Form Four Chem Notes

ACIDS, BASES AND SALTS
ACIDS
An Acid is a substance that dissociates in water to give hydrogen ions as the only
positively charged ions;
Or a substance which contain replaceable hydrogen, which can be wholly or
partially replaced by a metal.
HCl (aq) → H+(aq) + Cl- (aq)
CH3COOH(aq) → H+ (aq) + CH3COO-(aq)
OR: - An acid is a proton donor i.e. a substance which provides protons or

hydrogen ions.
STRENGTH OF ACIDS
Acids can be categorized as either strong or weak acids;
(a) Strong acids
A strong acid is one that dissociates completely in aqueous solution.
Are acids whose aqueous solutions contain a high number of hydrogen ions.
Examples
Hydrochloric acid; HCl(aq) → H+ (aq) + Cl- (aq)
Sulphuric(VI) acid; H2SO4(aq) → 2H+ (aq) + SO4 2-(aq)
Nitric(V) acid; HNO3(aq) → H+ (aq) + NO3- aq)
(b) Weak acids

A weak acid is one that dissociates partially in in aqueous solution.
Are acids whose aqueous solutions contain few hydrogen ions.
Examples:
Carbonic acid:
water
H2CO3(aq) → H+(aq) + HCO3-(aq)
Ethanoic acid
water
CH3COOH (aq) → H+(aq) + CH3COO-(aq)
Concentrated acid
Is an acid with a high number of acid molecules per given volume.
Dilute acid
Are acids with a low number of acid molecules per given volume.
chemf4@orwacollins Page 1
COMPARING THE STRENGTH OF ACIDS
(i). Using rate of evolution of hydrogen
A student placed 5cm3 of 2 M HCl and 5 cm3 of 2 M CH3COOH into separate
test tubes. The student then dropped 2 cm piece of clean magnesium strip
into each at the same time.
Questions
a) Explain why magnesium is cleaned before use.
To remove any coating of magnesium oxide on the surface.
b) State and explain the observations made.
(i) Effervescence produced in each case. This is due to formation of
hydrogen gas.
(ii) Hydrochloric acid evolves hydrogen much more quickly than Ethanoic
acid yet they were of equal concentration.
Conclusion
Hydrochloric acid is a strong acid;
Ethanoic acid is a weak acid.
Note: -
The same experiment can be repeated with marble chips (CaCO 3) in acids of same
concentration.
The marble chips dissolve more quickly in HCl, which is a strong acid.
(ii). Using electrical conductivity

Procedure:
50cm3 of 2M-hydrochloric acid solution is placed into a beaker and set up
apparatus as shown below.
The switch is closed and the deflection in the ammeter is noted. The experiment is
repeated using 2 M CH3COOH in place of 2 M HCl.
Diagram: Electrolytic circuit
Observations
The deflection is greater with HCl than with CH 3COOH
Explanations
Strong acids are completely dissociated and have more H+ in solution and hence
have got a higher electrical conductivity; than solutions of weak acids which are
only partially ionized thus have fewer hydrogen ions in solution.
(iii). Using pH
Procedure
2cm3 solutions of different acids of equal concentrations are poured into different
test tubes.
To each test tube 2 drops of universal indicator are added.
Acids tested: HCl, H2SO4, HNO3; ethanoic acid, carbonic acid, and tartaric acid.
All acids are of 2M solutions
The indicator colour and hence the PH number of each is noted; by comparing
against the indicator chart.
Observations
Colour of universal
Substance (1M) pH
indicator
Sulphuric acid Red 3
Hydrochloric acid Red 3
Nitric acid Red 3
Ethanoic Orange 5
Carbonic acid Yellow 6
Tartaric acid orange 5
Explanations
Solutions of strong acids contain a higher concentration of hydrogen ions than
those of weak acids
Strong acids have low pH usually less than 3.
Weak acids have higher pH values usually between 5 - 6.
BASES
A base is a substance that dissociates in water to produce OH- as the only
negatively charged ions.
Bases can also be defined as substances which accept the protons donated by
acids and are hence proton acceptors
NH3 (aq) + H+ (aq) → NH4+(aq)
CuO(s) + 2H+ (aq) → Cu 2+(aq) + H2O(l)
Alkalis
An alkali is a soluble base i.e. a base that is soluble in water.
They are compounds, which produce hydroxyl ions in aqueous solutions.
NaOH(aq) → Na+(aq) + OH- (aq)
Strength of an Alkali
Alkalis can be grouped as either strong or weak alkalis.
(a). Strong alkalis

Are alkalis that undergo complete dissociation in aqueous solution; yielding a large
number of hydroxyl (OH-) ions
Examples:
Sodium hydroxide.
Potassium hydroxide.
(b). Weak alkalis

Are alkalis that undergo only partial dissociation in aqueous solution (water)
yielding fewer numbers of hydroxyl ions.
Examples
Calcium hydroxide
Ammonium hydroxide
QUESTION: Why is calcium hydroxide a weak base?

