – Cl and hydrogen
chloride, H – Cl.

CHEMICAL PROPERTIES OF CHLORINE

1. Displacement of other halogens:With the exception of fluorine, chlorine
displaces other halogens from solutions of their acids and salts.
Cl2(g)+ 2NaBr(aq)→ 2NaCl(aq) + Br2(g)
Cl2(g) + 2HI(aq) → 2HCl(aq) + I2(g)
Cl2(g) + 2NaI(aq) → 2NaCl(aq) + I2(g)
Cl2(g) + 2KI(aq) → 2kCl(aq) + I2(g)

2. Combination with other elements:Chlorine combines directly with

most other elements to form chlorides. E.g

a. With metals:Metals react readily with chlorine, especially when heated, to

form their chlorides.
2Na(s) + Cl2(g) → 2NaCl(s)
Zn(s) + Cl2(g) → 2ZnCl2(s)
Where a metal forms more than one chloride, the higher chloride is usually
formed. E.g in the case of Iron. Iron (III) chloride is formed. This is due to the
oxidizing nature of chlorine.
2Fe(s) + 3Cl2(g) → 2FeCl3(s)

b. With non – metals:With the exception of oxygen, nitrogen, carbon and

noble gases, all other non – metals burn in chlorine to produce the corresponding
chlorides. E.g phosphorus burns in chlorine to produce a mixture of phosphorus
(V) chloride and phosphorus (III) chloride.
P4(s) + 8Cl2(g) → 2PCl3(s) + 2PCl5(g)
Chlorine has strong affinity for hydrogen. So, it combines explosively with
hydrogen in bright sunlight, although the reaction is slower in diffused light.
H2(g) + Cl2(g) → 2HCl(g)

3. As an oxidizing agent:Chlorine is a powerful oxidizing agent because of its

ability to remove hydrogen and readiness to accept electrons from reducing agents to
form chlorides.

24
 a. With Iron (II) salts:Chlorine oxidises green solution of iron (II) chloride
to yellow iron (III) chloride.
2FeCl2(aq)+ Cl2(g) → 2FeCl3(aq)

b. With trioxosulphate (IV) ion:When chlorine is bubbled through a

freshly prepared solution of trioxosulphate (IV) acid, it oxidizes the solution the
trioxosulphate (IV) ion to tetraoxosulphate (VI) acid.
H2SO3(aq) + H2O(l)+ Cl2(g) → H2SO4(aq) + 2HCl(aq)

4. Reaction with hydrogen:Chlorine has a very strong affinity for hydrogen. It

readily removes hydrogen from its compounds to form hydrogen chloride.

a. With Hydrocarbons:A piece of filter paper saturated with warm

turpentine [C10H16] will rapidly catch fire in a jar of chlorine, forming soot and
misty fumes of hydrogen chloride
C10H16(l) + 8Cl(g) → 10C(s) + HCl(g)
Under controlled conditions, substitution reaction occurs where chlorine reacts
with saturated hydrocarbons to produce chlorinated hydrocarbons and hydrogen
chloride.
CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g)

b. With ammonia:Chlorine removes hydrogen from ammonia to form a

nitrogen and hydrogen chloride.
2NH3(g) + 3Cl2(g) → N2(g) + 6HCl(g)
The hydrogen chloride produced then combines with excess ammonia to form
ammonium chloride
6HCl(g)+ 6NH3(g)→ 6NH4Cl(g)

c. With hydrogen sulphide:When hydrogen sulphide is mixed with

chlorine, a yellow deposit of sulphur is formed as a result of oxidation of the
sulphide by chlorine.
H2S(s) + Cl2(g) → 2HCl(g) + S(s)

d. With water:Chlorine dissolves in water to form chlorine water. The chlorine

water gives off oxygen, when exposed to sunlight. This is due to the formation of
oxochlorate (I) acid which decomposes slowly to hydrogen chloride and oxygen.
Cl2(g) + H2O(l) → HCl(aq) + HOCl(aq)

25
Oxochlorate (I) acid
Sunlight
2HOCl(aq)→ 2HCl(aq) + O2(g)

e. With iron (II) salt:Chlorine oxidizes a solution of green iron (II) chloride
to yellowish – brown iron (III) chloride.
2FeCl2+ Cl2(g)→ 2FeCl3(aq)

f. With trioxosulphate (IV) ion:Chlorine oxidizes freshly prepared

solution of trioxosulphate (IV) acid to tetraoxosulphate (VI) acid.
H2SO3(aq) + H2O(l) + Cl2(g) → H2SO4(aq) + 2HCl(aq)

5. As a bleaching agent:Chlorine is a common bleaching agent. It bleaches

most dyes and inks in the presence of water, except those containing carbon.
The bleaching action of chlorine is due to its ability to react with water to form
oxochlorate (I) acid, which is unstable and decomposes to release oxygen which
oxidises the dye to form a colourless compound.
HOCl(aq) → HCl(aq) + [O]
Dye + [O] → [Dye + O]
Coloured Colourless

6. Reaction with alkalis:

a. With dilute alkalis solutions:Chlorine forms pale – yellowish mixture
of the oxochlorate (I) and chloride of the metal, when bubbled into a cold solution
of sodium hydroxide.
Cl2(g) + 2NaOH(aq) → NaClO(aq)+ NaCl(aq) + H2O(l)
Sodium oxochlorate (I)

b. With hot concentrated alkali solution:When chlorine is bubbled

through a hot concentrated solution of sodium hydroxide, a mixture of the
trioxochlorate (V) and chloride of the metal is formed.
3Cl2(g) + 2NaOH(aq) → NaClO3(aq) + NaCl(aq) + H2O(l)
Sodium trioxochlorate (V)

c. With slaked lime:Bleaching powder is produced by bubbling chlorine

through a freshly prepared solution of calcium hydroxide.
Cl2(g) + Ca(OH)2(aq) → CaOCl2.H2O(g)

26
Bleaching powder

TEST OF CHLORINE
1. Moist litmus paper test:Chlorine readily bleaches moist litmus paper by
turning moist blue litmus paper to red before it is finally bleached. This is because
chlorine gas is acidic. If a moist red litmus paper is used, chlorine bleaches it directly.

2. Starch – iodide paper test:Chlorine turns moist starch iodide paper blue
because it displaces iodine from iodide. This iodine liberated, then turns the starch
blue.
2KI(aq)+ Cl2(g) → 2KCl(aq) + I(g)

USES OF CHLORINE
1. Chlorine is used as a bleaching agent for cotton, linen and wood – pulp.

2. It is a powerful germicide because of its oxidizing nature. It is also used in the

sterilization of water for domestic and industrial use.

3. Chlorine is used in the manufacture of important organic solvents such as

trichloromethane, CHCl3, tetracloromethane, CCl4, trichloroethene, C2HCl3 and
trichloroethanal, CCl3.CHO.

4. It is used in aerosol propellants

5. It is used in the manufacture of potassium trioxochlorate (V) which is used in making

matches and fire – work and sodium trioxochlorate (V), a weed – killer.

6. It is used in the manufacture of hydrochloric acid and domestic – antiseptic such as

acidified sodium oxochlorate (I) solution.

7. It is used in the manufacture of plastics such as poly (chloroethene), known as

polyvinyl chloride or P.V.C and synthetic rubber.

HYDROGEN CHLORIDE
Hydrogen chloride is an anhydride of chlorine which exist as a gas at s.t.p. It dissolves in
water to form hydrochloric acid. Hydrogen gas was first prepared by priestley in 1772.

27
LABORATORY PREPARATION OF HYDROGEN
CHLORIDE GAS.
Hydrogen chloride is prepared in the laboratory by the action of concentrated
tetraoxosulphate (VI) acid on sodium chloride.

Put some sodium chloride in a round bottom flask. Add concentrated tetraoxosulphate (VI)
acid through a thistle funnel and heat the mixture gently. The gas is dried by passing it
through concentrated tetraoxosulphate (VI) acid and is collected by downward delivery.
2NaCl(s)+ H2SO4(aq) → Na2SO4(aq) + 2HCl(g)

28
INDUSTRIAL PREPARATION OF HYDROGEN CHLORIDE
Hydrogen chloride is prepared in large amount by the direct combination of hydrogen and
chlorine gases obtained from the electrolysis of brine.
H2(g) + Cl2(g) →2HCl(g)

PHYSICAL PROPERTIES OF HYDROGEN CHLORIDE.

1. Pure hydrogen chloride gas is a colourless gas with an irritating smell.
2. It is slightly denser than air.
3. It turns moist blue litmus paper red, showing that it is an acidic gas.
4. It is very soluble in water, forming an aqueous solution of hydrochloric acid.
5. It fumes strongly in moist air, forming droplets of hydrochloric acid.
6. Hydrogen chloride does not burn or support combustion.
7. Dry hydrogen chloride dissolves readily in non – polar solvents like chloroform and
toluene, but does not ionize as it does in polar solvents.

CHEMICAL PROPERTIES OF HYDROGEN CHLORIDE

GAS.
1. Reaction with ammonia:
Hydrogen chloride gas reacts with ammonia gas to form dense white fumes of solid
ammonium chloride.
HCl(g)+ NH3(g) → NH4Cl(s)

2. Reaction with metals:

Hydrogen chloride gas on heating reacts with many metals, forming the
corresponding chlorides and hydrogen.
Zn(s) + 2HCl(g)→ ZnCl2(s) + H2(g)
If the metal can form two chlorides, the lower chloride is formed.
Fe(s) + 2HCl(g)→ FeCl2(s) + H2(g)

29
HYDROCHLORIC ACID
Hydrochloric acid is a solution of hydrogen chloride gas in water.

LABORATORY PREPARATION OF HYDROCHLORIC ACID

Hydrochloric acid is prepared in the laboratory by dissolving hydrogen chloride gas in water.
The gas is passed through an inverted funnel. Hydrochloric acid ionizes in aqueous solution
to give hydroxonium ion and chloride ion.

30
HCl(g) + H2O → H3O+ + Cl-

PROPERTIES OF HYDROCHLORIC ACID

1. As an acid:
Hydrogen chloride gas dissolves in water to form water to form hydrochloric acid
which exhibits all the usual properties of acids.

a. With metals:

31
 Metals which are more electropositive than hydrogen will liberate hydrogen gas
from the acid.
Mg + 2HCl → MgCl2 + H2
Zn + 2HCl → ZnCl2 + H2
A mixture of zinc and copper dust can be separated by adding dilute hydrochloric
acid to the mixture. Zinc which is more electropositive than hydrogen reacts with the
acid, leaving the copper dust.
Zn/Cu + HCl(aq)→ ZnCl2(aq) + H2(g) + Cu(s)

b. With bases:
Hydrochloric acid reacts with a base or an alkali to produce salt and water only.
ZnO(s) + 2HCl(aq)→ ZnCl2(aq) + H2O(l)
NaOH(aq) + HCl(aq)→NaCl(aq) + H2O(l)

c. With trioxocarbonate (IV):

Hydrochloric acid reacts with troxocarbonate (IV) and hydrogen trioxocarbonate
(IV) to liberate carbon (IV) oxide.
2HCl(aq)+ Na2CO3(s) → 2NaCl(aq) + H2O(l) + CO2(g)
HCl(aq) + NaHCO3(s)→NaCl(aq) + H2O(l) + CO2(g)

d. With trioxosulphate(IV):
Dilute hydrochloric acid reacts with potassium trioxosulphate (IV) and liberate
sulphur(IV) oxide.
K2SO3(s) +2HCl(aq)→ 2KCl(aq) + SO2(g) + H2O(l)

e. With iron (II) Sulphide:

Dilute hydrochloric acid reacts with iron (II) sulphide to liberate hydrogen
sulphide gas
FeS(s) + 2HCl(aq)→ FeCl2(aq) + H2S(g)

2. As a precipitating agent:
When hydrochloric acid is added to silver trioxonitrate (V) or lead (II) trioxonitrate
(V) solution, a white precipitate of silver chloride or lead (II) chloride is formed.
AgNO3(aq) + HCl(aq)→AgCl(s) + HNO3(aq)
Pb(NO3)2(aq) + 2HCl(aq)→ PbCl2(s) + 2HNO3(aq)

3. Reaction with strong oxidizing agent.

32
 Concentrated hydrochloric acid is easily oxidized by strong oxidizing agents, to
liberate chlorine. Hence, hydrochloric acid is never used for acidifying solutions of
oxidizing agent. Instead, tetraoxosulphate (VI) is used.

4. Action of heat:
Concentrated hydrochloric acid boils when heated to liberate hydrogen chloride
fumes, making the solution more dilute. Water is lost when hydrochloric acid is
heated, making the residual solution more concentrated.

TEST FOR HYDROGEN CHLORIDE.

1. With ammonia:
Hydrogen chloride produces dense white fumes in the presence of ammonia
and this consists of suspended particles of ammonium chloride.
NH3(g) + HCl(g)→ NH4Cl(s)

2. With silver trioxonitrate (V):

Hydrogen chloride forms a white precipitate of silver chloride. This precipitate is
insoluble in water but soluble in excess ammonia solution.
AgNO3(aq) + HCl(aq)→AgCl(s) + HNO3(aq)
Lead (II) trioxonitrate (V) can be used in place of silver trioxonitrate (V).

USES OF HYDROGEN CHLORIDE

1. Hydrogen chloride gas is used in the manufacture of chloroethene.
2. Hydrochloric acid is used in the manufacture of textiles and dyes.
3. Hydrochloric acid is used in the manufacture of gelatin and glue from tendous
of animals and in the hydrolysis of starch.
4. Hydrochloric acid is used in pickling. i.e removal of oxides from metals before
electroplating
5. Hydrochloric acid is used in the laboratory for the testing, analysis and
preparation of other compounds.

CHLORIDES
Chlorides are normal salts formed when the hydrogen ions in hydrochloric acid
are replaced by metallic ions. All chlorides except copper (I) chloride, CuCl,
mercury (I) chloride, Hg2Cl2 and silver chloride, AgCl are soluble in water.

33
 Lead (II) chloride, PbCl2, is insoluble in cold water, but dissolves gradually when
warmed.

LABORATORY PREPARATION OF CHLORIDES

Chlorides can be prepared in the laboratory using various methods. The method
used for the preparation depends on the position of the metal in the activity series
and the nature of the chloride.

(i) Action of hydrochloric acid or hydrogen chloride on

metals:
The chlorides of magnesium and zinc are prepared by the action of dilute
hydrochloric acid on the corresponding metals.
Mg(s) + 2HCl(aq)→ MgCl2(aq) + H2(g)
Zn(s) + 2HCl(aq)→ZnCl2(aq) + H2(g)
Anhydrous aluminium chloride, and iron (II) chloride are prepared by passing dry
hydrogen gas over the heated metals.
2Al(s) + 6HCl(aq)→ 2AlCl3(s) + 3H2(g)
Fe(s) + 2HCl(g)→FeCl(s) + H2(g)

(ii) Action of the acid on the oxides, hydroxides or

trioxocarbonate (IV) of metals:
The chlorides of potassium, sodium and calcium are prepared by neutralizing their
hydroxides with dilute hydrochloric acid or by adding the acid to their oxides or
trioxocarbonates (IV).
HCl(aq) + NaOH(aq)→ NaCl(aq) + H2O(l)
2HCl(aq) + K2CO3(aq) → 2KCl(aq) + H2O(l) + CO2(g)
2HCl(aq) + CaO(s) → CaCl2(aq) + H2O(l)
Copper does not react with dilute hydrochloric acid, because it is too reactive. Its
chloride, copper (II) chloride is prepared by the action of the acid on copper (II)
oxide trioxocarbonate (IV).
2HCl(aq) + CuO(s) → CuCl2(aq) + H2O(l)
2HCl(aq) + CuCO3(s) → CuCl2(aq)+ H2O(l) + CO2(g)

(iii) Double decomposition:

34
 Chlorides of metallic lead and silver are prepared by double decomposition.
Pb(NO3)2(aq) + 2KCl(aq)→ PbCl2(s) + 2KNO3(aq)
AgNO3(aq) + NaCl(aq)→ AgCl(s) + NaNO3(aq)
In double decomposition, the reactants decompose to form new substances by an
exchange of radicals. The two reactants are soluble, but one of the products is
soluble while the other is insoluble, volatile or gaseous.

(iv) Direct combination of the metal with chlorine:

Chlorine can react with any metal to produce the corresponding chlorides. E.g,
iron (III) chloride and mercury (II) chloride can be prepared by passing a stream
of dry chlorine gas over a heated iron and mercury respectively.
2Fe(s) + 3Cl2(g)→ 2FeCl3(s)
Hg(l) + Cl2(g) → HgCl2(l)

PROPERTIES OF CHLORIDES.
1. Action on heat:
Chlorides are not decomposed by the action of heat.

2. With tetraoxosulphate (VI) acid:

All chlorides react with hot concentrated tetraoxosulphate (VI) acid to produce
hydrogen chloride.
If a strong oxidizing agent is present, chlorine is produced.

TEST FOR CHLORIDES

Acidify the test solution with dilute trioxonitrate (V) acid. Then add a few drops of
silver trioxonitrate (V). A white precipitate of silver chloride, which dissolves readily
in aqueous ammonia indicates the presence of a chloride.
Lead (II) trioxonitrate (V) can also be used. A white precipitate of lead (II) chlorine
which dissolves when heated but reappears when cooled indicates the presence of a
chloride.

COMPARING THE PROPERTIES OF CHLORINE, BROMINE

AND IODINE.
CHLORINE [Cl2] BROMINE [Br2] IODINE [I2]

35
Physical state, Greenish – yellow, Dark – red Black crystalline
colour, smell and poisonous gas, poisonous liquid, solid; on heating,
nature. irritating smell volatile with sublimes to form
irritating smell. purple fumes;
poisonous.
Relative density 1.9 3.2 4.9
(of solid) gcm-3
Melting point. oC -102 -7 114
Boiling point oC -34 59 184
Solubility Moderately soluble Slightly soluble in Sparingly soluble
in water to yield water to yield in water but
acidic solution of acidic solution of soluble in ether,
HCl and HOCl HBr and HOBr ethanol and
potassium iodide.
Electronegativity Decreasing
and reactivity electronegativity
and decreasing
reactivity.
Affinity for Combines Combines on Combines
hydrogen explosively in heating or in the reversibly at
sunlight presence of a 400Oc in the
platinum catalyst. presence of a
platinum catalyst
Reaction with Vigorous Moderately Least vigorous
metals and non - vigorous
metals.
Reaction with Yields chlorides Yields bromides Yields iodides and
dilute dilute acids. and oxochlorates (I) and oxobromate (I) oxoiodates (I)
Reaction with Yields chlorides Yields bromides Yields iodides and
concentrated and trioxochlorates and trioxobromate trioxoiodides (V)
alkalis (V) (V)
Bleaching action Strong Weak -
Oxidizing action Strong Moderate Weak

36
 Displacement Displace bromine Displaces iodine -
reaction and iodine from from iodides
bromides and
iodides respectively
Hydrogen halide Colourless gas, Colourless gas, Colourless gas,
denser than air, denser than air, denser than air,
dissolves to give an dissolves to give dissolves to give
acidic constant an acidic constant an acidic constant
boiling mixture. boiling mixture. boiling mixture.
Thermal stability Decreasing thermal
and reducing stability and
power increasing reducing
power
Silver halide White solid, soluble Pale yellow solid, Yellow solid,
in aqueous sparingly soluble insoluble in
ammonia, reduced in aqueous aqueous ammonia,
to silver by light. ammonia, reduced reduced to silver
to silver by light. by light.

NITROGEN AND ITS COMPOUNDS

NITROGEN AS AN ELEMENT
Nitrogen is the most abundant element in the atmosphere as it constitutes about 78% by
volume of the atmosphere. Free nitrogen in the atmosphere is important because it dilutes the
oxygen to the point where combustion and oxidation of metals are reasonably slow. In the
combined form, nitrogen occurs abundantly in the soil as trioxonitrates (V) of sodium,
potassium and calcium, as well as ammonium salts. Combined nitrogen is also found in
organic matter such s proteins, urea and the vitamin B compounds.

BONDING CAPACITY OF NITROGEN

Free nitrogen exists in air as a diatomic molecules with triple covalent bonds between its
atoms (N ≡ N). The high bond energy of the triple bond accounts for the unreactive nature of

37
nitrogen under ordinary conditions. However, at very high temperature and pressure, nitrogen
combines directly with certain metals and non – metals.

PREPRATION OF NITROGEN

LABORATORY PREPARATION OF NITROGEN

Nitrogen is prepared in the laboratory by the following methods.