Answer: because it is slightly soluble in water and therefore produces few number
of OH- in solution.
Measuring the strength of alkalis

(i). Using electrical conductivity
Procedure
50 cm3 of 2 M sodium hydroxide solution is put into a beaker and the apparatus
set as shown below
Apparatus
Procedure
The same procedure is repeated using other alkalis like NH4OH; Ca (OH)2 e.t.c.
Observation
The deflection is greater with KOH and NaOH as electrolyte than with NH 4OH and
Ca(OH)2
Explanation
NaOH and KOH are strong alkalis and are completely dissociated and have more
ions in solution and hence have got a higher electrical conductivity than the weak
alkalis of NH4OH and Ca(OH)2(aq)
(ii). Using pH values

Procedure
2 cm3 of NaOH and 2 cm3 of NH4OH are each poured into 2 different test tubes
separately
Into each test tube 2 drops of universal indicator are added.
The colour change is noted and the corresponding pH scale recorded
Observations
Colour of universal
Alkali PH
indicator
Ammonium hydroxide (1M) Blue. 11
Calcium hydroxide (1M) Blue. 10
Sodium hydroxide (0.1M) Purple. 13
Sodium hydroxide (1M) Purple. 14
Potassium hydroxide Purple. 14
EFFECT OF A SOLVENT ON A SOLUTE
Experiment: - To find out if solutions of HCl in different solvents

display acidic properties
Procedure
Solutions of hydrogen chloride gas are made by bubbling the dry gas from a
generator into water and into methylbenzene contained in separate beakers.
The hydrogen chloride gas is passed into the solution using an inverted funnel to
prevent sucking back.
The resultant solutions are each separately subjected to various tests as shown
below and observations recorded
Tests and observations
Test. Solution of HCl in Solution of HCl in

water methylbenzene
A piece of dry blue litmus Blue litmus turns red Blue litmus remains
paper is dropped into solution blue
Dry universal indicator paper Turns red (strong acid) Turns green (neutral)
1. Add magnesium ribbon Evolution of hydrogen No reaction
2. Add small marble CO2 evolved No reaction

chips(CaCO3)
Explanation
The results show that the aqueous solution of hydrogen chloride behaves as an
acid; but the solution in methylbenzene lacks acidic properties
When HCl gas dissolves in water it changes from molecules to ions;
water
It is the hydrogen ions which give the acidic properties and these can only be
formed in the presence of water
HCl in water conducts electric current due to presence of mobile ions in solution
HCl gas in methylbenzene does not conduct electric current because the HCl exists
as molecules hence lack mobile ions
Note: - hydrogen chloride gas dissolves in water because both HCl and water
polar molecules;
- This causes mutual attraction of both ends of HCl molecule by different
water molecules causing the dissociation of HCl molecules into ions.
Hence:
HCl (g) + water → HCl (aq)
The presence of hydrogen ions in aqueous solution of hydrogen chloride explains

the electrical conductivity and acidic properties of hydrogen chloride.
In methylbenzene hydrogen chloride remains as molecules. The solution therefore

lacks mobile ions.
Bases
Effects of type of solvent on the properties of ammonium solution
Procedure
Ammonium solution is prepared by bubbling the gas from a generator into
methylbenzene (toluene) and into water contained in separate beakers
The solutions are each divided into 3 portions and tested with litmus paper;
universal indicator and for electrical conductivity
Observations
Test Solution of NH3 in water Solution of NH3 in
methylbenzene
(toluene)
Dry litmus paper Red litmus paper turns blue; No effect
Dry universal Colour turns purple (alkaline Turns green (Neutral PH)
indicator paper pH)
Electrical Poor conductor Non-conductor
conductivity
Explanations
When NH3(g) dissolves in water it changes from molecules to ions.
Equation:
NH3(g) + H2O(l) → NH4+(aq) + OH-(aq)
It is the hydroxide ions that cause alkaline properties.

Since ammonium hydroxide is a weak alkali, it dissociates partially releasing fewer
hydroxide ions hence the poor electric conductivity.
Ammonium gas in methylbenzene or trichloromethane exists as molecules without
free ions hence no alkaline properties and the electrical conductivity.
Amphoteric oxides and hydroxides

Oxides
An oxide is a binary compound of oxygen and another element.
Are of four categories:
a. Basic oxides
b. Acidic oxides
c. Neutral oxides
d. Amphoteric oxides
(i). Basic oxides

Are usually oxides of metals (electronegative elements)
They react with acids to form salt and water only.
Examples
CaO, MgO, CuO
(ii). Acidic oxides

Are usually oxides of non metals (electronegative elements).
Many of them react with water to form (give) acids and are known as acid
anhydrides
Examples
CO2; SO2; SO3; P2O5 and NO2
(iii). Amphoteric oxides

Are oxides, which behave as both bases and acids.
Examples
ZnO, Al2O3, PbO
Reaction of Metal oxides with acids and Alkalis
Observations when
Name of solid
acid is added hydroxide is added
Aluminium oxide Oxide dissolves Oxide dissolves
Zinc oxide Oxide dissolves Oxide dissolves
Lead II oxide Oxide dissolves Oxide dissolves
Zinc hydroxide Hydroxide dissolves
Lead hydroxide Hydroxide dissolves Hydroxide dissolves
Aluminium hydroxide Hydroxide dissolves Hydroxide dissolves
Explanations
These oxides are soluble in acids as well as in the alkalis (NaOH)
Reaction with acids
Oxides react with acids to form a salt and water only in a reaction called
neutralization reaction.
Equations
Oxides
(i). PbO(s) + 2HNO3(aq) → Pb(NO3)2(aq) + H2O(l)
(ii). Al2O3(s) + 6HNO3(aq) → 2Al(NO3)3(aq) + 3H2O(l)
(iii). ZnO(s) + 2HCl(aq) → ZnCl2(aq) + H2O(l)
Hydroxides:
(i). Pb(OH)2(s) + 2HCl(aq) → PbCl2(aq) + 2H2O(l)
(ii). Zn(OH)2(s) + 2HCl(aq) → ZnCl2(aq) + 2H2O(l)
(iii). Al(OH)3(s) + 3HCl(aq) → AlCl3(aq) + H2O(l)
Note: In these reactions the metal oxides are reacting as bases.
Reaction with alkalis

These oxides and hydroxides also react with alkalis e.g sodium hydroxide in which
case they are reacting as acids.
Their reactions with alkalis involve the formation of complex ions;
Equations
Oxides
(i). PbO(s) + 2NaOH(aq) → Na2PbO2(aq) + H2O(l)
(ii). Al2O3(s) + 2NaOH(aq) → 2NaAlO3(aq) + H2O(l)
(iii). ZnO(s) + 2NaOH(aq) → Na2ZnO2(aq) + H2O(l)
Hydroxides:
(i). Al(OH)3(s) + NaOH(aq) → NaAl(OH)4(aq)
(ii). Zn(OH)2(s) + 2NaOH(aq) → Na2Zn(OH)4(aq)
(iii). Pb(OH)2(s) + 2NaOH(aq) → Na2Pb(OH)4(aq)
SOLUBILITY AND SOLUBILITY CURVES
Solubility
Is the maximum mass of solute required to saturate 100g of solvent at a particular
temperature.
Solubility can also be expressed in moles per litre of a solution at a given
temperature.
Note: Saturated solution is a solution that cannot dissolve any more of the solid/
solute at a particular temperature
Example;
Experiment
Weigh an evaporating dish with a watch glass that fits over it. Measure 20 cm 3 of a
saturated solution of KNO3. Transfer it into the weighed dish. Record the
temperature of the solution. Weigh the dish together with the saturated solution
and the watch glass. Heat the solution gently to dryness. Allow it to cool and re-
weigh.
Results;
Temperature of solution = 15 oC
Mass of dish + watch glass = 55g
Mass of dish + watch glass + solution = 85g
Mass of dish + watch glass + solid salt = 61g
Mass of saturated solution = 85 – 55 = 30g
Mass of solute = 61 – 55 = 6g
Mass of solvent = 85 – (55 + 6) = 24g
From the results, it can be noted that 24g of the solvent (water) dissolves 6g of
solute at 15oC. This means that 100g of solvent will dissolve:
100 X 6
= 25g of solute
24
Thus the solubility of the salt is 25 g/100g H2O
If 100g (100 cm3 of water) dissolves 25g of KNO3