(i) From the atmosphere:

Since nitrogen makes up a large percentage of air, it can be obtained from air by removing
the other constituent. Carbon (IV) oxide is removed by passing the air through caustic soda.
2NaOH(aq) + CO2(g) → Na2CO3(aq) + H2O(l)
Oxygen can also be removed using heated copper turning.
2Cu(s) + O2(g) → 2CuO(s)
The nitrogen produced or obtained through this method contains about 1% by volume of rare
gases as impurities and is denser than pure nitrogen.

38
 (ii) Thermal decomposition of ammonium dioxonitrate (III)
NH4NO2
Pure nitrogen is obtained by thermal decomposition of ammonium dioxonitrate (III)
NH4NO2. The ammonium dioxonitrate (III) is unstable and decomposes exothermically.
However it is not heated directly as the reaction may get out of control and an explosion may
occur. A mixture of sodium dioxonitrate (III) and ammonium chloride solutions in a ratio of
7:5 is heated to produce ammonium dioxonitrate (III), which in turn decomposes to yield
nitrogen and steam.
NaNO2(aq) + NH4Cl(aq) → NH4NO2(aq) + NaCl(aq)
NH4NO2(aq) → N2(g)+ 2H2O(l)

(iii) From ammonium heptaoxodichromate (VI):

Ammonium heptaoxodichromate (VI) decomposes on heating to yield nitrogen.
(HH4)2Cr2O7(s)→ N2(g) + Cr2O3(s) + 4H2O(l)

(iv) Oxidation of ammonia gas by copper (II) oxide:

Nitrogen is liberated when ammonia is passed over hot copper (II) oxide.
2NH3(g) + 3CuO(s)→ 3Cu(s) + 3H2O(g) + N2(g)

(v) Reduction of oxides of nitrogen by heated copper:

When dinitrogen (I) oxide is passed over red – hot copper, the gas is reduced to nitrogen.

39
N2O(g) + Cu(s)→ CuO(s) + N2(g)

INDUSTRIAL PREPARATION OF NITROGEN

Nitrogen is prepared industrially by the fractional distillation of liquid air. After removal of
carbon (IV) oxide, the air is subjected to successive compression and cooling processes.
Upon distillation, nitrogen gas is evolved first at -196oC at standard pressure and is separated
from oxygen which boils at -183oC at standard pressure. The separated nitrogen is liquefied
and stored in steel cylinders and sold as liquid nitrogen.

PHYSICAL PROPERTIES OF NITROGEN

1. Nitrogen is a colourless, odourless and tasteless gas.
2. Pure nitrogen is less dense than air.
3. It is only slightly soluble in water.
4. Nitrogen has a melting point of -210oC and a boiling point of -196oC.
5. It exhibits oxidation states varying from -3 to +5 in its various compound.
6. Lighted splint is extinguished when plunged into nitrogen gas.
7. Nitrogen has no effect on lime water.

OXIDATION STATES OF NITROGEN IN ITS COMPOUNDS

NAME OF COMPOUND FORMULA OXIDATION STATE
Ammonia NH3 -3
Hydrazine N2H4 -2
Hydroxylamine NH2OH -1
Nitrogen (IV) Oxide NO2 +4
Dinitrogen (I) Oxide N2O +1
Nitrogen (II) Oxide NO +2
Trioxonitrate (V) ion NO3- +5
Dioxonitrate (III) ion NO2- +3
Dinitrogen (III) Oxide N2O3 +3

CHEMICAL PROPERTIES OF NTROGEN

(i) With metals:

40
Nitrogen combines directly with highly electrippositive metals at high temperature to form
nitrides. E.g. red hot magnesium combines directly with nitrogen to produce magnesium
nitrides.
3Mg(s) + N2(g)→ Mg3N2(s)
The nitride is hydrolysed readily when warmed with water to produce ammonia gas.
Mg3N2(s) +6H2O(l) → 3Mg(OH)2(s) + 2NH3(g)

(ii) With non - metals:

Nitrogen combines reversibly with hydrogen to produce ammonia.
N2(g) + 3H2(g) ↔ 2NH3(g)
It also combines directly with oxygen at very high temperature to form nitrogen (II) Oxide.
This reaction occurs in nature in the atmosphere when lightning flashes.
N2(g) + O2(g) → 2NO(g)

USES OF NITROGEN
1. Nitrogen is used in the manufacture of ammonia, trioxonitrate (V) acid, cyanide and
fertilizer.
2. Liquid nitrogen is used as a cooling agent.
3. Due to its inert nature, nitrogen is used:
(i) as a carrier gas in gas chromatography
(ii) in providing an inert atmosphere for certain industrial processes involving
easily oxidizable chemicals e.g in making electronic components such as
transistors and in annealing of metals.
(iii) as a preservative to prevent rancidity (due to the oxidation of fats) in packaged
foods.

COMPOUNDS OF NITROGEN.
Some compounds of nitrogen include the following:
1. Ammonia
2. Oxides of nitrogen
3. Trioxonitrate (V) acid
4. Trioxonitrate (V) salts.

AMMONIA

41
Ammonia is a hydride of nitrogen formed when an ammonium salt is heated with a non –
volatile base. Naturally, ammonia is produced when nitrogenous matter decays in the absence
of air by the action of heat or putrifying bacteria.

LABORATORY PREPARATION OF AMMONIA

Ammonia is prepared in the laboratory by heating a mixture of powdered ammonium salt and
a strong alkali.

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

42
(NH4)2SO4(s) + Ca(OH)2(s) → CaSO4(s) + 2NH3(g) + 2H2O(g)
Calcium hydroxide is preferred because it is cheap and not deliquescent. The ammonia gas
evolved on heating is dried by passing it through calcium oxide and the collected by upward
delivery.
Considering the alkalinity of the gas, the usual drying agent like concentrated
tetraoxosulphate (VI) acid and calcium chloride are not used for drying ammonia, because
they react with the gas as shown below:
2NH3(g) + H2SO4(aq) → (NH4)2SO4(s)
4NH3(g) + CaCl2(s) → CaCl2.4NH3(s)
Ammonia is also prepared conveniently in the laboratory by the hydrolysis of nitrides.
LiN(s) + 3H2O(l)→ 3LiOH(aq)+ NH3(g)
Ca3N2(s) +6H2O(l)→ 3Ca(OH)2(aq) + 3NH3(g)

INDUSTRIAL PREPARATION OF AMMONIA

Ammonia is prepared industrially by the Haber process, which is based on direct
combination of nitrogen and hydrogen.
N2(g) + 3H2(g)↔ 2NH3(g)
Since the reaction is reversible, special conditions of reaction are required for the optimum
yield of ammonia. The process involves mixing nitrogen and hydrogen in the volume ratio
of 1:3 at a relatively high pressure of about 200 atmosphere and passed over a finely
dividediron mixed with alumina as catalyst at a temperature of 450oC.
The ammonia produced is liquefied by cooling and stored for further use.

PHYSICAL PROPERTIES OF AMMONIA

1. Ammonia is a colourless gas with a characteristic pungent smell.
2. It is less dense than air.
3. It is an alkaline gas, therefore it turns moist litmus paper blue.
4. Ammonia is very soluble in water. The solubility is due to the readiness with which it
forms hydrogen bond with water to give aqueous ammonia. NH3.H2O. Aqueous
ammonia ionizes slightly to produce ammonium ion, NH4+ and hydroxide ion: OH-.
NH3(g)+ H2O(l)↔ NH3.H2O(aq)
On warming, aqueous ammonia decomposes readily to liberate ammonia gas.
5. Ammonia is a poisonous gas when in large quantity.

43
 6. It is easily liquefied into a colourless liquid at ordinary temperature.
7. Ammonia has a boiling point of -77.8oC and melting point of -34.4oC.

CHEMICAL PROPERTIES OF AMMONIA

1. Reaction with oxygen:
Ammonia burns readily in oxygen to form water vapour and nitrogen.
4NH3(g) + 3O2(g) → 6H2O(g) + 2N2(g)
In the presence of heated platinum catalyst, ammonia reacts with excess oxygen to produce
nitrogen (II) oxide and water.
Pt
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l)

2. Ammonia as a reducing agent:

(i) With copper (II) Oxide:
Ammonia is not a strong reducing agent. It reduces heated copper (II) Oxide to copper while
itself is oxidized to water and nitrogen.
3CuO(s)+ 2NH3(g) → 3Cu(s) + 3H2O(l) + N2(g)

(ii) With chlorine:

In the presence of excess ammonia, chlorine is first reduced to hydrogen chloride and
nitrogen.
2NH3(g) + 3Cl2(g)→ 6HCl(g) + N2(g)
The hydrogen chloride then reacts with the excess ammonia to produce dense white fumes of
ammonium chloride.
6NH3(g) + 6HCl(g)→ 6NH4Cl(s)
The overall reaction is as follows:
3Cl2(g) + 8NH3(g) → 6NH4Cl(s) + N2(g).
If chlorine is in excess, nitrogen trichloride, an explosive and oily liquid is formed.
NH3(g) + 3Cl2(g) → NCl3(l) + 3HCl(g)

3. Reaction with carbon (IV) Oxide:

Ammonia reacts with carbon (iv) oxide at 150oc and a high pressure of 150 atmosphere to
produce urea, an important organic compound.
2NH3(g) + CO2(g) → (NH2)2CO(s) + H2O(l)

44
 4. As a base:
Ammonia is a weak base. It reacts with acids to form ammonium salts.
2NH3(g) + H2SO4(aq) → (NH4)2SO4(s)
If hydrogen chloride is used, dense white fumes composed of suspended particles of
ammonium chloride are formed.
NH3(g) + HCl(g) → NH4Cl(s)

5. As a precipitating agent:
Aqueous ammonia precipitates the insoluble hydroxide of metals from solution of their salts.
Pb(NO3)2(aq) + 2NH3(aq)+ 2H2O(l) → Pb(OH)2(s) + 2NH4NO3(aq)
White

CuSO4(aq) + 2NH3(g)+ 2H2O(l) → (NH4)2SO4(aq) + Cu(OH)2(aq)

Blue

FeCl3(s) + NH3(g) +3H2O(l) → Fe(OH)3(aq) + 3NH4Cl(s)

Reddish brown

ZnSO4(aq) + NH3(g) + H2O(l) → Zn(OH)2(s) + (NH4)2SO4(aq)

White

6. Thermal decomposition:
Ammonia thermally decomposes at temperature above 500oC to yield nitrogen and hydrogen.
500oC
2NH3(g) ↔ N2(g) + 3H2(g)

TEST FOR AMMONIA

(i) Action of litmus paper:
Hold a damp red litmus paper into the jar containing the unknown gas. If the litmus paper
turns blue, then the gas is ammonia.

(ii) Action with hydrochloric acid:

Dip a glass rod in concentrated hydrochloric acid and then insert it in the gas jar containing
the unknown gas. White fumes are formed if the gas is ammonia

45
USES OF AMMONIA
1. Ammonia is used in the manufacture of trioxonitrate (V) acid and sodium
trioxocarbonate (IV) by solvay process
2. It is used in the manufacture of nitrogenous fertilizers.
3. Aqueous ammonia is used in softening temporary hard water.
4. Liquid ammonia is used in refrigerators as a cooling agent
5. Aqueous ammonia is also used in laundries as solvent for removing grease and oil
stains.
6. It is also used in the production of nylon.

AMMONIUM SALTS
Ammonium salts are prepared by dissolving ammonia in the appropriate acid or neutralizing
aqueous ammonia with the appropriate acid. The ammonium salts are then separated out of
solution by crystallization and not by evaporation because they are heat – liable. E.g
NH3(g) + HCl(aq) → NH4Cl(aq)
NH4(aq)+ + OH-(aq) + HCl(aq) → NH4Cl(aq)+ H2O(l)
NH3(g)+ HNO3(aq) → NH4NO3(aq)
NH4(aq)+ + OH-(aq) + HNO3(aq) → NH4NO3(aq) + H2O(l)
NH3(g)+ H2SO4(aq) → (NH4)2SO4(aq)
NH4(aq)+ + OH-(aq) + H2SO4(aq) →(NH4)2SO4(aq) + H2O(l)
Ammoniuntrioxocarbonate (IV) is prepared by heating a mixture of ammonium
tetraoxosulphate (VI) and calcium trioxocarbonate (IV).
(NH4)2SO4(aq) + CaCO3(s) → CaSO4(s) + (NH4)2CO3(aq)
Ammonium salts are electrovalent compounds which contain ammonium ion, NH4+ as the
cation.

PROPERTIES OF AMMONIUM SALTS.

1. Solubility:
All ammonium salts are white crystalline solids which dissolve readily in water. They ionize
completely in solution and are strong electrolytes.

2. Action of heat:
All ammonium salts decomposes when heated. Some however sublimes when heated.

46
 (i) Ammonium tetraoxosulphate (VI) decomposes on heating to liberate ammonia
and tetraoxosulphate (VI) acid.(NH4)2SO4(s) → 2NH3(g) + H2SO4(aq)
(ii) Ammonium dioxonitrate (III) decomposes on heating to produce nitrogen and
water
NH4NO2(s) → N2(g) + 2H2O(l)
(iii) Ammonium trioxonitrate (V) decomposes on heating to produce nitrogen (I)
oxide and water.
NH4NO3(s) → N2O(g) + H2O(g)
(iv) Ammonium chloride sublimes on heating and dissociates to form ammonia and
hydrogen chloride which recombine on cooling.

Heat
NH4Cl(s) ↔ NH3(g) + HCl(g)
Cool
(v) Ammonium trioxocarbonate (IV) is an unstable compound. It decomposes very
readily to yield ammonia, carbon (IV) oxide and water.
(NH4)2CO3(s) → 2NH3(g) + CO2(g) + H2O(l)

3. Reaction with bases:

All ammonium salts liberate ammonia when heated with bases or alkalis.
NH4+ + OH- → NH3(aq) + H2O(l)

TEST FOR AMMONIUM SALTS

Heat some of the unknown substance with sodium hydroxide solution. If the unknown
substance is an ammonium salt, ammonia gas will be evolved. The gas is recognised by its
smell and its action on red litmus paper.
NH4+(aq) + NaOH(aq)→ Na+(aq) + H2O(l) + NH3(g)

OXIDES OF NITROGEN
Oxides of nitrogen includes nitrogen (I) Oxide N2O, nitrogen (II) Oxide NO, nitrogen (III)
Oxide N2O3, Nitrogen (IV) oxide NO2 and Nitrogen (V) Oxide N2O5

DINITROGEN I OXIDE (N2O)

It is prepared by heating a mixture of sodium trioxonitrate v and ammonium chloride

47
NaNO3+ NH4Cl NH4NO3 + NaCl.
The ammonium trioxonitrate v decompose to form dioxonitrate I oxide and water.
NH4NO32H2O + N2O

PHYSICAL PROPERTIES OF N2O

1. It is colourless gas with sweet sickly smell
2. It is neutral to litmus paper
3. It rekindles a strong glowing splint
4. It is fairly soluble in cold water
5. It is insoluble in hot water

CHEMICAL PROPERTIES OF N2O

1. It support combustion, it also burn to release oxygen
N2O2N2+ O2
2. React with sulphur to form sulphur (iv) oxide and Nitrogen.
N2O + S  SO2+ N2
3. Reacts with magnesium to form magnesium oxide and nitrogen.
Mg + N2O MgO + N2
4. Heated copper tunings reduces the oxide to nitrogen
Cu + N2O CuO + N2

TEST FOR N2O

Like oxygen it rekindles a hot glowing splint

USES OF N2O
It is used as mild anaesthetics for minor surgical operations.

NITROGEN (II) OXIDES

It is prepared in the laboratory by the action of dilute trioxonitrate (v) acid on copper turnings
3Cu + 8HNO33Cu(NO3)2+ 4H2O + NO

PHYSICAL PROPERTIES OF NO
1. It is a colourless and poisonous gas
2. It is almost insoluble in water
3. It is slightly denser than air

48
 4. The gas is neutral to litmus

CHEMICAL PROPERTIES OF NO
1. It forms brown fumes of nitrogen (iv) oxide on exposure to the atmosphere
2NO + O22NO2:
This test distinguish oxygen from nitrogen (I) oxide which like oxygen rekindles a
lowing splint.
2. Nitrogen ii oxide reacts with a cold solution of iron ii tetraoxosulphate (vi) in dilute
tetraoxosulphate vi acid to give dark brown solution of FeSO4
3. It reacts with burning magnesium or phosphorus to form nitrogen as oxides of
phosphorus or magnesium
P4+ 10NO P4O10+ 5N2
2Mg + 2NO  2MgO + N2

NITROGEN (IV) OXIDE

Nitrogen (iv) oxide is prepared in the laboratory by the decomposition of lead (ii)
trioxonitrate (v) on heating
2Pb(NO3)22PbO + 4NO2+O2

49
The nitrogen (IV) oxide become liquefied in the u-tube while oxygen will escape through the
u-tube as gas

PHYSICAL PROPERTIES OF NO2

1. It is a reddish brown gas
2. It is poisonous with pungent smell
3. It condenses at 220C to give yellow liquid
4. It is readily soluble in water to give an acidic solution
5. It turns moist blue litmus paper red
6. It is denser than air

CHEMICAL PROPERTIES OF NO2

1. It dissolves in water to form mixture of dioxonitrate (III) and trioxonitrate (V) acids.
It is therefore a mixed anhydride.
2NO2+ H2O HNO2+ HNO3
2. The gas reacts with alkalis to form a mixture of dioxonitrate (iii) and trioxonitrate (v)
salts.
2KOH + 2NO2KNO3+ KNO2+ H20

50
 3. Nitrogen (IV) oxide is reduced to nitrogen by heated copper or iron.
Cu + NO24CuO +N2

TRIOXONITRATE (V) ACID (HNO3)

The acid is prepared in the laboratory by heating a mixture of potassium trioxonitrate (V) and
tetraoxosulphate (VI) acid.
It should be noted that all equipment to be used must be glass wares as HNO3 attacks rubber
or cork.
H2SO4+ KNO3KHSO4+ HNO3

INDUSTRIAL PREPARATION OF HNO3

Industrially the acid is prepared by the catalytic oxidation of ammonia. This can be achieved
through the following steps.
 Ammonia is passed overheated platinum/rhodium catalyst to obtain nitrogen ii
oxide.
4NH3 + 5O2 4NO + 6H2O
 The nitrogen ii oxide combines with excess oxygen to produce nitrogen iv oxide.
2NO + O2 2NO2
 The nitrogen (iv) oxide dissolves in water in the presence of more air to produce
trioxonitrate (v) acid solution.
4NO2 + O2 + H2O  4HNO3

PHYSICAL PROPERTIES OF HNO3

1. It is a fuming colourless liquid with chocking smell
2. It is soluble in water

51
 3. It has specific gravity of 1,5
4. It turns blue litmus paper red
5. It is highly corrosive and readily destroys organic matter.

CHEMICAL PROPERTIES OF HNO3

1. It is a strong acid with usual acidic properties
HNO3 + NaOH  NaNO3 + H20
2. It is a strong oxidixing agents that releases brown fumes of nitrogen iv oxide when
reacts with non - metals.
C + 4HNO3 CO2+ 2H20 + 4NO2
P + 5HNO3H3PO4+ H2O + 5NO2
3. Copper reacts with dilute trioxonitrate (v) acid to form nitrogen ii oxide.
3Cu + 8HNO33Cu(NO3)2+ 4H2O + 2NO
With concentrated HNO3 Nitrogen (iv) oxide is form
Cu + 4HNO3 Cu(NO3)2+ 2H2O + 2NO2
4. As a strong oxidising agent it undergoes redox reactions with common reducing
agents like H2S and Fe2SO4
(i) H2S + 2HNO3 S + 2H2O + 2NO2
(ii) 6FeSO4+ 3H2SO4+ 2HNO33Fe2(SO4)3+4H2O+2NO
Iron (II) tetraoxosulphate (VI) is oxidized to iron (III) tetraoxosulphate (VI) while
nitrogen (II) oxide is liberated. This reacts with oxygen of the atmosphere to form
nitrogen (IV) oxide.
The acid decomposed on heating to form nitrogen (IV) oxide.
4HNO3 2H2O + 4NO2+ O2
5. Reacts with benzene to form nitrobenzene. This takes place in the presence of
Concentrated H2SO4
C6H6 + HNO3 C6H5NO2 + H2O

USES OF HNO3
1. It is a starting material in the production of fertilizers
2. Used in the manufacture of explosives eg dynamic and trinitrotoluene (TNT)
3. Used as nitrating agent
4. Used as rocket fuel

52
 5. It is used in the production of Saqua raqia (mixture of HCl and HNO3)

TRIOXONITRATE (V) SALTS

They are series of normal salts of trioxonitrate (V) acid, prepared by neutralization reaction
of trioxonitrate (V) acid on appropriate alkali or action of trioxonitrate (V) acid on metals.
They cannot be prepared by precipitation because they are all water soluble.