1000 X 25
Then 1000 cm3 of water would dissolve = = 250 g/litre
100
250
= = 2.4755 moles/litre
101
Experiment: to determine the effect of temperature on solubility

of potassium chlorate
Weigh accurately 2 g of KClO3 and transfer into a dry clean boiling tube. Using a
burette add 5 cm3 of water into the boiling tube. Warm the mixture until all the
solid has dissolved.
Place a thermometer in the solution and remove the flame. Allow the solution to
cool while stirring with the thermometer. Note the temperature at which crystals
just appear. Add 5 cm3 of water into the mixture in the boiling tube and repeat the
procedure. Continue adding 5 cm3 portions of water until the total volume of water
i9s 40 cm3. Note the temperature at which crystals appear in each case and record
the observations in table below.
Total volume of water added 5 10 15 20 25

Mass of KClO3 in g/100g H2O 40.0 20.0 13. 10.0 8.0
3
Temperature at which crystals just appear 88.0 52.0 38. 31.0 25.0
0
When solubility is plotted against temperature, the following graph is obtained.
From the graph it is clear that an increase in temperature results in an increase in
solubility.
For most salts solubility increases with increase in temperature. However the
solubility of salts such as NaCl, CaSO4 remains almost constant with temperature
change.
The solubility of some salts such as calcium ethanoate (Ca(CH3COO)2) decreases
with an increase in temperature.
The Solubility curves for various salts
Solubility curves are useful since they give information that can be used to show
how crystals are obtained from saturated solutions.
Example;
If a saturated solution of KClO3 at 70oC is cooled to 30oC, crystallization occurs.

The mass of crystals is determined as shown below;
Mass of salt at 70oC = 124 g
Mass of salt at 0oC = 37 g
Mass of crystals deposited = 124 - 37 g
= 87 g
Fractional Crystallisation
The knowledge of solubilty curves is useful in the separation of a mixture of salts
with different solubilities. The separation of different salts by making use of the
differences in solubility in the same solvent is known as fractional crystallization.
Example;
A mixture of salts contain 20 g of potassium nitrate and 18 g of potassium chlorate
in 100 g of water at 50 oC, one of the salts can be separated using the information
in the table below.
Solubility at various temperatures

Salt
50 oC 20 oC
Potassium nitrate 86 g 31 g
Potassium chlorate 18 g 8g
If the mixture is cooled from 50 oC to 20 oC mass of potassium chlorate that

crystallizes = 18 – 8 = 8 g
But no potassium nitrate will crystallize. The solubility of one salt has no effect on
the solubility of the other.
Effect of Temperature on the solubility of KNO3 and Pb(NO3)2
Temperature (oC) 0 20 40 60 80 100

Solubility of KNO3 in 12.5 32.5 62.5 110.0 137.5
100 g of H2O
Solubility of Pb(NO3)2 in 37.5 52.5 69.0 87.5 110.0 131.0
100 g of H2O
If 100 cm3 of a saturated solution of KNO3 and Pb(NO3)2 is cooled from 70 oC to 40

o
C determine the amount of salt that crystallizes out.
At 70 oC the mass of;

i) Potassium nitrate = 138 g
ii) Lead (II) nitrate = 100 g
At 40 oC the mass of;
i) Potassium nitrate = 64 g
ii) Lead (II) nitrate = 70 g
Mass of potassium nitrate deposited = 138 – 64 = 74 g

Mass of Lead (II) nitrate deposited = 100 – 70 = 30 g
HARDNESS OF WATER
Hard water is water that does not lather easily with soap. The water contains Ca 2+
and Mg2+ ions.
The ions Ca2+ and Mg2+ react with soap to form an insoluble substance called
scum.
2C17H35COO-Na+(aq) + Ca2+(aq) → (C17H35COO-)2Ca(s) + 2Na+(aq)

Sodium stearate scum
2C17H35COO-Na+(aq) + Mg2+(aq) → (C17H35COO-)2Mg(s) + 2Na+(aq)
Sodium stearate scum
Types of water hardness
i) Temporary hardness
Is hardness due to the presence of Ca(HCO3)2 or Mg(HCO3)2 in water; and can
usually be removed by boiling.
ii) Permanent hardness
Is that due to presence of dissolved CaSO4 or MgSO4 or CaCl2 or MgCl2 and cannot
be removed by boiling.
Methods of Removing Hardness of Water
(i). Boiling: This method removes temporary hardness only

Heat
Ca(HCO3)2(s) CaCO3(s) + 2CO2(g) + H2O(l)
Heat
Mg(HCO3)2(s) MgCO3(s) + 2CO2(g) + H2O(l)
(ii). Distillation: This method removes both types of hardness.

Water containing dissolved salts is heated in a distillation apparatus;
Pure water distils over first leaving dissolved salts in the distillation flask.
However the process it is too expensive hence disadvantageous.
iii) By the addition of sodium carbonate
The Ca2+ and Mg2+ ions are precipitated out.
Sodium carbonate(washing soda softens hard water by causing the formation of
insoluble CaCO3 or MgCO3
The soluble sodium salts left in water do not react with soap.
Ca2+(aq) + CO32-(aq) CaCO3(s)
iv) Ion exchange Method
In this process hard water is passed through a column filled with some complex
sodium compounds which can be represented by the formula Na2X where X is a
complex.
Na2X(aq) + Ca2+(aq) CaX(s) + 2Na+(aq)
Na2X(aq) + Mg2+(aq) MgX(s) + 2Na+(aq)

The Ca2+ and Mg2+ ions are precipitated as CaX and MgX which remain in the
column as shown.
When all the Na+ ions in the permutit have been replaced by Ca2+ and Mg2+ ions the
permutit can not go on softening water.
It is then regenerated by washing the column with brine (a strong NaCl solution);
during which calcium and magnesium chlorides are washed away.
CaX(s) + 2NaCl(aq) CaCl2(aq) + Na2X(s)
MgX(s) + 2NaCl(aq) MgCl2(aq) + Na2X(s)
(v). Addition of calcium hydroxide:

Involves adding correct amount of lime water where CaCO 3 is precipitated out.
This method is cheap and can be used on large scale at water treatment plants.
However if excess lime (Ca2+) ions is added this will make water hard again.
Ca(HCO3)2(aq) + Ca(OH)2(aq) 2CaCO3(s) + 2H2O(l).
(vi). Addition of ammonia solution: Removes temporary hardness only

Addition of aqueous ammonia to water containing calcium and magnesium
hydrogen carbonates (temporary hard) precipitates calcium and magnesium ions
as corresponding carbonates.
Ca(HCO3)2(aq) + 2NH4OH(aq) CaCO3(s) +2H2O(l) + (NH4)2CO3(aq)
Advantages of hard water

(i). It is good for drinking purposes as calcium ions contained in it helps to form
strong bones and teeth.
(ii). When soft water flows in lead pipes some lead is dissolved hence lead
poisoning. However when lead dissolves in hard water insoluble PbCO 3 are formed,
coating the inside of the lead pipes preventing any further reaction; this reduces
any chances of lad poisoning.
(iii). It is good for brewing and the tanning industries; it improves wine or beer
flavour in brewing industries.
Disadvantages of hard water

(i). Soap forms insoluble salts with magnesium and calcium ions; scum
(calcium or magnesium stearate) thereby wasting soap.
For these reason soapless detergents are preferred to ordinary soaps
because they do not form scum; but rather form soluble salts with Mg 2+ and
Ca2+
(ii). Deposition of fur (CaCO3) in kettles, pipes and boilers. This reduces
efficiency in boilers and may make hot water pipes to burst.
(iv). Stains white cloths.
ENERGY CHNAGES IN PHYSICAL AND CHEMICAL PROCESSES
(THERMOCHEMISTRY)
Heat changes in chemical reactions can either be exothermic and endothermic.
(a). Endothermic reaction

Is a reaction accompanied by a fall in temperature and energy is absorbed from
the surroundings.
The enthalpy change is normally positive since heat of products (HProducts) is higher
than heat of reactants (Hreactants).
(b). Exothermic reactions.

Are reactions accompanied by a rise in temperature and energy is liberated to the
surroundings.
The enthalpy change is normally negative, since heat of reactants (H1) is normally
higher than heat of products (H2).
Examples:
(i). Manufacture of ammonia in the Haber process;
i.e. N2(g) + 3H2 (g) 2NH3(g); ∆H=-46Kjmol-
(ii) Dissolving sodium hydroxide pellets in water,