PROPERTIES OF TRIOXONITRATE (V) SALTS

1. Action of heat: all trioxonitrate (V) decompose on heating to varying products. All
metallic trioxonitrate(V) decompose to give the oxides, oxygen and brown fumes of
nitrogen (IV) oxide, except that of Na and K, while that of Ag, in addition gives
metallic Ag.
2. Action of H2SO4: all trioxonitrate (V) salts liberate HNO3 when reacted with conc.
H2SO4
NO3-+H2SO4HSO4-+HNO3
3. Formation of brown ring: when conc. H2SO4 is added slowly down the side of the test
tube of aqueous solution of trioxonitrate (V) and freshly prepared FeSO4. At the
junction of the two liquid layers, the three solution reacts to form a brown ring
compound.

STAGES INVOLVED
1. The NO3- in the solution reacts with the conc. H2SO4 to form HNO3 acid :
H2SO4+ NO3-HSO4- +HNO3
2. The HNO3 formed is reduced by FeSO4 to form Nitrogen ii oxide.
2HNO3+3H2SO4+6FeSO4 3Fe2(SO4)3 +4H2O +2NO
3. The NO then combine with more of FeSO4 to form a brow addition compound
(complex) which appears the junction of the two liquid layers as brown ring
FeSO4+NO FeSO4.NO
(This is a confirmatory test for trioxonitrate (V) ion (NO3-)

TEST FOR NITRATE ION (NO3-): brown ring test

53
NITROGEN CYCLE

54
SULPHURAS AN ELEMENT

55
Sulphur is a yellow, non – metallic solid element at room temperature which makes up about
0.1% of the earth’s crust. It is the second member in group (VI) of the periodic table. Sulphur
shows valencies of -2, +4 and +6.
It is found in the combined state as galena (PbS), zinc blende (ZnS), iron pyrites (FeS) and as
the tetraoxosulphate (VI) salts of calcium, magnesium and barium.

EXTRACTION OF SULPHUR
Sulphur can be produced industrially from the yellow deposits of sulphur by FRASCH
process. During the process, a hole of about 30cm in diameter is bored through the ground to
the sulphur deposit. The sulphur pump is inserted into the sulphur deposit through the hole.
The pump consists of three concentric tubes.
At this point, superheated water (about 170oC) is forced under pressure down the outer tube,
to the sulphur deposit. This melts the sulphur at a melting point of 115oC, which makes the
molten sulphur to enter the middle pipe. At this point hot compressed, air at a pressure of
15atmosphere is forced down the innermost or central pipe, forcing the molten sulphur to
flow to the top where it is run off to solidify. The sulphur obtained is about 99.5% pure. The
process of removal of the sulphur contained in petroleum during petroleum refining is known
as desulphurization of petroleum.

ALLOTROPES OF SULPHUR
Allotropy is the ability of an element to exist in two or more different forms in the same
physical state. The main allotropes of sulphur are rhombic sulphur (α – sulphur), monoclinic
sulphur (β – sulphur), amorphous sulphur (δ – sulphur), colloidal sulphur and plastic sulphur.

PREPARATION OF RHOMBIC SULPHUR (α – sulphur)

Dissolve powdered sulphur in carbon (IV) sulphide in a beaker. Warm and keep the
temperature below 95oC. Filter the solution into another beaker and allow the solvent to
evaporate as crystals of rhombic sulphur are being deposited.

PROPERTIES OF RHOMBIC SULPHUR

1. Rhombic sulphur is stable at temperature below 96oC.
2. It is pale yellow in colour
3. It is readily soluble in carbon (IV) sulphide.
4. It has a density of 2.06gcm-3and melting point of 113oC
5. It is crystalline and octahedral in shape
6. It contains S8 molecules with ring of eight sulphur atoms.

MONOCLINIC SULPHUR (β – sulphur)

Rhombic sulphur is melted and partially allowed to solidify. On pouring off the liquid, long -
needle like crystals (monoclinic sulphur) will be left behind.

PROPERTIES OF MONOCLINIC SULPHUR

56
 1. It has a density of 1.96gcm-3
2. Like rhombic, it contains S8 molecules.
3. It is a crystalline and the crystals are thin and needle – shaped.
4. It has a melting point of 119oC
5. It is stable between 96oC and 119oC

PLASTIC SULPHUR
This is prepared by heating yellow sulphur in a test tube and pouring the molten sulphur in a
thin continuous stream into cold water.

PROPERTIES OF PLASTIC SULPHUR

1. It is soft and elastic
2. It does not dissolve in carbon (IV) sulphide
3. It loses its plasticity on standing and reverts to rhombic sulphur. It is unstable and not
considered a true isotope of sulphur.

COLLOIDAL SULPHUR
This is prepared by adding dilute hydrochloric acid into dilute sodium trioxodisulphate (IV).
It is yellow in colour.
Na2S2O3(aq) + 2HCl(aq)→ 2NaCl(aq)+ H2O(l) + S(s) + SO2(g)

AMORPHOUS SULPHUR
This is prepared when a saturated solution of hydrogen sulphide (H2S) is exposed to air. It is
in form of white powder and is amorphous in shape.
2H2S(g) + O2(g) → 2H2O(l) + 2S(s)

EXTRACTION OF SULPHUR
Sulphur is produced in commercial quantity from the yellow deposits of sulphur in the earth
by the FRASCH PROCESS.
A hole of about 30cm in diameter is bored through the ground to the sulphur deposit. The
sulphur pump is then inserted into the sulphur deposit through the hole. The pump consists of
three concentric tubes.
Superheated water (about 170oC) is forced under pressure down the outer tube, to the sulphur
deposit. This melts the sulphur at the melting point of 115oC. The molten sulphur enters the
middle pipe. Hot compressed air at a pressure of 15 atmospheres is forced down the
innermost or central pipe, forcing the molten sulphur to flow to the top where it is run off to
solidify (about 99.8% pure)

57
PHYSICAL PROPERTIES OF SULPHUR
1. It is a yellow non – metallic solid
2. It has a melting point of 117oC and a boiling point of 444oC
3. It does not conduct heat and electricity.
4. It is insoluble in water but soluble in carbon (IV) sulphide.

CHEMICAL PROPERTIES OF SULPHUR

1. Direct combination with other elements
(i) With metals:
When heated in the absence of air, sulphur combines directly with many
metls to form sulphides.
Zn(s)+ S(s) → ZnS(s)
FeS(s) + S(s) → FeS(s)
2Cu(s) + S(s) → Cu2S(s)

(ii) With oxygen:

It burns in plentiful supply in a plentiful supply of oxygen, with a bright
blue flame to form sulphur (IV) oxide.
S(s) + O2(g)→ SO2(g)

58
 (iii) With Hydrogen:
Sulphur reacts with hydrogen at high temperature to form hydrogen
sulphide.
H2(g) + S(s) → H2S(g)

(iv) With carbon:

Sulphur combines with coke in an electric furnance to form a colourless
liquid known as carbon (IV) sulphide.
C(s) + 2S(s) → CS2(l)

(v) With other non – metals:

It combines with other non – metals to form various sulphides. E.g
tetraphosphorus trisulphide, P4S3, disulphide, S2Cl2 and sulphur
hexaflouride, SF6.
P4(s) + 3S(s) → P4S3(s)
Cl2(g) + 2S(s) → S2Cl2
6F(g) + S(g) → SF6

2. Action of oxidizing acids:

Sulphur is readily oxidised when warmed with concentrated tetraoxosulphate (VI)
acid to form sulphur (IV) oxide.
S(s) + 2H2SO4(aq) → 2H2O(l) + 3SO2(g)
With concentrated trioxonitrate (V) acid, using bromine as a catalyst, sulphur is
oxidised to tetraoxosulphate (VI) acid.
S(s) + 6HNO3(aq) → H2SO4(aq) + 6NO2(g) + 2H2O(l)

3. Action of hot concentrated alkalis:

Sulphur reacts with hot concentrated alkaline solition to form a mixture of sulphides
and trioxosulpates (IV)
3S + 6OH- → 2S2- + SO32-+ 3H2O
In the presence of excess sulphur, a polysulphide and a trioxothiosulphate (VI)are
formed respectively.
SO32- + S → S2O32-
Where n = 1 to 8

USES OF SULPHUR
1. It is used in the manufacture of matches, fireworks and gun powder
2. It is used in the manufacture of tetraoxosulphate (VI) acid.
3. It is used in the vulcanization of rubber.
4. It is used to manufacture the bleaching agent used in the pulp and paper industry.
5. It is used in preparing fungicides and insecticides
6. It is used for the production of carbon (IV) sulphide, skin ointments and dyes.

59
TETRAOXOSULPHATE (VI) ACID
Tetraoxosulphate (VI) acid is a dibasic acid obtained by bubbling sulphur (VI) oxide through
water. It is one of the most important heavy chemicals known and has very large scale use.

INDUSTRIAL PREPARATION OF TETRAOXOSULPHATE (VI) ACID

Industrially, tetraoxosulphate (VI) acid is prepared by the contact process. The sulphur (IV)
oxide is obtained by burning sulphur in dry air or by roasting sulphide ores.
S(s) + O2(g) ←→ SO2(g)
The sulphur (IV) oxide is then mixed with excess air and passed through electrostatic dust
precipitating chamber to remove impurities and dust which might poison the catalyst. The
mixture of sulphur (IV) oxide and air is then passed on to the reaction chamber where the
sulphur (VI) oxide combines with oxygen in the presence of vanadium (V) oxide,
V2O5catalyst at a temperature of 450oC to yield sulphur (VI) oxide.
Vandium (V) oxide
2SO2(g) + O2(g) ←→ 2SO3(g)
450oC
The sulphur (VI) oxide is cooled and passed into an absorption tower where it dissolves in
concentrated tetraoxosulphate (VI) acid to produce a very thick liquid called OLEUM.
SO3(g) + H2SO4(aq) → H2S2O7
The oleum formed is then diluted with a calculated amount of water to produce
tetroxosulphate (VI) acid of the required concentration.
H2S2O7(aq) + H2O(l) → 2H2SO4(aq)
The sulphur (VI) oxide is not dissolved directly in water because the heat evolved during the
process would cause the acid solution to boil, producing a mist of acid droplets which is
difficult to condense and dissolve in the bulk of solution.
Vanadium (V) oxide is used as the catalyst because it is cheaper and more resistant to the
action of “poisons” than the platinum catalyst, hence it is preferred.

PHYSICAL PROPERTIES OF H2SO4

1. Concentrated tetraoxosulphate (VI) acid is a colourless viscous liquid with a density
of 1.84gcm-3
2. It is very corrosive.
3. It turns blue litmus paper red.
4. Concentrated tetroxosulphate (VI) acid has a strong affinity for water. So, it dissolves
readily in water.
5. Concentrated tetraoxosulphate (VI) acid is hygroscopic, absorbing water vapour from
the surroundings and becoming more dilute in the process.
In a similar way, conc. H2SO4 acts on the skin and cloth.

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CHEMICAL PROPERTIES OF H2SO4

1. As an acid - H2SO4 is dibasic and ionizes almost completely in solution, this

makes it a strong acid. Due to it being dibasic, it forms two kinds of salts with alkalis.
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l) and
NaOH(aq) + H2SO4(aq) → NaHSO4(aq) + H2O(l)

2. Action of dilute H2SO4 with metals

Reactive metals would displace hydrogen from dilute tetraoxosulphate(VI) acid.
Zn(s) + H2SO4(aq)→ ZnSO4(aq) + H2(g)
Note:
*Less reactive metals such as copper will not displace hydrogen from dilute acid.
*Cold concentrated H2SO4 is not attacked by any metal in the complete absence of
water.

3. Action on trioxocarbonate(IV) and

hydrogentrioxocarbonate (IV)salts
Carbon(IV) oxide is liberated when H2SO4 is added onto a trioxocarbonate(IV).
Na2CO3(aq) + H2SO4(aq) → Na2SO4(aq) + H2O(l) + CO2(g)
On a piece of marble, which has the chemical formula CaCO3, the reaction obtained
is prematurely stopped due to the formation of the sparingly soluble salt, CaSO4,
which forms a deposit on the surface of the marble.

4. Conc. H2SO4 as an oxidizing agent

When hot and concentrated, the acid accepts electrons from reducing agents such as
Cu or Zn. It also oxidizes metals and non-metals, such as copper, zinc, carbon,
hydrogen sulphide and sulphur, and is reduced to SO2 in the process.
S(s) + 2H2SO4(aq)→ 2H2O(l) + 3SO2(g)
C(s) + 2H2SO4(aq)→ 2H2O(l) + 2SO2(g) + CO2(g)
Zn(s) + 2H2SO4(aq) → ZnSO4(aq) + 2H2O(l) + SO2(g)
Cu(s) + 2H2SO4(aq) → CuSO4(aq) + 2H2O(l) + SO2(g)
H2S(g) + H2SO4(aq) → SO2(g) + H2O(l) + S(s)
The SO2 given off is detected using a strip of filter paper moistened with potassium
heptaoxodichromate(VI) solution which turns green - this is one of the tests for SO2
discussed earlier.

5. As a dehydrating agent
Tetraoxosulphate(VI) acid has a strong affinity for water. The addition of the acid to
water (conc. acid should always be gradually added to water, with stirring of the
liquid as the acid is added - to prevent the acid from forming a lower layer) produces
a great amount of heat, hence the addition is not a physical change, but a chemical
change.
H2SO4 is hygroscopic, that is, it absorbs water from the air and becomes dilute. When
conc. H2SO4 is added to many compounds, it decomposes them by removing water
molecules from them, that is, it dehydrates them.

61
 An example is the removal of rust from iron, and the dehydration of sugar. The sugar
becomes a black mass of carbon.

C12H22O11(s) + nH2SO4(l) → 12C(s) + (11H2O(l) + nH2SO4(aq))

Sugar

C2H5OH(l)→C2H4(g) + (H2O + Conc. H2SO4)

Ethanol

HCOOH(l) → CO(g) + (H2O + Conc. H2SO4)

Methanoic acid

COOH
I → CO2(g) + CO(g) + ( H2O + Conc. H2SO4)
COOH(s)
Ethanedioic acid

6. Displacement of other acids from their salts:

Concentrated tetraoxosulphate (VI) acid displaces volatile acids from their salts. E.g
KCl + H2SO4(aq) → KHSO4(aq) + HCl(g)
NaNO3(s) + H2SO4(aq) → NaHSO4(aq) + HNO3(g)

Test for Tetraoxosulphate(VI) Ion

The characteristic test for any soluble tetraoxosulphate(VI) is the formation of white
precipitate (barium sulphate) when a solution of barium chloride, acidified with dilute HCl,
or when a solution of barium nitrate, acidified with dilute nitric acid is reacted with it.

BaCl2(aq) + H2SO4(aq) → 2HCl(aq) + BaSO4(s)

Ba(NO3)2(aq) + H2SO4(aq) → 2HNO3(aq) + BaSO4(s) - white precipitate

USES OF H2SO4
Below are some of the uses of H2SO4

1. For the manufacture of fertilizer, such as ammonium tetraoxosulphate(VI), NH4SO4,

and superphosphates.
2. For the manufacture of paints and pigments.
3. For the manufacture of artificial and natural fibre.
4. For the manufacture of metallic tetraoxosulphate(VI), HCl, HNO3, HF, and plastics.
5. For the manufacture of detergents, dyes, explosives and drugs.
6. For the extraction of metals, example, in pickling (cleaning) iron and steel before
plating them with tin or zinc.
7. As electrolyte in lead-acid storage battery.
8. In petroleum refining, where to is used to wash impurities out of gasoline and other
refinery products.

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HYDROGEN SULPHIDE [H2S]
Hydrogen sulphide is prepared both in the laboratory and industrially by the action of a dilute
acid on a metallic sulphide, e.g iron (II) sulphide.
2HCl(aq) + FeS(s) → FeCl2(aq) + H2S(g)
H2SO4(aq) + FeS(s) → FeSO4(aq) + H2S(g)
It involves putting iron (II) sulphide in a flat bottomed flask and covers it with water. Add
some concentrated hydrochloric acid or tetraoxosulphate (VI) acid through a thistle funnel.
Effervescence and hydrogen sulphide gas is produced and collected over water when the acid
reaches the iron (II) sulphide. Hydrogen sulphide is rather soluble in cold water but, like all
other gases, it is less soluble in hot water. The gas obtained is passed through a U – tube
containing fused calcium chloride, if required dry and collected in the gas jar.

SULPHUR (IV) OXIDE

Suphur (IV) oxide is prepared in the laboratory by the action of HCl on sodium
triososulphate SO2 is collected by passing it through conical flask containing H2SO4. The gas
is collected by downward delivery because it is denser than air.
Na2SO3+HCl  2NaCl +H2O + SO2

PHYSICAL PROPERTIES OF SO2

1. It turns moist blue litmus paper red
2. It is colourless and poisonous as with an irritating smell

63
 3. It dissolves in water to form acidic solution
4. It is denser than air and has boiling point of -100c

CHEMICAL PROPERTIES
1. Acidic properties:
(i) Dissolved in water to form acid
SO2+ H2O H2CO3
(ii) neutralise alkalis to form salt and water
SO2+ NaOHNa2SO3+H2O
2. Reacts with metallic oxides to form its salts
PbO2 + SO2 PbSO4

3. Oxidizing properties
(i) Oxidize H2S to yellow sulphur
2H2S + SO2 2H2O + 3S
(ii) Reacts with some metals to form their oxides
Mg+SO2 2MgO + S

4. Bleaching agent:
It dissolve in water to form trioxosulphate iv acid, this donate electron to dye and get
oxidized in the process to form H2SO4
SO2 + H2O  H2SO3
H2SO3 + DYE(coloured)  H2SO4 + Bleached dye (colourless)
5. It reacts with oxygen in the presence of catalyst to form
sulphur (VI) oxide
SO2 + O2 SO3
6. Reducing properties:
(i) It reduces the brown iron iii chloride to green iron ii chloride
2FeCl3 + SO2 + H2O  2FeCl2 + H2SO4 + 2HCl
(ii) It reduces concentrated trioxonitrate v acid to brown nitrogen iv oxide gas
2HNO3 + SO2 H2SO4 + 2NO2
(iii) Coloured solutions of halogens are reduced to colourless solution of halide
ions
Cl2 + SO2 + 2H2O SO42-+ 2Cl-+4H+

TEST FOR SULPHUR (IV) OXIDE

1. It has an irritating smell
2. It decolourise acidified form of KMnO4 without yellow deposit of sulphur
3. It changes the orange colour of acidified potassium heptaoxodichromate (VI) to green
without a yellow precipitate of sulphur

USES OF SULPHUR (IV) OXIDE

1. Used in the manufacture of H2SO4

64
 2. Used as bleaching agent for dyes and clothes
3. Used for killing termites
4. Used as germicides or fumigants
5. Used as refrigerant
6. Liquid SO2 is solvent for iodine, sulphur, potassium iodide etc

SULPHUR (VI) OXIDE

It is a colourless acidic oxide with an irritating smell, the formular is SO3

LABORATORY PREPARATION OF SO3

It is prepared in the laboratory by passing SO2 and O2 over vanadium v oxide catalyst. The
gas is dried by passing it through concentrated H2SO4

INDUSTRIAL PREPARATION OF SULPHUR (VI) OXIDE

The process can be divided into five stages:

1. Combining of sulphur and oxygen (O2) to form sulfur (IV) oxide

S(g)+ O2(g) 2SO2(g)
2. Purifying the sulfur dioxide in a purification unit, in an electric chamber to remove
impurities and dust, the purified form is passed through H2SO4 to dry the gas.
3. Adding an excess of oxygen to sulfur (IV) oxide in the presence of the catalyst

2SO2(g) + O2(g)⇌ 2SO3(g) : ΔH = -197 kJ·mol−1

vanadium pentaoxide (vanadium(V) oxide) at 450 °C and 1-2 atm

4. The sulfur (VI) oxide formed is added to tetraoxosulphate (VI) acid which gives rise
to oleum (disulfuric acid)
65
 5. The oleum is then added to water to form sulfuric acid which is very concentrated.
PHYSICAL PROPERTIES OF SO3
1. Exist as white crystals at room temperature
2. It is an acidic oxide
3. It dissolve in water to form acidic solution
4. Aqueous solution turns blue litmus paper red
5. It fumes strongly in moist air

CHEMICAL PROPERTIES OF SO3

1. It neutralize alkalis to form salt and water
SO3+ NaOH Na2SO4+2H2O

2. It dissolves in H2SO4 to form oleum (fuming H2SO4)

SO3+H2SO4 H2S2O7 (OLEUM)

3. It reacts with basic oxides to form Tetraoxosulphate (VI)

SO3(g) + CaO(s) CaSO4(s)

USES OF SO3
1. It is used in the manufacture of H2SO4
2. It is used on a large scale (Industrial scale) for sulphonating organic compounds

INDUSTRIAL PREPARATION OF SO3

It is prepared industrially by contact process, the following steps are used
1. SO2 is obtain by burning sulphur in air
2. The sulphur (IV) oxide formed is mixed with excess air and passed through electric
chamber to remove impurities and dust
3. The mixture is now dried by passing it through Concentrated H2SO4
4. The heated mixture is now passed over vanadium (v) oxide catalyst

PHYSICAL PROPERTIES OF SULPHUR (IV) OXIDE

1. It is an acidic oxide.
2. It exists as white crystals at room temperature
3. It is readily soluble in water to give H2SO4
4. It fumes strongly in moist air
5. Aqueous solution turns blue litmus paper red

DEFINITIONS OF OXIDATION AND REDUCTION:

STEP 1: ADDITION OF OXYGEN
Oxidation and reduction are two opposing, yet complementary processes that occur
simultaneously. Oxidation was initially defined as a reaction that involves addition of oxygen
to a substance while reduction is a reaction in which oxygen is removed from a substance.