The temperature of the resulting NaOH(aq) is higher than the temperature of water
at room temperature.
Bond Breaking and Bond Formation in Physical and Chemical

processes
For reactions to occur between substances the bonds must be broken and new
bonds formed.
What Energy changes take place when solids and liquids are
heated to melting point and boiling point?
Effect of Heat on pure ice
Point AB: Temperature of ice rises with time. This is because the molecules absorb
heat energy. The heat energy absorbed is converted to kinetic energy. This makes
the molecules vibrate more vigorously.
Point BC: Temperature of ice remains constant with time. This is because the heat
energy absorbed is used to change the state from solid to liquid at its melting
point.
The amount of heat energy required to convert a given amount of a solid substance
to a liquid at its melting point is called latent heat of fusion.
Molar latent heat of fusion is the amount of heat energy required to convert one
mole of a solid substance to a liquid at its melting point.
Point CD: Temperature of the liquid rises with time. This is because the molecules
absorb heat energy. The heat energy absorbed is converted to kinetic energy. This
makes the molecules move faster and further away from each other.
Point DE: Temperature of the liquid remains constant with time. This is because
the heat energy absorbed is used to change the state from liquid to gas at its
boiling point.
The amount of heat energy required to convert a given amount of a liquid
substance to a gas at its boiling point is called latent heat of vaporisation.
Molar latent heat of vaporization is the amount of heat energy required to convert
one mole of a liquid substance to a gas at its boiling point.
Examples
1. Reaction between Methane and chlorine
Products are at lower level than reactants hence the reaction is exothermic.
2. Reaction between hydrogen gas and chlorine gas
Worked example
Use the following bond energies to determine whether the reaction below is
exothermic or endothermic.
H2(g) + Cl2(g) → 2HCl(g)
Bond Energy in kJ mol-1

H-H +436
Cl-Cl +244
H-Cl +432
Working
Heat of reaction = Bond breaking energy + Bond formation energy

= +680 + -864
= -184 kJ
The reaction is exothermic.
Determination of Enthalpy Changes
1. Heat of solution/ enthalpy of solution.

Is the heat change when a given mass (moles) of a substance is dissolved in a
stated amount of solvent (water).
Molar enthalpy of solution:

It is the heat change when one mole of a substance dissolves in water to give an
infinitely dilute solution i.e. (a solution which shows no change in its properties
when more water is added).
∆Hsolution = ∆Hlattice + ∆Hhydration
Note: ∆Hlattice is always positive ; ∆Hhydration is always negative
Lattice energy
Is the heat evolved when one mole of a compound is formed from its separate
gaseous ions. or
It is the energy required to break the ionic bonds within a crystal (solid) lattice.
Hydration (solvation) energy,

Is the heat evolved when one mole of ions are hydrated by water molecules.
Heat of solution can either be exothermic or endothermic depending on the
magnitude of hydration and lattice energies.
Solution process occurs into two stages.
Examples:
1. Consider the dissolution of sodium chloride solid.
Energy is taken in to break the crystalline lattice.
NaCl(s) Na+(g) + Cl-(g)

∆H = +∆Hlattice
=+776KJ.
Heat is evolved when one mole of ions are hydrated by water molecules.
Na+(g) + Cl-(g) H2O(l) Na+(aq) + Cl-(aq) ∆H hydration=-771KJ
Na+(g) + Cl-(g) + H2O(l)
Step II
Step I ∆Hhydration
Enthalpy (kJ)
∆Hlattice Na+(aq) + Cl-(aq)

Final state
∆H solution
NaCl(s) + H2O(l)
Initial state
Reaction pathway
∆Hsolution = ∆Hlattice + ∆Hhydration
= +776KJ + -771KJ
= +5 KJ
2. The lattice and hydration enthalpies for lithium chloride and potassium chloride
are given below.
Salt ∆Hlattice ∆Hhydration.

LiCl -861 -884
KCl -719 -695
(a). Calculate the enthalpy of solution, ∆Hsolution; Kj mol- for;

I. Lithium chloride.
II. Potassium chloride:
Solution:
I. Lithium chloride.
Hsolution = ∆Hlattice + ∆Hhydration

= (+861) + (-884)
= 861- 884;
= -23Kjmol-
II. Potassium chloride:
Hsolution = -∆Hlattice + ∆Hhydration