66
The substance that donates the oxygen is the oxidizing agent (O.A) while the substance that
accepts the oxygen is the reducing agent (R.A). Example,
C(s) + 2ZnO(s)→ CO2(g) + 2Zn(s)
R.A O.AO.S R.S
3Fe(s) + 4H2O(g)→ Fe3O4(s) + 4H2(g)
R.A O.A O.S R.S
While CO2(g) is the oxidized substance (O.S) and Zn(s) is the reduced substance (R.S).

STEP 2: REMOVAL OF HYDROGEN

Oxidation was later defined as a reaction that involves removal of hydrogen from a substance
while reduction is a reaction in which hydrogen is added to a substance. The substance that
donates the hydrogen is known as the reducing agent (O.A) while the substance that accepts
the hydrogen is known as the oxidizing agent (O.A). Example,
H2S(g) + Cl2(g) → 2HCl(g) + S(s)
R.A O.A R.S O.S

STEP 3: ADDITION OF ELECTRONEGATIVE ELEMENTS

Definition of Oxidation was later extended to include addition of electronegative elements to
a substance and removal of electropositive elements from a substance while reduction is
includes the removal of electronegative elements from a substance as well as the addition of
electropositive elements to a substance. Electronegative elements are those elements that
ionize by electron gain while electropositive elements are those elements that ionize by
electron loss. Example,
2Na(s) + Cl2(g)→ 2NaCl(s)
R.A O.A
H2S(g) + Br2(g)→ 2HBr(g) + S(s)
R.A O.A R.S O.S
In a reaction where two electronegative elements are present, the more electronegative of the
two is regarded as the oxidizing agent.

Elements:
(Non – metals) F, O, Cl, N, Br, S, C, I, P
→ Electronegativity decreases
(Metals) K, Na, Ca, Mg, Al, Zn, Fe, Pb, Cu
→ Electropositivity decreases

STEP 4: TRANSFER OF ELECTRONS

Oxidation and reduction was currently defined using the most concise definition based on the
concept of transfer of electrons. Oxidation is therefore defined as a process involving loss of
electron(s) while reduction is a process that involves gain of electron(s). A substance is
reduced when it gains electrons and oxidized when it loses electrons. During oxidation, a
substance loses electron(s) and its oxidation number increases in the positive direction while
a substance gains electron(s) when reduced and its oxidation number decreases in the
positive direction. The substance that loses electron(s) is known as the reducing agent (R.A)
while the substance that gains electron(s) is known as the oxidizing agent (O.A). Example,

67
Iron (II) chloride reacts with chlorine to form iron (III) chloride.
2FeCl2(s) + Cl2(g)→ 2FeCl3(s)
R.A O.A

4FeO(s) + O2(g)→ 2Fe2O3(s)

The fundamental change is this reaction is that iron (II) ion, Fe2+ changes to iron (III) ion,
Fe3+ which corresponds to the change from iron (II) oxide to iron (III) oxide. This is an
indication of oxidation reaction.

REDOX REACTION
Redox reaction is basically a reaction that involves transfer of electrons from the reducing
agent to the oxidizing agent. Oxidation occurs at the anode where the anions lose electrons.
This reaction at the anode is known as anodic half – reaction. The cathodic half – reaction
takes place simultaneously at the cathode is a reduction reaction since the cations gain
electrons. A reducing agent is a substance that donates electron. It is also a substance which
is oxidized, thereby bringing about reduction. A substance in which its oxidation number
increases in the positive direction. An oxidizing agent is a substance that accepts electron. It
is also a substance which is reduced, thereby bringing about oxidation. A substance in which
its oxidation number decreases in the positive direction. Example,
Reaction between potassium iodide solution and iron(III) tetraoxosulphate (VI). The reaction
mixture turns brown due to the liberation of iodine.
2KI(aq) + Fe2(SO4)3(aq)→ I2(s) + K2SO4(aq)+2FeSO4(aq)

Which is represented ionically as:

2I-(aq) + 2Fe3+(aq) → I2(s) + 2Fe2+(aq)

In this reaction, iodide ions are oxidized to iodine molecules while iron (III) ions are reduced
to iron (II) ions.
Ionic half equation for the reaction is:
2I-(aq) → I2(aq) + 2e- (Oxidation half equation)
3+ - 2+
2Fe (aq) + 2e → 2Fe (aq) (Reduction half equation)

OXIDATION NUMBER
Oxidation number of an element is the electrical charge it appears to have both in the free
and combined states, as determined by a set of rules. These rules are:
1. All elements in the free or uncombined state have an oxidation number of zero.
E.gKo, Nao, Cl2o, P4o, S8o etc.
2. The oxidation number of a simple ion has the same size and sign as the charge of the
ion. E.g the oxidation number of K+, Zn2+, Al3+, Cl-, O2- are +1, +2, +3, -1 and -2
respectively. The sign always comes before the number.
3. When an ion consists of more than one element, its oxidation number is the sum of
the oxidation numbers of all the elements in the ion. This must be equal in size and
sign to the overall charge on the ion. Therefore, the sum of the oxidation states of the
atoms in a polyatomic ion is equal to the charge on the ion. E.g. ammonium ion, NH4
[Oxidation Number of N] + 4[Oxidation Number of H] = +1

68
 (-3) + 4(+1) = +1
(-3) + (+4) = +1
The overall charge is +1
Therefore, the oxidation number of OH-, SO42-, PO43- and MnO4- are -1, -2, -3 and -1
respectively.
4. The sum of all the oxidation numbers of elements in a compound is zero. E.g
Determination of oxidation number of H2SO4 as shown below:
2[Oxidation number of H] + [Oxidation number of S] + 4[Oxidation number of O] =
O
2(+1) + (+6) + 4(-2) = 0
(+2) + (+6) + (-8) = 0
(+8) + (-8) = 0
5. The oxidation number of hydrogen is +1 (except in metallic hydrides where the
oxidation number is -1). Example,
Oxidation state of hydrogen in NH3 = +1 and oxidation number of hydrogen in NaH =
-1
The oxidation number of oxygen is -2 (except in peroxides where the oxidation
number where the oxidation number is -1). Example,
The oxidation state of oxygen in MgO = -2 and oxidation state of oxygen in H2O2 = -
1

CALCULATIONS INVOLVING DETERMINATION OF OXIDATION

NUMBERS OF CENTRAL ELEMENTS IN SOME COMPOUNDS.

QUESTION 1
Find the oxidation number of chromium atom in potassium heptaoxodichromate (VI),
K2Cr2O7

SOLUTION
Oxidation number of Cr atom in K2Cr2O7
2[Oxidation number of K] + 2[Oxidation number of Cr] + 7[Oxidation number of O] = 0
2[+1] + 2[Cr] + 7[-2] = 0
+2 + 2Cr - 14 = 0
2Cr + 2 - 14 = 0
2Cr - 12 = 0
2Cr = 12
Cr = 12
2
Cr = +6
The oxidation number of chromium atom in potassium heptaoxodichromate (VI) is + 6.

QUESTION 2
Determine the oxidation number of Mn in MnO4-

69
SOLUTION
Equate the oxidation number of elements to the net charge in the compound.
MnO4- = -1
Mn + 4[-2] = -1
Mn + [-8] = -1
Mn - 8 = -1
Mn = -1 + 8
Mn = +7
NAMING COMPOUNDS BY USING OXIDATION STATES
Oxidation states are used in the systematic nomenclature of compounds which is set out by
the IUPAC (International Union of Pure and Applied Chemistry).

NAMING OF COMPOUNDS CONTAINING ELEMENTS

WITH VARIABLE OXIDATION STATE
Oxidation numbers of elements which have variable oxidation states are represented using
roman numerals in parentheses immediately following its name. Consider the chlorides and
oxides of iron such as FeCl2, FeCl3, FeO and Fe2O3. The oxidation states of the atoms present
in a compound, add up to zero. In both FeCl2 and FeCl3, each chlorine atom exists as the
chloride ion [Cl-] with an oxidation state of -1. This means that the iron in FeCl2 and FeCl3
has an oxidation state of +2 and +3 respectively. Hence FeCl2 is named as iron (II) chloride
while FeCl3 is named as iron (III) chloride. The oxidation number of oxygen is -2 in FeO and
Fe2O3. Hence FeO is named iron (II) oxide while Fe2O3 is named iron (III) oxide. In naming
an ionic compound, the name of the cation always comes first, followed by that of the anion.
In covalent compounds, we determine the oxidation number of the central atom (i.e. the atom
to which other atoms are attached in the compound). The carbon (central atom) in CO 2 has an
oxidation state of +4. That’s why the IUPAC name of CO2 is carbon (IV) oxide.

NAMING OF POLYATOMIC ANIONS CONTAINING

OXYGEN
For polyatomic anion containing oxygen, the number of oxygen atoms attached to the central
atom is denoted by the prefix di – for two, tri – for three, etc. The oxidation state of the
central tom is indicated by a roman numeral (I, II etc) in parenthesis following the name of
the element. A table of polyatomic anions and their names is shown below:
ANIONS CENTRAL ATOM OXIDATION STATE OF IUPAC NAME
CENTRAL ATOM
CO32- Carbon +4 Trioxocarbonate(IV) ion
2-
SO3 Sulphur +4 Trioxosulphate(IV) ion
2-
SO4 Sulphur +6 Tetraoxosulphate(VI)
ClO3- Chlorine +5 Trioxochlorate(V) ion
-
ClO Chlorine +1 Oxochlorate(I) ion
NO2- Nitrogen +3 Dioxonitrate(III)
-
NO3 Nitrogen +5 Trioxonitrate(V)

70
Therefore, the IUPAC name of Pb(NO3)2 is lead(II) trioxonitrate (V) while that of FeSO4 is
iron (II)tetraoxosulphate (VI).

NAMING OF HYDRATED COMPOUNDS

Name the compound without the water of crystallization by using the rules for naming
compounds, followed by stating the number of water molecules present in the formula unit.
For example, the hydrated compound FeSO4.7H2O contains seven water molecules. So, it is
named iron (II) tetraoxosulphate(VI) heptahydrate. Complex ion consists of a central ion
bonded to ligands.

DETERMINATION OF FORMULAE OF COMPOUNDS

FROM THEIR IUPAC NAMES
Chemical formula of an ionic compound can be determined from its name by identifying the
cation and anion present in the compound. For covalent compounds, we identify the types of
atoms (i.e elements) present in it and name them according to the rules stated.

OXIDISING AND REDUCING AGENTS

A substance that brings about oxidation in another substance is called an oxidizing agent. In
bringing about oxidation, an oxidizing agent is itself reduced.
A substance that brings about reduction in another substance is called a reducing agent. The
reducing agent is itself oxidized in the process.
Some common oxidizing and reducing agents are shown below:
OXIDISING AGENTS REDUCING AGENTS
Oxygen (O2) Hydrogen (H2)
Ozone (O3) Sulphur (IV) oxide (SO2)
Chlorine (Cl2) Hydrogen sulphide (H2S)
Trioxonitrate (V) acid (HNO3) Carbon (II) oxide (CO)
Concentrated tetraoxosulphate (VI) acid Carbon (C)
(H2SO4)
Potassium tetraoxomanganate (VII) (KMnO4) Ammonia (NH3)
Potassium heptaoxodichromate (VI) Potassium iodide (KI)
(K2Cr2O7)
Manganese (IV) oxide (MnO2) Iron (II) salts
Hydrogen peroxide (H2O2) Sodium and any metal atom high in the
reactivity series
Sulphur (S)
Silver salts and any metal atom low in the
reactivity series.

TEST FOR OXIDISING AGENTS

An oxidizing agent is also called an oxidant.

1. ACTION ON POTASSIUM IODIDE

71
Most oxidizing agents liberate iodine from acidified potassium iodide solution. This results
in the formation of a brown solution which turns blue – black upon the addition of starch. E.g
-e-
I- →Io

2. ACTION ON HDROGEN SULPHIDE

Bubble hydrogen sulphide through a solution of an oxidizing agent. Yellow sulphur is
deposited due to the oxidation of the sulphide ions by the oxidizing agent, E.g
-2e-
S2-→ So
3. ACTION ON IRON (II) CHLORIDE
An oxidizing agent turns a green solution of iron (II) chloride into a brown coloured iron (III)
chloride. The iron (II) ion donates an electron each to the oxidizing agent and becomes
oxidized to iron (III) ions. E.g
-e-
Fe2+→ Fe3+

TEST FOR REDUCING AGENTS

A reducing agent is known as a reductant.
1. ACTION ON ACIDIFIED POTASSIUM
TETRAOXOMANGANATE (VII) KMnO4
Reducing agents on warming with acidified potassium tetraoxomanganate(VII) decolourise
the purple colour of the solution. This is because the tetraoxomanganate (VII) MnO4-which is
purple in colour has been reduced to manganese (II) ion, Mn2+ which is colourless.
MnO4-(aq) + 8H+(aq) + 5e-→ Mn2+(aq) + 4H2O(l)
2. ACTION ON ACIDIFIED POTASSIUM
HEPTAOXODICHROMATE (VI) K2Cr2O7
Reducing agents on warming with acidified potassium heptaoxodichromate (VI), reduced the
orange colour of heptaoxodichromate (VI) ion, Cr2O72- to chromium (III) ion, Cr3+ which is
green in colour.
Cr2O72-(aq) + 14H+(aq) + 6e-→ 2Cr2+(aq) 7H2O(l)

BALANCING REDOX EQUATIONS

Redox equations are balanced using basically two methods namely:
1. Half - cell reaction method
2. Oxidation number method

BALANCING REDOX EQUATIONS USING HALF - CELL

REACTION METHOD
Steps involved are as follows:
STEP 1
Identify the oxidizing agent and reducing agent and deduce what the product should be.
STEP 2

72
Write the half equation for each of oxidation and reduction.
STEP 3
Balance the atoms and charges for each half equation by;
(i) Adding the correct number of H2O, H+ or OH- to the appropriate side of the
equation if necessary
(ii) Adding the correct number of electrons on the right hand side for the oxidation
half equation, and on the left hand side for the reduction half equation.
(iii) Adding appropriate numerical coefficient.

STEP 4
Ensure that the electron loss in the oxidation half equation is balanced by the electron gain in
the reduction half equation.
STEP 5
Add the two half equations to eliminate the electrons and get the overall redox equation.

QUESTION 1
Write a balanced ionic equation for the redox reaction between acidified heptaoxodichromate
(VI) ion and chloride ion.

SOLUTION
STEP 1
(a)Heptaoxodichromate (VI) ion is the oxidizing agent, so it is reduced to chromate (III) ion
as shown below:
Cr2O72-(aq)→ Cr3+(aq)
(b) Chloride ion is the reducing agent, so it is oxidized to chlorine atom.
2Cl-(aq) → Cl2(g)

STEP 2
Write the half - cell equation as shown below:
(a) Reduction half – cell equation:
2-
Cr2O7 (aq)→ Cr3+(aq)
(b) Oxidation half – cell equation:
-
2Cl (aq) → Cl2(g)

STEP 3
Balance the number of atoms and charges as shown below:
(c) Reduction half – cell reaction:
Add correct number of H+ and H2O on the appropriate side as shown below:
Cr2O72-(aq) + 14H+(aq)+ 6e-→2Cr3+(aq) + 7H2O(l)
Total number of charges on the left hand side = -2 + 14 -6
= +6
Total number of charges on the right hand side = +6
(d) Oxidation half – cell reaction:

73
2Cl-(aq) → Cl2(g) + 2e-

STEP 4
Balance the number of electrons loss in oxidation half – cell reaction to correspond to the
number of electron gain in reduction half – cell reaction.
Multiply the oxidation half - cell reaction by 3
6Cl-(aq) → 3Cl2(g) + 6e-
Therefore, the number of electron loss in oxidation half - cell equation is equal to the number
of electron gain in reduction half - cell reaction.

STEP 5
Add the two half - cell reactions to eliminate the number of electrons as shown below:
Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O(l)
And
6Cl-(aq) → 3Cl2(g) + 6e-
Overall net reaction:
Cr2O72-(aq) + 14H+(aq) + 6Cl-(aq) → 2Cr3+(aq) + 3Cl2(g) + 7H2O(l)
NOTE: H+ and H2O used to balance the number of oxygen and hydrogen, since the reaction
occurs in the acidic medium, by adding both on the appropriate sides.
However, to balanceredoxreaction that takes place in alkaline solution is slightly different
from those that occur in acidic solution. All the steps are the same, except the second step
where OH- is used instead of H+ to balance the oxygen and hydrogen.

QUESTION 2
Write a balanced ionic equation for the redox reaction between tetraoxomanganate (VII) ion,
MnO4- and hydrazine, N2H4 in alkaline solution.

SOLUTION
STEP 1
Tetraoxomanganate (VII) ion, MnO4- is the oxidizing agent, so it is reduced to manganite
(IV) oxide as shown below;
MnO4-→ MnO2 (Reduction reaction)
Hydrazine, N2H4 is reducing agent, since it is oxidized to Nitrogen as shown below;
N2H4→ N2
STEP 2
Write the half – cell equation as shown below;
(a) Reduction half – cell equation:
MnO4-→ MnO2
(b) Oxidation half – cell equation:
N2H4→ N2
STEP 3
Balance the number of atoms and charges by adding the correct number of OH- and H2O on
the appropriate side:
(a) Reduction half – cell equation:

74
Balance the number of atoms:
MnO4- + 2H2O → MnO2 + 4OH-
Balance the number of charges:
MnO4- + 2H2O + 3e- → MnO2 + 4OH-
(b) Oxidation half – cell equation:
Balance the number of atoms:
N2H4 + 4OH-→N2 + 4H2O
Balance the number of charges:
N2H4 + 4OH-→ N2 + 4H2O + 4e-

STEP 4
Balance the number of electron gain in reduction half – cell reaction to correspond to the
number of electrons loss in oxidation half – cell reaction.
(a) Reduction half – cell equation:
MnO4- + 2H2O → MnO2 + 4OH-
Multiply the equation by 4,
4MnO4- + 8H2O + 12e-→ 4MnO2 + 16OH-
(b) Oxidation half – cell equation:
N2H4 + 4OH-→ N2 + 4H2O + 4e-
Multiply the equation by 3,
3N2H4 + 12OH-→ 3N2 + 12H2O + 12e-
STEP 5
Add the two half - cell equation together to eliminate the number of electrons.
(a) Reduction half – cell equation:
4MnO4- + 8H2O + 12e-→ 4MnO2 + 16OH-
(b) Oxidation half – cell equation:
3N2H4 + 12OH-→ 3N2 + 12H2O + 12e-
Net Equation:
4MnO4- + 8H2O + 3N2H4 + 12OH-→4MnO2 + 16OH- + 3N2 + 12H2O
Eliminate the excess OH- and H2O
4MnO4- + 3N2H4→4MnO2 + 3N2 + 4OH- + 4H2O
BALANCING REDOX EQUATION USING OXIDATION – NUMBER METHOD.
Three steps are involved in this method of balancing redox equations:
1. The oxidation numbers of the atoms in the equation are determined in order to
identify those undergoing oxidation and reduction.
2. Numerical coefficients are placed before the appropriate formulas so that the total
decrease in oxidation number is equal to total increase in oxidation number.
3. Complete balancing by placing the correct number of H2O and H+ on the appropriate
side to ensure that there are so many atoms of each element on the left as there are on
the right.

QUESTION 1
Write a balanced equation for the redox reaction between trioxonitrate (V) acid and hydrogen
sulphide.

75
SOLUTION
Unbalanced Equation:
HNO3(aq) + H2S(g)→ NO(g) + S(s) + H2O(l)

STEP 1
Determine the oxidation number of each element.
HNO3(aq) + H2S(g)→ NO(g) + S(s)+ H2O(l)
I III
N = +5 S = -2 N = +2 S=0
STEP 2
The oxidation number of nitrogen changes from +5 to +2 (a decrease in the positive
oxidation number by +3, representing reduction) while that of sulphur changes from -2 to 0
(an increase in positive oxidation number by +2, representing oxidation).
STEP 3
Since the increase in oxidation number of sulphur is not equal to the decrease in the oxidation
number of N. It means that 3 atoms of sulphur must react with 2 atoms ofnitrogen as shown
below:
2HNO3(aq) + 3H2S(g)→ 2NO(g) + 3S(s) + H2O(l)
The number of 8 hydrogen atoms on the reactant side has to be balanced by adding 4
molecules of water on the product side of the equation.
2HNO3(aq) + 3H2S(g)→ 2NO(g) + 3S(s) + 4H2O(l)

IONIC THEORY
The concept of ionic theory as proposed by Arrhenius is of the view that when an electrolyte
is melted or dissolved in water, some if not all of the substance breaks up (dissociate) into
freely moving charged particles called ions. The process of dissociation into ions is known as
ionization. Ionization occurs before the passage of electric current into the electrolyte as the
atoms move about at random in all direction. The number of electric charges carried by an
ion is equal to the valency of the corresponding atom or group. Due to the electronic charges
carried by these ions, their properties are quite different from those of their corresponding
atoms which are electrically neutral.
When an electric current is passed through the electrolyte, the free ions lose their random
movement. The positive ions become attracted to the cathode (negative electrode) and are
known as cations (i.e cathode ions). The negative ions are attracted to the anode and are
called anions (i.e anode ions). The current through the electrolyte is carried by the movement
of ions to the electrodes and not by the flow of electrons in the electrolyte. Arrhenius’
version of the ionic theory has been modified since X – diffraction studies show that strong
alkalis consist of oppositely charged ions even in the solid state. The modern theory proposes
that the ions in such solids are pulled away from one another either as a result of the heat
energy applied when the solid melts, or with the help of the solvent molecules when the solid
dissolves. Thus
Arrhenius Theory: NaCl(s)→ Na+(aq) + Cl-(aq)
Modern theory: Na+Cl-(s) → Na+(aq) + Cl-(aq)
76
DIFFERENCES BETWEEN ELECTROVALENT
COMPOUNDS AND COVALENT COMPOUNDS
ELECTROVALENT COMPOUNDS COVALENT COMPOUNDS
*Ionic compounds do not contain molecules, *Covalent compounds consist of molecules
instead they consist of aggregates of positive which have a definite shape
and negative ions arranged in an orderly
pattern of three dimensional crystal lattices.
*They are solids at room temperature and do *They are gases or volatile liquids because
not vapourise easily. their molecules being electrically neutral are
not bound by strong attractive forces.
*They have high melting and boiling points *They have low melting and boiling points
because of the strong electrovalent bonds
between the ions.
*Ionic compounds readily dissolve in water *Covalent compounds readily dissolve in
and other polar solvents. non – polar organic solvents such as
benzene, toluene and carbon disulphide.
*They are good conductors of electricity *Covalent compounds do not conduct
when in molten state or in solution. i.e they electricity, i.e, they are non – electrolyte.
are electrolytes, indicating that ions are free This is because the molecules do not contain
to move about when the compound is in a charged particles.
liquid state.
*They do not dissolve in non – polar solvents
such as toluene, benzene, ether,
trichloromethane etc.

ELECTROLYTES AND NON- ELECTROLYTES

This is a compound which conducts electricity and is decomposed in the process. For a
compound to behave as an electrolyte, it must be in a liquid form either as a molten
compound or an aqueous solution of the compound. Electrolytes conduct electricity by the
movement of ions to the electrodes and their subsequent reactions at the electrode.
Electrolytes are classified into two (strong electrolytes and weak electrolytes), which is
dependent on their ability to conduct electricity.

STRONG ELECTROLYTES
A strong electrolyte dissociates completely to form ions in the molten or aqueous state.
Strong electrolytes are good conductors of electricity.They conduct large current of
electricity, since they are composed entirely of free moving ions. Examples of strong
electrolytes are most soluble salts, mineral acids and alkalis.E.g sodium hydroxide dissociate
completely in solution to form sodium ions and hydroxide ions.
NaCl(aq)→ Na+(aq) + Cl-(aq)

WEAK ELECTROLYTES
Weak electrolytes dissociate incompletely (partially) to form ions in the molten or aqueous
state. So they do not conduct electricity readily. Example, a solution of ammonia in water,
contains only a small proportion of ammonium and hydroxide ions.
NH4OH(aq)↔ NH4+(aq) + OH-(aq)

77
Other examples of weak electrolytes include water and most organic acids such as ethanoic
acid, citric acid and tartaric acid.
Further examples of strong electrolytes and weak electrolytes are:
STRONG ELECTROLYTES WEAK ELECTROLYTES
Aqueous Sodium hydroxide (NaOH) Aqueous ammonia (NH4OH)
Aqueous Sodium chloride (NaCl) Ethanoic acid (CH3COOH)
Hydrochloric acid (HCl) Trioxocarbonate (IV) acid (H2CO3)
Tetraoxosulphate (VI) acid (H2SO4) Hydrocyanic acid (HCN)
Copper (II) tetraoxosulphate(VI) CuSO4 Hydrofluoric acid (HF)

NON ELECTROLYTES
These are those substances which do not conduct electricity under any condition, since they
do not ionize. They are mostly covalent and organic compounds. Example, urea, benzene,
trichloromethane, cane sugar, ether and tetrachloromethane.

ELECTROCHEMICAL SERIES
Electrochemical series is the grouping or arrangement of elements in the order of their
increasing or decreasing reactivity.

PREFERENTIAL DISCHARGE OF IONS

Factors to be considered during preferential discharge of ions are:
1. Position of ions in the electrochemical series
2. Concentration of ions and
3. Nature of the electrodes

POSITION OF IONS IN THE ELECTROCHEMICAL SERIES

Considering other factors to be constant, ions lower in the electrochemical series are
discharged in preference to those higher up in the series. A cation which is lower in the
electrochemical series (less electropositive) will show a greater tendency to be discharged
than another which is higher up (more electropositive). The more electropositive a metal is,
the more it has the greater tendency to give up electron(s). So, it is expected that it will have
the least tendency to accept electron(s) and remain in solution as a positive ion while the less
electropositive metal becomes discharged as a neutral atom. H+ ion will be discharged in
preference to Zn2+ ion in solution where both are present in the same concentration during
electrolysis.
Therefore, the more electronegative an ion is, the greater the tendency to accept electrons.
Conversely, it will be expected to have the least tendency to donate or give up electrons to
the anode. In a solution containing SO42- and OH- ions, the OH- will be discharged in
preference to the SO42- which is left behind as a negative ion.

CATIONS (To Cathode)ANIONS (To Anode)

78
K+Electronegativity decreases downward F-
Na+SO42-
Mg2+ NO3-
Al3+Cl-
Zn2+ Br-
Fe2+I-
Sn2+ OH-
Pb2+
H+
Cu2+
Hg2+
Ag+
Au+Electropositivity increases upward

79
CONCENTRATION OF IONS
Increase in concentration of a given ion tends to promote its discharge from solution. The
influence of concentration is effective only when the two competing ions are closely
positioned in the electrochemical series, while it is minimal if the ions are widely spread in
their positions. In the electrolysis of brine (concentrated sodium chloride solution), Cl - ions is
discharged at the anode in preference to OH- ion due to the higher concentration of Cl- over
OH- and the closeness in their position in the series. At the cathode, the concentration of Na +
ion is far greater than that of H+ ion, yet H+ is preferentially discharged because of the great
distance between the positions of Na+ and H+ in the series which has rendered the effect of
concentration less important.

NATURE OF ELECTRODE
Inert electrodes do not take part in electrolytic reaction. Platinum and carbon (graphite)
usually behave as inert electrodes, though platinum is attacked by liberated chlorine and
carbon attacked by liberated oxygen. Some electrodes however influence the discharge of
ions because they have strong affinity for certain ions. For example in the electrolysis of
aqueous sodium chloride using platinum electrodes, H+ ions are preferentially discharged in
accordance with its position in the electrochemical series. If on the other hand a mercury
cathode is used, the mercury will associate itself with the Na+ ions to form the sodium
amalgam, Na/Hg. The discharge of sodium requires less energy than that of H+ ions,
therefore occur in preference.
Na+(aq) + Hg(l) + e- → Na/Hg(l)
Changing electrodes may influence preferential discharge because the electrodes possess
certain properties similar to those of the ion in the electrolyte. For example, the electrolysis
of copper (II) tetraoxosulphate(VI) using copper anode, neither SO42- nor OH- is discharged.

80
Instead, copper (II) atoms from the anode go into solution as Cu2+ions because the copper
atoms will give up their electrons more readily than SO42- or OH-. This principle is applied in
the extraction and purification of some metals.

ELECTROLYSIS
Electricity is generated by a chemical change using electrochemical cell, making it possible
for same electricity to be used up to bring about a chemical change using electrolytic cell.
Therefore electrolysis is defined as the chemical decomposition of an ionic compound
brought about by the passage of direct current through either a solution of the compound or
the molten compound.

TERMS USED IN ELECTROLYSIS

ELECTROLYTE:
This is a compound which conducts electricity and is decomposed in the process. For a
compound to behave as an electrolyte, it must be in a liquid form either as a molten
compound or an aqueous solution of the compound. Electrolytes conduct electricity by the
movement of ions to the electrodes and their subsequent reactions at the electrode. Some
terms used in electrolysis include the following:

ELECTRODES:
Electrode are defined as conductor inform of wires, rods or plates through which an electric
current enters or leaves the electrolyte. There are basically two types of electrodes:
* Anode electrode andCathode electrode

ANODE
This is the positive electrode by which the conventional current enters the electrolyte (or by
which electrons leave an electrolyte). It is the electrode which is joined to the positive
terminal of the electric supply.

CATHODE
This is the negative electrode by which the conventional current leaves the electrolyte (or by
which electrons enter the electrolyte). It is the electrode which is joined to the negative
terminal of the electric supply.

ELECTROLYTIC CELL

81
This is an assembly of two electrodes in an electrolyte and is used for the electrolysis of a
Substance. Electrolytic cell set up is also known as voltameter. In electrolytic cell, oxidation
takes place at the anode (positive electrode) while reduction takes place at the cathode
(negative electrode).

MECHANISM OF ELECTROLYSIS
Electrolysis is the chemical change brought about by the passage of direct current through an
electrolyte via electrodes.
Before the passage of current, the ions move about randomly in the electrolyte. When
electrolysis begins, the battery or generator of electric current pumps electrons from its
negative terminal (anode) to the cathode of the electrolytic cell. The negatively charged
cathode then attracts cations in the electrolyte to itself. The cations accept electrons to
become electrically neutral and are eventually discharged. The positive terminal (cathode) of
the battery drawselectronsfrom the anode of the electrolytic cell. Anions in the electrolyte are
then attracted to the positively charged anode, where they give up their electrons to become
electrically neutral and are also finally discharged. Hence, an electric current passes through
the complete circuit.

ELECTROCHEMICAL CELL
Electrochemical cell is a set - up of two different metals dipped into a solution of their salts
and are connected by a conductor. This arrangement gives an electrochemical cell. A
combination of two or more electrochemical cells gives a battery.

82
In any electrochemical cell, there are always two half cells, one undergoing reduction and the
other oxidation. Electricity is generated by a chemical change using electrochemical cell. In
both electrolytic cell and electrochemical cell, oxidation always occurs at the anode while
reduction takes place at the cathode. Electrons always flow from the anode to the cathode. In
an electrochemical cell, the negative electrode is the anode while the positive electrode is the
cathode. However in an electrolytic cell, the negative electrode is the cathode while the
positive electrode is the anode.

ELECTROLYSIS OF ACIDIFIED WATER (DILUTE

TETRAOXOSULPHATE (VI) ACID)

Acidified water is made by adding a few drops of tetraoxosulphate (VI) acid to water.
Electrolysis of acidified water is the same as the electrolysis of dilute tetraoxosulphate (VI)
acid.

83
The electrolytic cell used is designed for the collection of gaseous products at the two
electrodes and is known as HofmanVoltameter. The electrodes used are platinum foils. The
ions present in the electrolyte are:
H2SO4 H2O
+
Cations 2H (aq) H+(aq)
2-
Anions SO4 (aq) OH-(aq)
Concentration of ions High Low
-
Position in electrochemical OH ions are lower in the
series series than SO42-.

AT THE CATHODE:
H+ ion migrates to the cathode where they accept electron each to form neutral hydrogen
atoms. The hydrogen atoms then combine in pair to produce the diatomic molecules of
gaseous hydrogen.
H+(aq) + e-→ H
H + H →H2(g)

AT THE ANODE:
Both SO42- and OH- ions migrate to the anode. OH- being lower in the electrochemical series
is preferentially discharged and loses its electrons to the anode to become a neutral - OH
group. Each OH- loses its electrons to the anode to become a neutral – OH group.
OH-(aq) → OH + e-
Two neutral – OH groups react to form one molecule of water and one atom of oxygen.
OH + OH →H2O(l) + O
Gaseous oxygen is produced when the oxygen atoms combine in pairs to form diatomic
molecule.
O + O →O2(g)

SUMMARY OF REACTIONS
Cathodic half – reaction:
4H+(aq) + 4e-→ 2H2(g)

Anodic - half – reaction:

4OH-(aq)→ 2H2O(l) + O2(g) + 4e-

Overall reaction:
4H+(aq) + 4OH-(aq)→ 2H2O(l) + O2(g) + 2H2(g)
Electrolysis of dilute tetraoxosulphate(VI) acid produces 2 volumes of hydrogen at the
cathode and 1 volume of oxygen at the anode. i.e the ratio of hydrogen to oxygen by volume
is 2 : 1 respectively.
Although the percentage of ionization of water is very low, the discharge of OH- during
electrolysis disturbs the ionic equilibrium of water. To restore the equilibrium, more water
molecules ionize.
H2O(l)→ H+(aq) + OH-(aq)

84
The total amount of acid in the solution remains the same (unchanged) at the end of the
electrolysis, but its concentration increases due to the removal of water molecules.

ELECTROLYSIS OF COPPER (II) TETRAOXOSULPHATE

(VI) SOLUTION (USING DIFFERENT ANODES)

The electrolytic cell is designed to collect solid copper deposit at the cathode and a gas at the
anode. The electrolyte contains the following ions:

CuSO4 H2O
Cations Cu2+ H+
Anions SO42- OH-

85
Concentration of ions High Low
Position in the Cu2+ is just below H+ in OH- is lower in the series than
electrochemical series the series, SO42-
(i) With carbon or platinum electrode:
At the Cathode:
Both Cu2+ and H+ migrate to the cathode where Cu2+ being lower than H+ in the
electrochemical series are preferentially discharged. The Cu2+ acquires two electrons each
from the cathode to be deposited as metallic copper on the cathode as a result the cathode
gradually grows thicker. This reaction is the same whether a platinum, carbon or copper
cathode is used.
Cu2+(aq) + 2e- → Cu(s)

At the Anode (carbon or platinum):

Both SO42- and OH- migrate to the anode where OH- is preferentially discharged as oxygen
gas because it is lower in electrochemical series. The position of ions in the electrochemical
series dominates over their concentrations.
Each OH- loses its electrons to the anode to become a neutral – OH group.
OH-(aq) → OH + e-
Two neutral – OH groups react to form one molecule of water and one atom of oxygen.
OH + OH →H2O(l) + O
Gaseous oxygen is produced when the oxygen atoms combine in pairs to form diatomic
molecule.
O + O→O2(g)

SUMMARY OF THE REACTION:

Cathodic half – reaction:
2Cu2+(aq) + 4e- → 2Cu(s)

Anodic half – reaction:

4OH-(aq)→ 2H2O(l) + O2(g) + 4e-

Overall Reaction:
2Cu2+(aq) + 4OH-(aq)→2Cu(s) + 2H2O(l) + O2(g)
The electrolysis of aqueous copper(II) tetraoxosulphate (VI) solution produces copper
depositsat the cathode and oxygen at the anode. As the Cu2+ and OH- are gradually
discharged, the solution becomes acidic with tetraoxosulphate(VI) ion SO42-and hydrogen ion
H+ which remain in solution. This change is seen in the gradual fading away of the blue
colour of copper(II) tetraoxosulphate (VI) solution. Continuous passage of current will result
in subsequent electrolysis of dilute tetraoxosulphate(VI) acid, producing Hydrogen at the
cathode and oxygen at the anode.

At the anode (Copper):

Three possible mechanisms are possible when copper is used as the anode.
(a) Sulphation of the anode:
It involves discharge of SO42- by loss of electrons.

86
SO42-(aq) → SO4(s) + 2e-

(b) Discharge of OH-

OH-(aq) →OH(g) + e-
(c)Conversion of copper atoms of the anode to copper ions.
Cu(s) → Cu2+(aq) + 2e-
In all these three possible mechanism, the conversion of copper atoms to copper ions occurs
most readily because it requires least energy. Hence, no ions are discharged and there is no
change in the disposition and colour of the electrolyte, since copper is merely transferred
from the anode to the cathode during electrolysis.
Anode Electrolyte Cathode
- -
-2e +2e
Cu(s)→ Cu2+(aq)→ Cu(s)

ELECTROLYSIS OF BRINE (CONCENTRATED SODIUM

CHLORIDE SOLUTION)

The cathode used may be platinum or carbon but the anode must be carbon to resist attack by
chlorine.
NaCl H2O
Cations Na+ H+
Anions Cl- OH-
Concentration of ions High Low
Position in the Na is above H in the OH- is lower in the series than Cl-, but the
+ +

electrochemical series series, effect of concentration will be

pronounced.
At the cathode:
Na+ and H+ migrate to the cathode. Although Na+ is higher in the electrochemical series and
higher in concentration than H+, the effect of position in the electrochemical series will

87
dominate. So H+ is preferentially discharged because of its lower position in the
electrochemical series.
H+(aq) + e-→ H
Hydrogen gas molecules are formed by the combination of the atoms in pairs.
H + H →H2(g)
Hydrogen gas is obtained at the cathode.

At the Anode:
OH- and Cl- migrate to the anode. Cl- is preferentially discharged because of its higher
concentration than OH-. The effect of concentration is important here because Cl- and OH-
are close to each other in the electrochemical series.
Cl-(aq)→Cl(g) + e-
The chlorine atoms then combine in pairs to produce chlorine gas molecules.
Cl(g) + Cl(g)→ Cl2(g)
Chlorine gas is obtained at the anode.

SUMMARY OF THE REACTION

Cathodic half – reaction:
2H+(aq) + 2e-→ H2(g)
Anodic half – reaction:
2Cl-(aq)→Cl2(g) + 2e-
Overall reaction:
2H+(aq) + 2Cl-(aq)→ H2(g) + Cl2(g)
Equal volumes of chlorine and hydrogen are produced at the electrodes and the solution
gradually becomes alkaline due to the Na+ and OH- which are left behind in the solution.

Electrolysis of Fused Sodium Chloride, NaCl.

The ions present are: Na+ + Cl- (water is not present to provide the ions: H+ + OH-)
At the Cathode
2Na+ gains electrons and become reduced to the metal: 2Na+(aq) + 2e-(aq) → 2Na(s)
At the Anode
Cl- gives off electrons and becomes oxidized:
2Cl-(aq) → Cl2(g) + 2e-(aq)
This method is used for the commercial preparation of sodium metal and chlorine gas.