= (+719) + (-695)
= 719- 695;
= -24Kjmol-
(b) Which of these two salts above has a higher solubility in water? Give
reasons for your answer.
Solution:
Potassium chloride; the difference in ∆Hsolution is greater;
Experiment: To measure the molar enthalpy change for the dissolution
(enthalpy of solution) for various compounds.
(i) Procedure;
A clean 250 cm3 glass or plastic beaker is wrapped with a newspaper leaf.
About 100 cm3 of distilled water is measured into the beaker and the steady
temperature noted.
The beaker is held in a tilted position and 2 cm3 of and sulphuric acid added into
the water.
Conc. Sulphuric acid
Tap water
The mixture is then carefully but vigorously stirred using a thermometer and the
highest temperature of the solution recorded.
The experiment is repeated with other compounds:
2.5 g Sodium nitrate solid
2.0 g Sodium hydroxide pellets.
Results and observations.
Conc. H2SO4 Sodium Sodium

nitrate solid hydroxide
pellets
Temperature of water(˚c) 24.0 21.0 21.5
Highest temp of solution (˚c) 29.5 19.5 26.5
Change in temperature(˚c) 4.5 1.5 5.0
Calculate the enthalpy change (∆Hsoln) in each experiment done.
Additional information;
Density of water =1gcm-3
No change in volume when any of the solids dissolved in water
The specific heat capacities of the solutions=4.2kjkg-1k-1
(a). Sulphuric acid:
Density of concentrated Sulphuric acid =1.84gcm-3
Total volume of solution = (100 +2) =102 cm3
Temperature change =A rise of 4.5ºC
C = 4.2kjkg-1k-1
Enthalpy change; ∆Hsoln; =MC∆T
102 X 4.2 X 4.5

=
1000
= - 1.9278kj
Calculating molar enthalpy of solution of concentrated sulphuric acid:

Mass of acid used = density x volume
= 1.84 x 2 = 3.68g;
3.68
Moles of H2SO4 = = 0.03755
98
−1.9278
Molar enthalpy of solution = = - 51.34 kJ/mole
0.03755
(b). Sodium nitrate:

Data:
Volume of water used = 100 cm3
Mass of sodium nitrate = 2.5g
Initial temperature of water = 21.0ºC
Final temperature of solution =19.5ºC
∆T = 1.5ºC
Enthalpy change = MC∆T

100 x 4.2 x 1.5
=
1000
= + 0.42Kj
Molar heat of dissolution;

2.5
Moles of NaNO3 = = 0.02941
85
+ 0.42
Molar heat of dissolution = = + 14.28 kJ/mole
0.02941
Assignment
Draw energy level diagram for the dissolution of sodium nitrate based on the
results above.
2. Enthalpy of combustion (∆Hc)
Molar enthalpy of combustion is the enthalpy change that occurs when one
mole of a substance is completely burned in oxygen.
Example; Enthalpy of combustion of Ethanol

Pour 100 cm3 of distilled water into a 250 ml glass beaker. Record the temperature
of the water. Half fill a small bottle with ethanol and close the bottle with a lid
fitted with a clean wick.
Weigh the bottle and its contents and arrange the apparatus as shown below.
Light the wick to start heating the water. Stir the water carefully with the
thermometer and extinguish the flame when the temperature of the water has
risen by 15 oC. Record the temperature of the water. Weigh the bottle and its
contents again. Record the results obtained.
Initial mass of bottle + contents = 28.25 g

Final mass of bottle + contents = 28.02 g
Mass of ethanol burnt = 0.23 g
Final temperature of water = 43.0 oC
Initial temperature of water = 28.0 oC
Rise in temperature of water = 15.0 oC
Enthalpy change = MC∆T

100 x 4.2 x 15
=
1000
= - 6.3Kj
Molar heat of combustion;
0.23
Moles of C2H5OH = = 0.005
46
−6.3
Molar heat of combustion = = - 1260 kJ/mole
0.005
Assignment
1. Draw energy level diagram for the of combustion of Ethanol based on the results
above.
2. When 0.6g of element J were completely burned in oxygen, all the heat evolved
was used to heat 500 cm3 of water, the temperature of the water rose from 23.0 oC
to 32.0oC. Calculate the relative atomic mass of element J given that the specific
heat capacity of water = 4.2jg-1k-1, density of water=1.0gcm-3 and molar heat of
combustion of J is 380JMol-
Fuels:
A fuel is a compounds that produces useful energy when it undergoes a chemical
or nuclear reaction.
Fuels can be:-
Solids; such as charcoal, wood, coal.
Liquids; such as ethanol, gasoline
Gaseous; such as methane, water, gas etc.
Heating value of a fuel:

Is the amount of heat energy given out when a unit mass or unit volume of a fuel
is completely burnt in oxygen.
Molar heat of combustion

Heating value =
molar mass
Factors to consider when choosing a fuel.