Electrolysis of CuCl2 Solution

The ions present are: H+ + OH- from water; Cu2+ + Cl- from CuCl2
At the Cathode
Cu2+, being lower in the electrochemical series is discharged in preference to H+
I.e., Cu2+(aq) + 2e-(aq) → Cu(s)
Note: copper metal is deposited as brown layer at the cathode.
At the Anode
The nature of anode used will determine the ions to be discharged. If carbon anode is used
Cl- will be discharged in preference to OH- because it is in greater concentration.
I.e. 2Cl-(aq) → Cl2(g) + 2e-(aq) Chlorine gas is produced.

88
But if copper metal is used as anode, where Cl- or OH- is discharged, but the copper anode
decomposes into solution
Cu(s) → Cu2+(aq) + 2e-(aq)
The total concentration of the solution (i.e. Cu2+ and Cl- will remain the same) if copper
anode is used. Generally, reduction occurs at the cathode while oxidation occurs at the anode.
Electrolysis is not a spontaneous reaction as electricity is needed to drive the reactions at
both electrodes, hence work is done on the system.

SUMMARY OF PRODUCTS DISCHARGED AT

ELECTRODES DURING ELECTROLYSIS OF COMMON
ELECTROLYTES
Electrolyte Cathode Product Anode Product Effect on
discharged discharged electrolyte
at cathode at anode
Acidified water(dilute Platinum Hydrogen Platinum Oxygen Concentrati
tetraoxosulphate(VI) gas(2 gas(1 on of H+
acid) volumes) volume) and SO42-
increase as
water is
removed
making
electrolyte
more acidic
Concentrted Copper Copper Carbon Chlorine Removal of
copper(II)chloride deposits gas Cu2+ and Cl-
dilutes
electrolyte
Dilute copper(II)chloride Copper Copper Carbon Oxygen gas Concentrati
solution deposits on of H+
and Cl-
increases,
making
electrolyte
acidic
Concentrated Copper Copper Copper Copper Concentrati
copper(II)chloride or deposits anode on of
copper(II)tetraoxosulphat dissolves electrolyte
e(VI) solution remains
unchanged
Concentrated Copper Copper Platinum Oxygen gas Concentrati
copper(II)tetroxosulphate deposits on of H+
(VI)solution and SO42-
increase,
making
electrolyte
acidic
Concentrated Carbon Hydrogen Carbon Chlorine Removal of

89
hydrochloric acid gas(1 gas H+ and Cl-
volume) dilutes
electrolyte,
making it
less
Concentrated sodium Carbon Hydrogen Carbon Chlorine Concentrati
chloride solution(brine) gas(1 gas(1 on of Na+
volume) volume) and OH-
increase,
making the
electrolyte
alkaline
Molten sodium chloride Carbon Sodium Carbon Chlorine Concentrate
gas d remains
unchanged.
Concentrated sodium Platinum Hydrogen Platinum Oxygen Concentrati
hydroxide solution gas(2 gas(1 on of Na+
volumes) volume) and OH-
increase as
water is
removed,
making
electrolyte
more
alkaline

LAWS OF FARADAYS
Faraday’s law of electrolysis states that the amount of substance liberated at the electrodes
during electrolysis depends on:
i. the magnitude of the steady current passed
ii. the time of passing the steady current
iii. the charge on the ion of the element liberated

FARADAY’S FIRST LAW OF ELECTROLYSIS

Faraday’s first law of electrolysis states that the mass (m) of a substance discharged at an
electrode during electrolysis is directly proportional to the quantity of electricity (Q) passing
through the electrolyte.
Mathematically;
M αQ
Where;
Q = It
So,
M α It
The first law of electrolysis can also be stated as the mass of element discharged during n
electrolysis is directly proportional to the magnitude of the current and the time of flow of the
current
Therefore,

90
M α Ixt
m = EIt
E = m
It
Therefore;
1 = It (i)
E m
Where:
m = Mass of the substance expressed in grams
E = Electrochemical equivalent of the substance which is the mass in grams of the
substance discharged by the passage of 1 coulomb of electricity.
Reciprocal of E is the charge to the mass ratio is cF.It is constant for a particular element.
M
Therefore; It= cF
MM
M = Molar mass of the substance in gmol-1
Rearranging;
m = It
M cF
Where
Number of moles (n) = m
M
n = It
cF
1 mole of electron = 1 Faraday (1F) of electricity = 96500C = 6.02 x 1023 electrons
For 1 mole (molar mass) of a substance to be discharged, cF coulombs of electricity will be
required.
Where;
C = Charge on the element (number of Faradays)
F = Faraday’s number
1F liberates 1 mole of K+, charge = +1
2F liberate 1 mole of Cu2+, charge = +2
3F liberate 1 mole of Al3+, charge = +3
Molar mass (m) require charge (c) x faraday (F) coulomb
M →cF
cF = M
When, c = 1, F = 1, we have
1 =M
cF
But, c = 1, F = 1, means thatcF = Z
Therefore, 1 = cF (ii)
Z M
Equate equation (i) and (ii), we have:
It = cF
m M

91
M = Molar mass of the substance in gmol-1
Rearranging;
m = It
M cF
Number of moles (n) = m
M
n = It
cF

FARADAY’S SECOND LAW:

Faraday’s second law of electrolysis states that when the same quantity of electricity is
passed through different electrolytes, the relative number of moles of the elements
discharged is inversely proportional to the charges on the ions of the elements.
Mathematically, n α 1
c
Where; nc = constant
n is the amount in moles, of the element liberated, and
c is the charge on its ion
For two or three different elements
n1c1 = n2c2 = n3c3
The amount of electricity in coulombs required to produce 1 mole of a substance is a simple
whole number multiple of2 96 500
That is the amount of electricity (Q) in coulombs divided by 96,500 is a simple whole
number
To produce 1 mole quantity of
of underlined electricity Q/96,500
substance required (Q)
96,500/96,500
In each example,
Na+ + e- → Na 96,500 coulombs
=1 Q/96,500 is a simple
193,000/96,500 whole number.
Cu2+ + 2e- → Cu 193,000 coulombs If n represents that
=2 simple whole number,
and Q is the quantity of
289,500/96,500 electricity in coulombs,
Fe3+ + 3e- → Fe 289,500 coulombs then
=3 n = Q/96,500
The quantity 96,500 is given the name the Faraday (or Faraday Constant) and the symbol F
F is equal to the quantity of electricity carried by one mole of electrons:
F = Avogadro's Number × charge on electron in coulombs
= 6.022 × 1023 mol-1 × 1.602192 × 10-19 C
= 96,484 C mol-1 (usually rounded up to 96,500 C mol-1 in high school chemistry)
 Faraday's Laws of Electrolysis Calculations:
Q = n(e-) × F
Q = quantity of electricity measured in coulombs (C)
n(e-) = moles of electrons used
F = the Faraday (Faraday constant) = 96,500 C mol-1

92
We can calculate the mass of a substance produced during an electrolysis experiment by:
i. calculating the moles of electrons used: n(e-) = Q/F
ii. using the moles of electrons to calculate the moles of substance produced using
the balanced reduction (or oxidation) half reaction equation
iii. using the moles of substance to calculate the mass of substance:
mass = moles × molar mass

USES OF ELECTROLYSIS
Electrolysis is of great importance in the industry. Its applications are:
There are several uses for electrolysis, these include:
1. Purification of Metals such as Cu, Hg, Ag and Au.
Purification of copper is carried out using CuSO4 solution as electrolyte, the impure copper
as the anode and the cathode a strip of pure copper. During the process, the anode (impure
copper) decomposes and goes into solution as Cu2+,
i.e. Anode reaction: Cu(s) → Cu2+(aq) + 2e-(aq) - oxidation reaction.
While at the cathode, pure copper is deposited i.e. Cathode reaction:
Cu2+(aq) + 2e-(aq) → Cu(s) - reduction reaction
The impurities, which include silver (Ag) and gold (Au) are not discharged in the process,
but collect in a sludge at the bottom of the cell and are recovered from it.

2. Extraction of metals such as Na, Mg, Ca and Al

In the production of aluminium, pure aluminium oxide, Al2O3 (alumina) is obtained from the
chief raw material – bauxite, Al2O3.2H2O. The purified Al2O3 is then electrolyzed in solution
in molten cryolite (Na3AlF6 – sodium hexaflouroaluminate (III)) to obtain pure aluminium.
Cryolite is unchanged in the process and can therefore be used indefinitely.
Cathodic reaction: 2Al3+(aq) + 6e-(aq) → 2Al(s)
Anodic reaction: 3O2-(aq) → 3/2 O2(g) + 6e-(aq)
Note: The carbon anodes are constantly attacked by the oxygen produced at the anode.
Hence, the anodes are usually changed.
The cryolite serves to dissolve the Al2O3, thereby enabling it to conduct electricity and
decompose. Alumina, Al2O3 is not dissolved in water because it reacts vigorously with water.

3. Industrial preparation of certain chemicals such as NaOH,

H2 and Cl2
We have already discussed the electrolysis of fused NaCl (without water). Sodium and
chlorine are produced commercially by the electrolysis of NaCl in the molten condition
(Down’s process). Due to high melting point of sodium chloride (about 800oC), calcium
chloride is added to it to lower it to about 600oC.
Cathodic reaction: 2Na+(aq) + 2e-(aq) → 2Na(s) – reduction.
Anodic reaction: 2Cl-(aq) → Cl2(g) + 2e-(aq) – oxidation
Chlorine can also be produced through the electrolysis of conc. sodium chloride solution
(Brine).

93
 (a) Production of Oxygen
The electrolysis of dilute H2SO4 and CuSO4 solutions produce oxygen at the anode.

(b) Production of NaOH

The electrolysis of conc. sodium chloride solution using carbon electrodes results in the
solution being highly concentrated of sodium hydroxide. Sodium hydroxide may be prepared
commercially by this method.
Also, using mercury cathode, Na+ is discharged, and then reduces to the metal. i.e.
Na+(aq) + e-(aq) → Na(s)
Then Na(s) combines with the mercury to for a mixture - sodium amalgam Na/Hg.
The sodium amalgam is run into water, resulting in the reaction of sodium with water to form
NaOH solution, while the mercury is dissociated from it.

1. Extraction of metals:
Many metals such as (Na, Ca, K, Mg, Al, Zn) and non – metals such as (H2, F2, Cl2) are
obtained either by the electrolysis of their ores or the electrolysis of their fused compounds or
their aqueous solutions.
An example is the extraction of aluminiumfrom purified bauxite (Al2O3)

2. Purification of metals:
The less electropositive metals, e.g copper, mercury, silver and gold, tend to occur in the
uncombined form in ores. These ores are contaminated with impurities such as sand,
limestone and iron compounds. Example is the extraction of copper from copper ore.
Electrolytic process is employed where the impure ore serves as the anode and a pure copper
plate serves as the cathode while the electrolyte can be any soluble copper salt, such as
copper (II) tetraoxosulphates (VI).

At the anode:
The metallic copper atoms in the ore give up two electrons each to go into solution as copper
ions.
Cu(s) → Cu2+(aq) + 2e-

At the cathode:
The copper ions in the solutionsare attracted to the cathode where they receive two electrons
each from the cathode to become neutral copper atoms which are then deposited on the
cathode.
Cu2+(aq) + 2e-→ Cu(s)

The summary is the transfer of copper atoms from the impure ore (anode) to the
cathode.Similar arrangements are used in the extraction and purification of silver, mercury
and gold. The electrolyte is always the soluble salt of the metal being extracted or purified,
the anode is the metallic ore or impure metal, while the cathode is a pure piece of the metal
on which the pure metallic atoms can be deposited.

3. Electroplating:

94
Electroplating is a method of coating the surfaceofone metal with another metal such as
copper, silver, chromium, nickel or gold, by means of electrolysis, for decoration, improved
appearance or decoration against corrosion. Materials to be coated include table ware,
cutlery, jewellery, iron or steel objects, such as metallic parts of motor – cars.
The object to be electroplated is first cleaned and coated with graphite, if it is not a conductor
of electricity. It is then made the cathode in an electrolytic cell. That means the cathode is the
metallic object which is to be coated or plated. The anode is the pure metal to be deposited
on the object while electrolyte is the solution of the soluble salt of the pure metal used as the
anode.
In silver – plating a spoon,
*The cathode is the spoon
*The anode is the silver rod
* The electrolyte is a soluble salt of silver, usually a silver trioxonitrate (V) solution.
When current is passed through the cell, the plating metal dissolves at the anode, and the ions
produced migrate to the cathode, where they are discharged and deposited as a layer on the
object.
At anodeInsolutionAt cathode
-e- +e-
Silver – plating Ag(s) → Ag+(aq) → Ag(s)
+
Copper – plating Cu(s) → Cu (aq) → Cu(s)

The thickness of the plating may be controlled by adjusting the magnitude of the current and
the duration of the process.
Sometimes, a series of plating may be necessary. Chromium does not adhere well to steel and
allow moisture to pass through it so it is eventually stripped off. So in chromium plating
steel, the steel is first coated with copper which provides adhesion. This is followed by
coating with a layer of nickel to for protection against corrosion and finally with a layer of
chromium for a -tarnish - free work.
4. Preparation of certain important compounds, such as
sodium hydroxide and sodium trioxochlorate (V)
5. In the production of gases such as hydrogen, chlorine and
oxygen.

ELECTRODE POTENTIAL
Electrode potential is the potential difference set up between an element and a solution of its
ions. It is a measure of the tendency of an element to form ions.
When a metal plate is dipped inside a solution containing its ions, some of the atoms from the
metal plate will ionize and enter the solution as positively charged ions, leaving behind their
valence electrons on the surface of the plate. For example, in a univalent ion;

M(s) → M+(aq) + e- (i)

Plate SolutionPlate

95
Also, some metallic ions in the solution may take up the electrons from the metal plate and
deposit on the plate as neutral atoms, leaving behind an excess of anions in the salt solution,
as shown below;

M+(aq) + e- → M(s) (ii)

SolutionPlate Plate
When reaction (i) occurs, then the metal plate or electrode potential becomes negatively
charged with respect to the solution or electrolyte. This is common with metals above
hydrogen in the electrochemical series. If reaction (ii) occurs, the plate becomes positively
charged with respect to the solution. This is common with metals below hydrogen in the
electrochemical series. This will result to setting up an electrode potential called electrode
potential for the metal ion/metal system between the metallic electrode and the electrolyte.
For example,
Silver ions/silver system:
When silver plate is dipped into a solution of silver trioxonitrate (V), the reaction will be:

Ag+(aq) + e-→ Ag(s)

Solution Plate Plate

The silver ion from the solution acquires an electron from the silver plate to become
deposited as a neutral silver atom on the plate. Thus, the silver plate will become positively
charged on its surface because of electron deficit while the solution becomes negatively
charged due to excess of the negatively charged trioxonitrate (V) radical (NO3-)
The silver plate is said to be positively charged with respect to the solution. A potential
difference, is therefore set up between the silver plate and solution.

Zinc ions/Zinc system:

When zinc plate is dipped into a solution of zinc tetraoxosulphate (VI), the net reaction is:

Zn(s) → Zn2+(aq) + 2e-

Plate Solution Plate

The neutral zinc atomon the plate gives up two electrons to the plate and enters into the
solution as positively charged zinc ion. This leads to the zinc plate becoming negatively
charged due to the excess electrons on its surface while the solution becomes positively
charged because of the excess zinc ions inside it. The zinc plate thus becomes negatively
charged with respect to the solution. A potential difference called electrode potential is also
set up between the plate and the solution.

96
 Electrode potential varies from one metal ion/metal system to another. Electrode potential
for a given system depends on:
1. The overall energy change:
Metals that are far apart in their position on the series will give high energy change when
combined in electrochemical cell. Thus, a high emf will be obtained from the cell.
2. The concentration of ions in solution:
Higher concentration gives lower electrode potential (voltage) and vice versa.

3. The temperature:
Moderate temperature gives high potential difference when a metal rod is dipped into a
solution of its salt, the reduced and oxidized forms of the metal come into contact.
For example, a zinc rod dipped into a solution of zinc sulphate – there are two possible
tendencies:
1. For zinc ions in solution near the rod to draw electrons from the natural zinc atom in the
rod and become reduced and deposited as neutral zinc atoms.
i.e. Zn2+(aq) + 2e-(aq) → Zn(s) – reduction.
2. For neutral zinc atom in the rod to go into solution as zinc ions, each leaving two electrons
behind on the metal rod.
i.e. Zn(s) → Zn2+(aq) + 2e-(aq) – oxidation

97
Due to the above possible tendencies, there will exist a double layer of positive zinc ions and
electrons on the rod.

A potential will exist across this layer- this is called electrode potential. Note: the tendency
for a neutral metal to go into solution as ions depends on the relative ease with which
electrons can be removed from it (ionization potential) and on the available energy when
these ions are hydrated (hydration energy).
The more electropositive a metal is (example: Zn, with high ionization potential), the greater
the tendency to go into solution as ions – oxidation.
The solution becomes more concentrated with the positive ions, and the electrode becomes
more negative compared with the solution because electrons are deposited on it.
On the other hand, a less electropositive metal (example, copper) in the solution of its salt,
will have its ions more likely to acquire electrons from its rod and become reduced – rather
than being oxidized.
Therefore, the concentration of Cu2+ in solution is less, and the concentration of electrons on
the rod becomes less compared with the solution.

Standard Electrode Potential

Standard electrode potential of a metal ion/metal system is the potential difference set up
between the metal and one – moldm-3 solution of its ions at 25oC with reference to standard
hydrogen electrode with zero volts.
By convention, the standard electrode potential must be reduction potential and are the emf
of electrochemical cells in which there is a hydrogen electrode on the right. E.gConsider the
cell notation below:
(Pt) H2/H+ // Cl-/Cl2 (Pt)
Pt = Platinum
// = porous partition or salt bridge connecting the two half cells together.
/ = Phase boundaries
On the left of the above cell is a hydrogen electrode and on the right is a chlorine electrode.
Half - cell reaction for the left:

98
1/2H2 → H+ + e- (Oxidation) Eo(lhs)
Half - cell reaction for the right:
1/2Cl2 + e- → Cl-(reduction) Eo(rhs)
Net (Overall) ionic reaction:
1/2H2 + 1/2Cl2 → H+ + Cl-
Emf of the cell Eo(cell) is the difference between the right hand side electrode potential Eo(rhs)
and the left hand side electrode potential Eo(lhs)
i.eEo(cell)=Eo(rhs) - Eo(lhs)
Where:
Eo = Electrode potential
lhs = Left hand electrode (Anode)
rhs = Right hand electrode (Cathode)
Eo(cell) = Eo(cathode) - Eo(anode)
Considering Daniel cell notation as shown below:
Zn/Zn2+//Cu2+/Cu
At the right hand electrode, the half - cell reaction is:
Zn(s) → Zn2+(aq) + 2e-(Oxidation)
At the left hand electrode, the half - cell reaction is:
Cu2+(aq) + 2e- → Cu(s) (Reduction)
Net (Overall) reaction:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Supposing the following values were given:
Zn(s) → Zn2+(aq) + 2e-Eo = -0.763V
Cu2+(aq) + 2e- → Cu(s)Eo = +0.33V
NOTE:
Eo(cell) = Eo(rhs) - Eo(lhs)
From the cell notation:
Zn/Zn2+//Cu2+/Cu
The electrode on our right hand side (rhs) is the copper while the one on our left hand side
(lhs) is the zinc.
Eo(rhs) = +0.33V and Eo(lhs) = -0.763V
Substituting we have:
Eo(cell) = 0.337 - (- 0.763)
Eo(cell) = 0.337 + 0.763
Eo(cell) = +1.1V
To measure the standard electrode potential, EƟ of a metal in its salt solution (1 M) standard
hydrogen electrode (at standard conditions – 1 M ion concentration, temperature of 298 K
and a pressure of 1.013 x 105 N M-2) is coupled with it to form an electrochemical cell.
Example, to determine the standard electrode potential, EƟ of zinc immersed in a solution of
1 Molar Zn2+. This is coupled with the standard hydrogen electrode. Note: standard hydrogen
electrode is composed of pure hydrogen at 1.013 x 105 N M-2 (standard pressure) passed over
platinized platinum dipped into a molar solution of H+(aq).

99
When the two electrodes are connected by a wire, a spontaneous reaction occurs and
electrical energy is generated. The following reactions occur at the different electrodes:
hydrogen been lower in the electrochemical series – reduction would occur at the standard
hydrogen electrode, i.e. electrons flow from the zinc electrode (anode – due to excess
electrons on the zinc rod) to the hydrogen electrode (cathode).
The half-cell reactions are:
Zn(s)→Zn2+(aq)+ 2e-(aq) – oxidation (Anode)
2H+(aq)+ 2e-(aq)→ H2(g)– reduction (Cathode)
Net reaction: Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
Both electrodes are standard. The measured e. m. f. is the sum of the standard electrode
potentials of the two electrodes.
Note: the standard electrode potential of hydrogen electrode is zero. Hence, the measured e.
m. f. of the cell is also the standard electrode potential, EƟ of the standard electrode of the
metal in its salt solution (i.e. of Zn in 1 molar Zn2+ solution).
By convention, a +ve sign is assigned to the EƟ value if the electrode is that of a metal which
is more reduced than hydrogen, or which is less oxidized than hydrogen.
A –ve sign denotes EƟ for electrode of a metal which is less reduced than hydrogen, or which
is more oxidized than hydrogen.
Therefore, EƟ is based on reduction, and the standard EƟ of Zn/Zn2+(1M) electrode is -0.76
volt.

Cell of zinc electrode coupled with hydrogen electrode.

Note: The cell is represented as Zn(s)/Zn2+(aq) (1 M) // 2H+(aq)(1 M)/ H2(g) Anode (oxidation)
Cathode (reduction)
Electrons flow from the anode to the cathode
VOLTAIC OR GALVANIC CELL
When two electrode potentials are joined together by a wire, an electrochemical, voltaic or
galvanic cell is produced.
Example, a Zn metal in a Zinc salt solution joined to a Cu metal in a Cu salt by a conducting
wire.

100
From the electrochemical series, it is clear that Cu2+ is more reduced than Zn2+.
This means that Cu2+ will acquire electrons and become reduced more readily than Zn2+.
Hence by connecting their electrode potentials, the Zn electrode will lose electrons and
become oxidized.
Zn(s) → Zn2+(aq) + 2e-(aq)
These electrons will flow from the Zn rod through the conducting wire into the Cu electrode,
where they are picked up by the Cu2+ to become reduced.
Cu2+(aq) + 2e-(aq) → Cu(s)
Thus electricity is generated. The U-tube, which connects the two electrode potentials
contains a salt (e.g. KCl), and is called a salt bridge.
The essence of the salt bridge is to provide oppositely charged ions in each electrode
potential to neutralize the ions formed and maintain electrical neutrality.
That is, the positive Zn2+ ions which are formed and accumulated at the anode are neutralized
by Cl- of the salt (KCl) in the bridge. In the same way, the negative ions, SO42-) which
accumulate at the cathode as a result of the reduction of Cu2+ to Cu(s) are neutralized by K+
of the salt, KCl in the bridge.
By this, a continuous flow of current is ensured. The e.m.f. of the cell is the sum of the
electrode potentials of the two components of the cell, that is, oxidation potential of Zn/Zn 2+
(+0.76 volt) and reduction potential of Cu2+/Cu (+0.34 volt).
I.e. 0.76 + 0.34 = +1.10 volts.
Note: This process is spontaneous, which means, no electricity or any other external aid is
applied to effect the changes at both electrodes, and useful work is done by the system.
Chemical energy is converted into electrical energy (this is different from electrolysis in
which electrical energy is obtained from an external source to cause chemical change (i.e.,
decomposition) at the electrodes – non spontaneous).
Electrons flow from the anode to the cathode (in electrolysis, conduction of electricity is as a
result of migration of opposite ions to the electrodes, i.e., anions to anode and cations to
cathode).
The voltaic cell above is denoted as Zn/Zn2+(aq)(1 M) Anode (oxidation) // Cu2+(aq)/Cu(s)
Cathode (reduction)

Using a single electrolyte

101
A cell which is composed of two different electrolytes (e.g. the one above) is not efficient as
a result of what is commonly known as liquid junction potential, which arises from the
exchange of ions between the two electrolytic solutions through the junction.
The reversible nature of the cell is affected by this junction. A salt bridge eliminates this
effect to a large extent, but not completely. This effect can be completely eliminated by
avoiding liquid junctions altogether by using a single electrolyte.
For example: considering the simple cell below

Anodic reaction: Zn being higher in the electrochemical series (i.e. with lower reduction
potential than Cu) ionizes, leaves electrons on its plate and goes into solution
Zn(s) → Zn2+(aq) + 2e-(aq)
The electrons move through the wire to the cathode.
Cathode reaction: The cathode is the Cu plate. Here, the hydrogen ions from the dissociation
of the electrolyte, H2SO4(aq) → 2H+(aq) + SO42-(aq) pick up the electrons (from the anode) and
become discharged.
2H+(aq) + 2e-(aq) → H2(g)
In fact, the formation of hydrogen gas is a proof of the process occurring. The electrons from
the anode move through the external wire into the cell, hence the bulb lights up of course.
Note:
The single electrolyte to be used must be one with the positive end of greater reduction
potential than the anodic metal ion and lower reduction potential than cathodic metal ion (i.e.
H+ from H2SO4 has greater reduction potential than Zn2+ and lower reduction potential than
Cu2+) – this is to ensure that electrons move from the anode to the cathode through the
conducting wire.
The use of NH3 is to take Zn2+ away from the solution by forming a complex ion with it: Zn2+
+ 4NH3 → Zn(NH3)42+
Ammonia should always be present whenever zinc is used as the anode.
The cathode is a metal of higher reduction potential than the anode, and is thus reduced in the
process.

102
The anode generally wears out as the process goes on (due to its dissolution), and would
therefore need to be changed after sometime.
A practical application of the use of a single electrolyte is in the construction of Leclanche
Dry Cell.
The Cell is contained within a cylindrical zinc can, which serves as the anode. The cathode is
a carbon rod and is surrounded by an electrolytic paste mixture of ammonium chloride, zinc
chloride, and manganese dioxide with porous inert material such as paper pulp or cotton
waste.

Leclanche Dry Cell

A paper liner separates the zinc can from the paste; therefore, the electrons required for the
cathode reaction must pass through the external circuit and enter the cell through the carbon
rod. The cell is sealed with sealing wax to prevent loss of water from the paste by
evaporation – water must be present in the paste to permit movement of ions.
The only reason for calling it a ‘dry cell’ is that the sealed zinc can prevents the moist
electrolyte from leaking out.
At the Anode: The zinc atoms are oxidized: Zn(s) → Zn2+(aq) + 2e-(aq)
The electrons move to the cathode, to be taken up by the positive end of the electrolyte,
NH4Cl (NH4+), i.e.,
NH4Cl → NH4+ + Cl- which is of higher reduction potential than Zn2+
At the Cathode: 2NH4+ + 2e- → 2NH3 + H2
2MnO2 + H2 → Mn2O3 + H2O
The NH3 that is formed combines with Zn2+ ions from the anode reaction to form complex
ions: Zn2+ + 4NH3 → Zn(NH3)42+
Note: The presence of zinc chloride is to establish a potential at the anode. i.e. Zn in its salt
solution

103
MnO2 oxidizes the hydrogen formed at the cathode to H2O. This is because hydrogen
polarizes the cathode.

PREDICTION OF SPONTANEOUS REDOX REACTIONS

To determine whether or not a combination of two electrode potentials will generate
electricity (i.e. spontaneous) by the direction in which they are applied, take the sum of their
standard electrode potentials, i.e. oxidation potential + reduction potential, to obtain the
e.m.f. of the cell.
A positive value of the. e.m.f. indicates that the combination will generate electricity (i.e.
spontaneous). This is because, by the expression, ∆GƟ = - n FEƟ, ∆GƟ will be –ve since EƟ
(standard. e.m.f. of the cell) is +ve.
F is Faraday, n is the number of moles of electrons transferred in the half reactions as written.
If the e.m.f. value is –ve, then ∆GƟ will be +ve – this indicates that the combination will not
produce electricity (non- spontaneous).
Note: when EƟ value is +ve, ∆GƟ value will be –ve – spontaneity. When EƟ value is –ve, ∆GƟ
value will be +ve – non-spontaneity.
Examples: 1. Consider a cell of Fe in its salt solution as the anode and Ni in its salt solution
as the cathode. Will this cell be spontaneous?
Solution:
Anode reaction: Fe → Fe2+ + 2e- ; EƟ = +0.44 volt – oxidation potential
Cathode reaction: 2e- + Ni2+ → Ni; EƟ = -0.25 volt – reduction potential
Net reaction: Fe + Ni2+ → Fe2+ + Ni ; EƟ = +0.19 volt.
The value of e.m.f. (EƟ) is +ve, then the process is spontaneous (i.e., electricity will be
generated).
2. Consider a cell of hydrogen electrode as cathode, and the anode Ag in solution of silver
salt. Determine if its spontaneous.
Solution:
Anode reaction: 2Ag → 2Ag+ + 2e- ; EƟ = -0.80 volt – oxidation potential
Cathode reaction: 2e- + 2H+ → H2 ; EƟ = 0.00 volt – reduction potential
Net reaction: 2Ag + 2H+ → 2Ag+ + H2 ; EƟ = -0.80 volt.
Here, the value of e.m.f. (EƟ) of the cell is –ve.
This indicates that the cell as arranged is not spontaneous. I.e., electricity will not be
generated.
However, to make the system spontaneous, the direction of arrangement must be reversed.
I.e., the cathode should be Ag in the solution of its salt, and hydrogen electrode the anode.
This goes to confirm the order of reduction as given by the electrochemical series.
I.e. Ag is lower than H, hence its ions are more reduced, and will make the cathode for this
system to be spontaneous. Thus, the standard electrode potential value of Ag as the cathode
changes to +ve (+0.80 volt) Note: when you change the direction of the electrodes, their EƟ
values also change to the opposite sign.
General note:
Electrolytic cells and voltaic cells are types of electrochemical cells; i.e., electric current and
chemical reactions are involved in the operation of both of them.

104
In electrolytic cells, a direct electric current from an outside source causes non-spontaneous
oxidation-reduction reactions to take place, but in voltaic cells, oxidation- reduction reactions
take place simultaneously, producing electric current.
In either types of electrochemical cell, oxidation occurs at the anode, and reduction occurs at
the cathode.

CORROSION AS AN ELECTROLYTIC PROCESS

Corrosion in metals have been found to be electrochemical process – simple half-cell
reactions are involved. Example, the corrosion of iron (also called rusting).
Rusting in iron is promoted by the following factors:
(a). The presence of water and air.
(b). The presence of H+ ions, which speeds up the process.
(c). The presence of less reactive metals such as tin and copper.
(d). The presence of strain points in the metal.
(e). The presence of certain salts solutions, which are believed to be catalytic in their
reactions.
Rusting process can be explained thus:
1. The presence of less reactive metals as impurities in the iron set up a potential difference at
a strain point between iron atoms, and in the presence of water, the iron readily loses
electrons in the aqueous solution, which acts as electrolyte.
I.e. Fe(s) → Fe2+(aq) + 2e-(aq)
Hence, the iron becomes a kind of an anode while the cathode is the metal impurities. The
iron(II) ion in the solution is readily oxidized by oxygen to iron(III) oxide, which becomes
hydrated.
The overall reaction may be represented as: 4Fe + 3O2 + 2xH2 → 2Fe2O3 . xH2O
Note: Fe2O3.xH2O is the rust.
Corrosion affects all reactive metals. i.e., metals that can easily oxidize.
M(s) → Mx+ + xe- - this process enables corrosion to affect them.
Examples of such metals with relative high oxidation potential are Al, Zn and Fe.
The rust layer on the iron is soft and porous, allowing water and air to continue the rusting
process, unlike the corrosion layer of oxides of metals like Al and Zn.
Pure ion will not rust, because the possibility of local potential difference promoted by
impurities will not arise.

Prevention of Corrosion
Corrosion will be prevented if at least one of the processes involved in causing it is
disallowed from occurring. Thus, all methods used to prevent corrosion are based on this
principle. The most effective method of preventing corrosion in iron is the cathodic
protection.
By this method, a more electropositive (or more reactive) metal (e.g. Zn or Mg) is made the
anode and the iron, the cathode. A conducting wire is connected between them. Thus, the
iron is prevented from going into solution as Fe2+, i.e. the reaction:
Fe(s) → Fe2+(aq) + 2e-(aq) is prevented from taking place.
I.e. Anodic reaction: Zn(s) → Zn2+(aq) + 2e-(aq)
Cathodic reaction: Fe2+(aq) + 2e-(aq) → Fe(s)

105
This method is applied in the protection of buried iron petrol tank reservoir from rusting. the
iron. Also, Zn2+ reacts with oxygen to form a film of zinc oxide, which protects the surface
from further corrosion.

Other methods of preventing corrosion are:

(1). Galvanizing with zinc:– Zinc is used to galvanize (i.e. coat) iron in steel to prevent
rusting of pipes in many plumbing systems. In the presence of moisture and when galvanized
iron is scratched, the Zn being higher in the electrochemical series losses electrons and goes
into solution as Zn2+ ions – it therefore corrodes instead of iron
(2). Tinning: - Tin is used to protect iron from rusting, as in tin cans. This is possible because
tin is very resistance (i.e. unreactive) to chemical attack.
However, this is only sustained if the can is not scratched. If it is scratched, a very high
potential difference is set up between the tin and iron, with the tin pulling electrons from
iron, thereby causing the reaction Fe→ Fe2+ +2e- to occur (i.e. iron begins to rust and at a
faster pace than usual).
(3). Electroplating: - This is the electrical precipitation of one metal onto the surface of
another to give improved appearance or greater resistance to corrosion. The metal to be
electroplated is made the cathode and the anode is the metal (pure), which is required.
A direct current is passed through the solution (electrolyte, which is a solution of the salt of
the required metal). Example: in electroplating a metal with silver, the cathode is the metal
(iron) to be electroplated, the anode is the pure silver and the electrolyte is either sodium or
potassium dicyanoargentate(I) solution, KAg(CN)2.
By passing a direct current into the solution, the following reactions occur at the electrodes:
Cathodic reaction: Ag+(aq) + e-(aq) → Ag(s)
Silver deposited on the cathode (iron) Anodic reaction: Ag(s) → Ag+(aq) + e-(aq) - Silver
dissolved
Note: The process is the transfer of pure Ag from the anode to the cathode.
(4). Greasing, painting or spraying the iron bar – the essence is to prevent water and oxygen
from getting to it.
(5). By surrounding the metal (iron) with fumes from a material that discourages rust, such as
camphor (C10H16O) or mothballs. Some mothballs are naphthalene (C10H8) while others are
Para dichlorobenzene.
(6). By storing iron is a tight wooden box – wood acts as a fairly good barrier to humidity
and absorbs moisture.
(7). By preventing the gathering of dust on iron - dust absorbs moisture.

106
REMOVAL OF RUST FROM IRON
When iron begins to rust, it will puff up and expose clean metal to the open air, allowing rust
to continue to the depths of the metal. The following methods can be applied to remove rust:
Sand Blasting or Bead Blasting
This is the crudest method of removing rust from metals and it is a standard practice in auto
body repair-shops. Sand blast will also remove some good metal and will work – harden the
metal surface. Hence, glass beads blasting is used for more delicate parts. Immediately after
any blasting, the metal surface is clean and exposed; so it is essential to rust proof it. In auto
bodywork, the metal is often treated with acid-metal wash (a solution of phosphoric acid and
alcohol) to remove moisture, followed by self - etching primer.
Sandpaper and steel wool will also remove rusting, but they don’t get into tiny crevices.
Rubber abrasive sanding blocks are good at removing a thin coat of rust and can also remove
rust from minute pores in the metal.

Etching with Phosphoric Acid

Phosphoric acid has a unique property of dissolving hydrated iron oxide (i.e. rust) quickly
while etching iron very slowly (by removing molecules of water from it). This means that
metal can be left in the acid for much longer time than necessary with very little damage.
However, the acid will attack bare metal slowly and will start the process of hydrogen
embrittlement, hence the minimum etch time that removes all rust should be used. Another
advantage of phosphoric acid is that it leaves a fine coating of iron phosphate behind. (iron
phosphate prevents rust) and leaves a hard, bright metal finish – this is because it will etch
the surface slightly, exposing new, bare metal.
Common products which contains phosphoric acid are cola drinks, such as Coca cola. Cola
drinks also contain carbonic acid, which etch rust as well. This is why when you leave a coin
in some quantity of cola drinks, the coin comes up with shiny surfaces.
Other Acids (e.g. H2SO4, HCl and oxalic acid) will etch rust, but not as selectively. These
acids will etch rust quickly, but if metal is left in them a bit too long, they will attack
significant amount of metal. Also, the acids do not leave a protective film behind.
Oxalic acid operates to remove rust by forming a water-soluble complex ion. (called a
Chelate) round each iron ion. Note: All acids contribute some hydrogen to the metal structure
by a process called hydrogen embrittlement – this weakens iron or steel.

Electrolytic Rust Removal

Rust can be electrically etched off iron or steel in a bath of mild alkali, such as sodium
carbonate. The rusty part is connected to the –ve terminal of a 12V battery charger, and a
scrap piece of steel or iron is connected to the positive terminal. A table-spoon of sodium
carbonate per gallon of water is used.
Advantages of this method include:
(1). The alkaline solution is much safer than some acids mentioned earlier.
(2). It has no effect on good metal – the metal can be left in the alkaline for a long time and
not damaged.
(3). There is no risk of hydrogen embrittlement.
Electrolytic rust removal will leave a black oxide surface, which is the result of a process that
doesn’t remove any good metal but loose rust and embedded oxygen.

107
ELECTROCHEMICAL CELL
Electrochemical cell is a set up in which chemical energy is converted to electrical energy. It
is an arrangement that consists of two different metals dipped into a solution of their salts and
connected by a conductor. A combination of two or more electrochemical cells gives a
battery.
Example of an electrochemical cell is zinc electrode dipped into a solution of zinc
tetroxosulphate (VI), connected to a copper electrode dipping into a solution of copper (II)
tetraoxosulphates (VI). The solutions are separated by a porous partition. The porous
partition allows electrical contact but prevents excessive mixing of the electrolytes by inter
diffusion.
The atom at the zinc electrode undergoesesoxidation and loses two electrons to form zinc
ions (Zn2+) which go into the solution. The zinc electrode becomes negatively charged and
functions as the negative electrode or anode. The copper (II) ions (Cu2+) become reduced by
gaining two electrons each to form metallic copper which is deposited on the copper
electrode. The copper electrode thus becomes positively charged and functions as the
positive electrode or cathode.
At the zinc electrode:
Zn(s) → Zn2+(aq) + 2e-

The anode slowly becomes reduced in size as the metallic zinc is converted to zinc ions.
At the copper electrode:
Cu2+(aq) + 2e- → Cu(s)
The cathode gradually increases in size due to the deposition of metallic copper.
Net (Overall) reaction:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

A piece of filter paper soaked in sodium chloride or potassium chloride solution can serve as
a salt bridge. Its functions are to complete the electric circuit and allow the movements of
ions from one half – cell to the other so as to maintain electrical neutrality in the solution
when current flows in the set – up.
Simple electrochemical cells widely used to generate small current for everyday purposes are
*Daniel cell

108
*Leclanche cell
Both Daniel cell and Leclanche cell are primary cells.

DANIEL CELL
In the Daniell cell, copper and zincelectrodes are immersed in a solution of copper(II) sulfate
and zinc sulfate respectively. At the anode, zinc is oxidized per the following half reaction:

The two half-cell form of the Daniell cell for classroom demonstrations
Zn(s) → Zn2+(aq) + 2e− . . (Standard electrode potential −0.7618 V )
At the cathode, copper is reduced per the following reaction:
Cu2+(aq) + 2e− → Cu(s) . . (Standard electrode potential +0.340 V )
The total reaction being:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) . . ( Open-circuit voltage 1.1018 V )
In classroom demonstrations, a form of the Daniell cell known as two half cells is often used
due to its simplicity. The two half cells each support one half of the reactions described
above. A wire and light bulb may connect the two electrodes. Electrons that are “pulled”
from the zinc anode travel through the wire, providing an electrical current that illuminates
the bulb. In such a cell, the counterions play an important role. Having a negative charge, the
anions build up around the anode to maintain a neutral charge. Conversely, at the cathode the
copper(II) cations discharge to maintain a neutral charge. These two processes accompany
the accumulation of copper solid at the cathode and the corrosion of the zinc electrode into
the solution as zinc cations.
Since neither half reaction will occur independently of the other, the two half cells must be
connected in a way that will allow ions to move freely between them. A porous barrier or
ceramic disk may be used to separate the two solutions while allowing the flow of sulfate
ions. When the half cells are placed in two entirely different and separate containers, a salt
bridge is often used to connect the two cells. The salt bridge typically contains a high
concentration of potassium nitrate (a salt that will not interfere chemically with the reaction
in either half-cell). In the above wet-cell during discharge, nitrate anions in the salt bridge
move into the zinc half-cell in order to balance the increase in Zn2+ ions. At the same time,
potassium ions from the salt bridge move into the copper half-cell in order to replace the Cu 2+
ions being discharged.

109
 In the Daniell cell, the porous barrier cannot prevent the flow of copper ions into the zinc
half-cell. Hence, recharging (reversing the current flow by an external source of EMF) is
impossible because, if the zinc electrode is made to become the cathode, copper ions, rather
than zinc ions, will be discharged on account of their lower potential.
LECLANCHE CELL


The redox reaction in a Leclanché cell involves the two following half-reactions:
– anode (oxidation of Zn): Zn → Zn2+ + 2e−
– cathode (reduction of Mn(IV)): 2 MnO2 + 2NH4+ + 2e− → 2 MnO(OH) + 2 NH3
The chemical process which produces electricity in a Leclanché cell begins when zinc atoms
on the surface of the anode oxidize, i.e. they give up both their valence electrons to become
positively charged Zn2+ions. As the Zn2+ ions move away from the anode, leaving their
electrons on its surface, the anode becomes more negatively charged than the cathode. When
the cell is connected in an external electrical circuit, the excess electrons on the zinc anode
flow through the circuit to the carbon rod, the movement of electrons forming an electric
current.
After passing through the whole circuit, when the electrons enter the cathode (carbon rod),
they combine with manganese dioxide (MnO2) and water (H2O), which react with each other
to produce manganese oxide (Mn2O3) and negatively charged hydroxide ions. This is
accompanied by a secondary acid-base reaction in which the hydroxide ions (OH–) accept a
proton (H+) from the ammonium ions present in the ammonium chlorideelectrolyte to
produce molecules of ammonia and water.[9]
Zn(s) + 2 MnO2(s) + 2NH4Cl(aq) → ZnCl2(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l),
or if one also considers the hydration of the Mn2O3(s) sesquioxide into Mn(III) oxy-
hydroxide:
Zn(s) + 2MnO2(s) + 2 NH4Cl(aq) → ZnCl2(aq) + 2 MnO(OH)(s) + 2 NH3(aq)
*Alternately, the reduction reaction of Mn(IV) can proceed further, forming Mn(II)
hydroxide.
Zn(s) + MnO2(s) + 2 NH4Cl(aq) → ZnCl2(aq) + Mn(OH)2(s) + 2 NH3(aq)

110
USES
The electromotive force (e.m.f.) produced by a Leclanche cell is 1.4 volts, with a resistance
of several ohms where a porous pot is used.[6] It saw extensive usage in telegraphy, signaling,
electric bells and similar applications where intermittent current was required and it was
desirable that a battery should require little maintenance.
The Leclanché battery wet cell was the forerunner of the modern zinc-carbon battery (a dry
cell). The addition of zinc chloride to the electrolyte paste raised the e.m.f. to 1.5 volts. Later
developments dispensed with the ammonium chloride completely, giving a cell that could
endure more sustained discharge without its internal resistance rising as quickly (the zinc
chloride cell).
SECONDARY CELLS
These are cells which can be recharged by passing a direct current through them. They
supply steady current for a period of time. The chemical reaction involved in the generation
of electric current is reversible. Etc. Examples of secondary cells include:
*Lead – acid accumulator
*Alkaline accumulator

LEAD – ACID ACCUMULATOR

The French scientist Nicolas Gautherot observed in 1801 that wires that had been used for
electrolysis experiments would themselves provide a small amount of "secondary" current
after the main battery had been disconnected.[9] In 1859, Gaston Planté's lead–acid battery
was the first battery that could be recharged by passing a reverse current through it. Planté's
first model consisted of two lead sheets separated by rubber strips and rolled into a spiral.[10]
His batteries were first used to power the lights in train carriages while stopped at a station.
In 1881, Camille Alphonse Faure invented an improved version that consisted of a lead grid
lattice, into which a lead oxide paste was pressed, forming a plate. This design was easier to
mass-produce. An early manufacturer (from 1886) of lead–acid batteries was Henri Tudor.
Using a gel electrolyte instead of a liquid allows the battery to be used in different positions
without leakage. Gel electrolyte batteries for any position date from the 1930s, and even in
the late 1920s portable suitcase radio sets allowed the cell vertical or horizontal (but not
inverted) due to valve design (see third Edition of Wireless Constructor's Encyclopaedia by
Frederick James Camm). In the 1970s, the valve-regulated lead–acid battery (often called
"sealed") was developed, including modern absorbed glass mat types, allowing operation in
any position.

Electrochemistry

DISCHARGE

111
Fully discharged: two identical lead sulfate plates
In the discharged state both the positive and negative plates become lead(II) sulfate(PbSO4),
and the electrolyte loses much of its dissolved sulfuric acid and becomes primarily water.
The discharge process is driven by the conduction of electrons from the negative plate back
into the cell at the positive plate in the external circuit.
Negative plate reaction
+
Pb(s) + HSO−4(aq) → PbSO4(s) + H (aq) + 2e−
Release of two conducting electrons gives lead electrode a net negative charge
As electrons accumulate they create an electric field which attracts hydrogen ions and repels
sulfate ions, leading to a double-layer near the surface. The hydrogen ions screen the charged
electrode from the solution which limits further reactions unless charge is allowed to flow out
of electrode.
Positive plate reaction
+
PbO2(s) + HSO−4(aq) + 3H (aq) + 2e− → PbSO4(s) + 2H2O(l)
The total reaction can be written as
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
The sum of the molecular masses of the reactants is 642.6 g/mol, so theoretically a cell can
produce two faradays of charge (192,971 coulombs) from 642.6 g of reactants, or 83.4
ampere-hours per kilogram (or 13.9 ampere-hours per kilogram for a 12-volt battery). For a 2
volts cell, this comes to 167 watt-hours per kilogram of reactants, but a lead–acid cell in
practice gives only 30–40 watt-hours per kilogram of battery, due to the mass of the water
and other constituent parts.
CHARGING

Fully recharged: Lead negative plate, Lead dioxide positive plate and sulfuric acid electrolyte
In the fully charged state, the negative plate consists of lead, and the positive plate lead
dioxide, with the electrolyte of concentrated sulfuric acid.
Overcharging with high charging voltages generates oxygen and hydrogen gas by electrolysis
of water, which is lost to the cell. The design of some types of lead-acid battery allow the
electrolyte level to be inspected and topped up with any water that has been lost.
112
Due to the freezing-point depression of the electrolyte, as the battery discharges and the
concentration of sulfuric acid decreases, the electrolyte is more likely to freeze during winter
weather when discharged.
Ion motion
+
During discharge, H
produced at the negative plates moves into the electrolyte solution and then is consumed into
the positive plates, while HSO4−
4 is consumed at both plates. The reverse occurs during charge. This motion can be by
electrically driven proton flow or Grotthuss mechanism, or by diffusion through the medium,
or by flow of a liquid electrolyte medium. Since the density is greater when the sulfuric acid
concentration is higher, the liquid will tend to circulate by convection. Therefore, a liquid-
medium cell tends to rapidly discharge and rapidly charge more efficiently than an otherwise
similar gel cell.

113
QUALITATIVE INORGANIC ANALYSIS
SOLUBILITY OF SALTS IN WATER
Salts are ionic solids. They dissolve in water to produce ions, hence, they are electrolyte.
However, the extent of solubility of some salts in water is so small that they are regarded as
insoluble salts.

SOLUBILITY RULE
1. All sodium, potassium and ammonium salts are soluble in water
2. All acid salts are soluble in water
3. All trioxonitrate (V) salts, NO3- are soluble in water
4. All chlorides, Cl- are soluble in water, except those of Ag, Pb and Hg(II)
5. All tetraoxosulphate (VI) salts, SO42- are soluble, except those of Pb and Ba. CaSO4 is
slightly soluble in water
6. All trioxosulphate (IV) salts, SO32- are insoluble, except those of sodium, potassium
snd ammonium salts that are soluble in water
7. All trioxocarbonate (IV) salts, CO32- are insoluble, except those of sodium, potassium
snd ammonium salts that are soluble in water
8. All sulphides, S2- are insoluble except those of sodium, potassium, ammonium,
calcium, magnesium and barium salts that are water soluble.

TEST FOR THE PRESENCE OF ZINC ION, Zn2+.

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: White gelatinous precipitate formed in drops of NaOH(aq), which
dissolves in excess NaOH(aq)
INFERENCE: Zn2+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: White gelatinous precipitate formed in drops of NH3(aq), which is
soluble in excess NH3(aq)
INFERENCE: Zn2+ present

3. TEST: To 1.0cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then
pass hydrogen sulphide gas
OBSERVATION: White gelatinous precipitate formed in drops of NaOH(aq), which
is insoluble in hydrogen sulphide gas
INFERENCE: Zn2+ present

114
 4. TEST: To the solution of sample in a test tube, add potassium hexacyanoferrate (II)
K4Fe(CN)6 (potassium ferrocyanide) solution.
OBSERVATION: White gelatinous precipitate formed
INFERENCE: Zn2+ present

TEST FOR THE PRESENCE OF ALUMINIUM ION, Al3+

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: White gelatinous precipitate formed in drops of NaOH(aq), which
dissolves in excess NaOH(aq)
INFERENCE: Al3+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: White gelatinous precipitate formed in drops of NH3(aq), which is
insoluble in excess NH3(aq)
INFERENCE: Al3+ present

3. TEST: To the solution of sample in a test tube, add few drops of ammonia solution,
then add ammonium chloride solution.
OBSERVATION: White gelatinous precipitate formed
INFERENCE: Al3+ present

4. TEST: To the solution of sample in a test tube, add few drops of dilute HCl, followed
by one drop by drop of litmus solution. Then add ammonia solution drop by drop
until the solution is alkaline
OBSERVATION: Blue gelatinous precipitate formed
INFERENCE: Al3+ present

TEST FOR THE PRESENCE OF LEAD (II) ION, Pb2+

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: White chalky precipitate formed in drops of NaOH(aq), which
dissolves in excess NaOH(aq)
INFERENCE: Pb2+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake

115
 OBSERVATION: White chalky precipitate formed in drops of NH3(aq), which is
insoluble in excess NH3(aq)
INFERENCE: Pb2+ present

3. TEST: To the solution of sample in a test tube, add few drops of dilute HCl.
OBSERVATION: White precipitate of PbCl2 formed which dissolves on heating the
mixture, and reappears on cooling.
INFERENCE: Pb2+ present
Pb2+(aq) + 2Cl-(aq)  PbCl2(s) [White]
[This test can be used to distinguish between Pb2+ and Al3+ in a solution. Al3+ does not
form precipitate with HCl(aq)]

4. TEST: To the solution of sample in a test tube, add few drops of potassium iodide
solution.
OBSERVATION: Bright yellow precipitate of PbI2 formed
INFERENCE: Pb2+ confirmed
Pb2+(aq) + 2l-(aq)  Pbl2(s) [Yellow]

5. TEST: To the solution of sample in a test tube, add few drops of potassium
tetraoxochromate (VI) solution.
OBSERVATION: Yellow precipitate of PbCrO4 formed
INFERENCE: Pb2+ confirmed
Pb2+(aq) + CrO42-(aq)  PbCrO4(s) [Yellow]

6. TEST: To the solution of sample in a test tube, pass hydrogen sulphide gas into the
solution.
OBSERVATION: Black precipitate of PbS formed
INFERENCE: Pb2+ confirmed
Pb2+(aq) + S2-(aq)  PbS(s) [Black]

7. TEST: To the solution of sample in a test tube, add few drops of dilute H2SO4
solution.
OBSERVATION: White precipitate of PbSO4 formed
INFERENCE: Pb2+ present
Pb2+(aq) + SO42-(aq)  PbSO4(s) [White]
These tests show that almost all the salts of lead are insoluble in water.

TEST FOR THE PRESENCE OF CALCIUM ION, Ca2+

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: White chalky precipitate formed in drops of NaOH(aq), which
insoluble in excess NaOH(aq)
INFERENCE: Ca2+ present

116
 2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: No precipitate or no visible reaction
INFERENCE: Ca2+ present

3. TEST: To the solution of sample in a test tube, add few drops of ammonia solution,
then add ammonium trioxocarbonate (IV) solution, (NH4)2CO3(aq)
OBSERVATION: White gelatinous precipitate formed
INFERENCE: Ca2+ confirmed

TEST FOR THE PRESENCE OF IRON (II) ION, Fe2+

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: Dirty green gelatinous precipitate formed in drops of NaOH(aq),
insoluble in excess NaOH(aq)
INFERENCE: Fe2+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: Dirty green gelatinous precipitate formed in drops of NH3(aq),
which is insoluble in excess NH3(aq)
INFERENCE: Fe2+ present

3. TEST: To the solution of sample in a test tube, add few drops of potassium
hexacyanoferrate (III) solution, K3Fe(CN)6(aq) to the solution of sample.
OBSERVATION: Blue - black precipitate or dark – blue precipitate or Prussian -
blue precipitate formed.
INFERENCE: Fe2+ present

4. TEST: To the solution of sample in a test tube, add few drops of concentrated HNO3
to the solution and boil for a while.
OBSERVATION: Brown solution formed
INFERENCE: Fe2+ present
REASON: The Fe2+ is oxidized to Fe3+
Fe2++ 2H++ [O] 2Fe3+ + H2O
5. TEST: To the solution of sample in a test tube, add few drops of acidified KMnO4(aq)
to the solution.
OBSERVATION: Purple colour of KMnO4(aq) is decolourised.
INFERENCE: Fe2+ present
REASON: Fe2+ is a reducing agent

TEST FOR THE PRESENCE OF IRON (III) ION, Fe3+

117
 1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: Brown gelatinous precipitate formed in drops of NaOH(aq),
insoluble in excess NaOH(aq)
INFERENCE: Fe3+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: Brown gelatinous precipitate formed in drops of NH3(aq), which is
insoluble in excess NH3(aq)
INFERENCE: Fe3+ present

3. TEST: To the solution of sample in a test tube, add few drops of potassium
hexacyanoferrate (II) solution, K4Fe(CN)6(aq) to the solution of sample.
OBSERVATION: Brown solution formed.
INFERENCE: Fe3+ confirmed

4. TEST: To the solution of sample in a test tube, add few drops of potassium
thiocyanate solution, KSCN(aq)
OBSERVATION: Blood – red colouration formed
INFERENCE: Fe3+ confirmed

TEST FOR THE PRESENCE OF COPPER (II) ION, Cu2+

1. TEST: To 2cm3 of the solution of sample in a test tube, add NaOH(aq) in drops, then,
in excess and shake
OBSERVATION: Light blue gelatinous precipitate formed in drops of NaOH(aq),
insoluble in excess NaOH(aq)
INFERENCE: Cu2+ present

2. TEST: To 2cm3 of the solution of sample in a test tube, add NH3(aq) in drops, then, in
excess and shake
OBSERVATION: Light blue gelatinous precipitate formed in drops of NH3(aq),
which dissolves in excess NH3(aq) to form a deep blue solution
INFERENCE: Cu2+ present
In drops: Cu2+(aq) + 2NH4OH(aq)  Cu(OH)2(s) + 2NH4+(aq)
In excess: Cu(OH)2(s) + 2NH4OH(aq)  Cu(NH3)4(OH)2(aq) + 2H2O(l)
(Deep blue)

3. TEST: To the solution of sample in a test tube, add few drops of potassium
hexacyanoferrate (II) solution, K4Fe(CN)6(aq) to the solution of sample.
OBSERVATION: Brown precipitate formed.
INFERENCE: Cu2+ confirmed
4. TEST: To the solution of sample in a test tube, add few drops of potassium iodide
solution.

118
 OBSERVATION: Brown solution and a dirty white precipitate
INFERENCE: Cu2+ confirmed
2Cu2+(aq) + 4I-(aq)  2CuI(s) + I2(g)
(White) (Brown)
TEST FOR THE PRESENCE OF TETRAOXOSULPHATE (VI) ION,
SO42-
1. TEST: To the solution of the sample, add few drops of dilute HCl, followed by BaCl2
solution.
OBSERVATION: Awhite precipitate formed
INFERENCE: SO42- confirmed

2. TEST: To the solution of the sample, add few drops of BaCl2, followed by HCl
solution.
OBSERVATION: Awhite precipitate formed insoluble in dilute HCl
INFERENCE: SO42- confirmed
Equation of reaction: SO42-(aq) + BaCl2(aq)  2Cl-(aq) + BaSO4(s)[White]
NOTE: In the confirmatory test for SO42-,the solution of sample is first acidified with dilute
HCl before the addition of BaCl2 solution, in order to remove interfering ions, such as SO32-,
CO32- and S2- that also form white precipitate with BaCl2 solution.

TEST FOR THE PRESENCE OF TRIOXOSULPHATE (IV) ION,

SO32-
1. TEST: To the solution of the sample, add few drops of dilute HCl, followed by BaCl2
solution.
OBSERVATION: Awhite precipitate formed
INFERENCE: SO32- confirmed

2. TEST: To the solution of the sample, add few drops of BaCl2, followed by HCl
solution.
OBSERVATION: Awhite precipitate formed soluble in dilute HCl
INFERENCE: SO32- confirmed
Equation of reaction: SO32-(aq) + BaCl2(aq)  2Cl-(aq) + BaSO3(s)[White]

3. TEST: To the solution of the sample, add few drops of acidified KMnO4(aq) solution.
OBSERVATION: The purple colour of acidified KMnO4(aq) solution is decolourised
to colourless
INFERENCE: A reducing agent present. SO32- is a reducing agent,
TEST FOR THE PRESENCE OF TRIOXOCARBONATE (IV) ION,
CO32-
1. TEST: To the solution of the sample, add few drops of BaCl2, followed by HCl
solution.

119
 OBSERVATION: Awhite precipitate dissolves in dilute HCl with a brisk
effervescence of a colourless, odourless gas, which turns blue litmus paper red and
turns lime water milky
INFERENCE: The gas is acidic, the gas is CO2. CO32- present
Equation of reaction: CO32-(aq) + BaCl2(aq)  2Cl-(aq) + BaCO3(s)[White]

2. TEST: To the solution of the sample, add few drops of phenolphthalein indicator
OBSERVATION: The solution turns pink, solution is alkaline
INFERENCE: CO32- present

TEST FOR THE PRESENCE OF HYDROGEN TRIOXOCARBONATE

(IV) ION, HCO3-
1. TEST: To the solution of the sample, add few drops of BaCl2, followed by HCl
solution.
OBSERVATION: No visible reaction or no precipitate formed. But on boiling the
mixture, awhite precipitate formed dissolves in dilute HCl with a brisk effervescence
of a colourless, odourless gas, which turns blue litmus paper red and turns lime water
milky.
INFERENCE: The gas is acidic, the gas is CO2. HCO3- present
Equation of reaction: HCO3-(aq) + BaCl2(aq)  2Cl-(aq) + Ba(HCO3)2(s)
White
2. TEST: To the solution of the sample, add few drops of phenolphthalein indicator
OBSERVATION: The solution remains colourless or no change in colour; but on
boiling turns pink.
INFERENCE: HCO3- present

TEST FOR THE PRESENCE OF HALIDES [Cl-, Br- and I-]

1. TEST: To the solution of the sample, add few drops of dilute HNO3, followed by
drops of AgNO3 solution.
OBSERVATION: White precipitate of AgCl formed which is soluble in ammonia
solution.
INFERENCE: Cl- confirmed
Equation of reaction: Cl-(aq) + AgNO3(aq)  NO3-(aq) + AgCl(s)
White

2. TEST: To the solution of the sample, add few drops of dilute HNO3, followed by
drops of AgNO3 solution.
OBSERVATION: Creamy - white precipitate of AgBr formed which is slightly
soluble in ammonia solution.
INFERENCE: Br- confirmed
Equation of reaction: Br-(aq) + AgNO3(aq)  NO3-(aq) + AgBr(s)
Creamy – white

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 3. TEST: To the solution of the sample, add few drops of dilute HNO3, followed by
drops of AgNO3 solution.
OBSERVATION: Pale yellow precipitate of AgI formed which is insoluble in
ammonia solution.
INFERENCE: l- confirmed
Equation of reaction: l-(aq) + AgNO3(aq)  NO3-(aq) + Agl(s)
Pale – yellow
NOTE: The solution of sample is first acidified with dilute HNO3 before the addition of
AgNO3 solution, in order to remove interfering ions, such as SO32-, CO32- and S2- that also
form white precipitate with AgNO3 solution.

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