(i) Heating value,
(ii) Ease and rate of combustion.
(iii) Availability
(iv) Ease of transportation
(v) Ease of storage
(vi) Environment effects.
3. Enthalpy of displacement
Molar enthalpy of displacement is the enthalpy change that occurs when one mole
of substance is displaced from a solution of its ions.
Experiment: To determine the molar enthalpy change when zinc reacts with
copper (II) sulphate solution
Procedure:
A plastic beaker is wrapped with a newspaper leaf.
25 cm3 of 0.2M copper (II) sulphate solution is transferred into the beaker.
The steady temperature of the solution is noted.
0.5g of zinc powder are carefully transferred into the plastic beaker and stirred
with a thermometer.
The highest temperature attained by the solution is recorded.
Observations:
The blue colors of copper (II) sulphate fades.
Brown deposits of copper metal are formed.
Explanation:
Zinc is higher in the electrochemical series than copper;
Zinc therefore displaces copper ions from its solution.
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
Ionically:
Zn(s) + Cu2+(aq) → Zn2+ + Cu(s)
Results:
Initial temperature of copper sulphate solution, T1 = 23˚C
Highest temperature of the mixture T2 = 33ºC
Temperature change, ∆T; = T2-T1 =10ºC
Volume of copper sulphate solution used = 25.0 cm3.
Mass of zinc powder taken = 0.5g
Density of the solution = 1gcm-3.
Specific heat capacity of the solution = 4.2Kjkg-1k-1.
Assumptions:
The volume of the solution remains unchanged after the reaction.
(Cu = 63.5, S = 32, O =16, Zn = 65, Fe =56)
Question:
Using the above data, calculate, calculate the;
(i). Heat change for the above reaction.
(ii). The molar heat of displacement of copper (II) ions.
Solutions:
(i) Heat change = MC∆T
Mass = density x volume
1gcm -3 x 25cm3 =25g.
∆H = 25 x 4.2 x 10
1000
= - 1.050Kj
(ii). Molar heat of displacement of Cu2+ displacement.
Moles = 0.2 x 25 = 0.005moles

1000
−1.050
Molar heat change = = - 210 kJ/mole
0.005
Thermochemical equation:
Zn(s) + Cu2+(aq) → Cu(s) + Zn2+(aq); ∆H=-210kJmol-1
Note:
The experimental value for the heat liberated in this reaction is lower than the
theoretical value of 216Kjmol-1.
Reasons:
The heat lost to the surroundings and the heat absorbed by the apparatus is not
accounted for in the calculations.
4. Heat of neutralization;
Molar Heat of neutralization is the heat change that occurs when an acid and a
base react to produce one mole of water.
Equation:
OH-(aq) + H+(aq) → H2O(l)
Neutralization reactions are exothermic.
Experiment: - To determine the heat of neutralization of hydrochloric acid by

sodium hydroxide.
A clean dry 250 cm3 glass or plastic beaker is wrapped with a newspaper leaf.
Exactly 50 cm3 of 2.0M hydrochloric acid solution is transferred into the beaker.
The temperature T1 of the acid solution is noted.
Using another clean dry measuring cylinder, exactly 50 cm3 of 2.0M NaOH solution
is measured and its steady temperature T2 is noted.
The contents of the beaker (acid), are carefully stirred with a thermometer while
adding NaOH.
The highest temperature T4 attained by the resulting mixture is noted.
Results:
Temperature of hydrochloric acid solution T1= 22.5oC;
Temperature of sodium hydroxide solution T2 = 23.0oC;
T 1+T 2
Average temperature of acid and alkali = T3 = 22.75 oC;
2
Highest temperature of alkali and acid mixture, T4 = 36.50oC;

Temperature change, ∆T= T4 – T3 = (36.5 – 22.75)oC;
=13.75 oC;
Note;
i) The specific heat capacity of the solution= 4.2KJKg-1K-1.
ii) Taking density of the resultant solution to be 1gcm -3,
(i) Heat change = MC∆T
∆H = 100 x 4.2 x 13.75

1000
= - 5.775Kj
(ii). Molar heat of neutralisation.
Moles = 2 x 50 = 0.1moles
1000
−5.775
Molar heat change = = - 57.75 kJ/mole
0.1
Standard conditions for measuring enthalpy changes

Enthalpy changes are affected by physical states of the reactants, temperature,
concentration and pressure.
Consequently, for comparison purposes certain conditions have been chosen as
standard for measurement and determination of enthalpy changes.
These conditions are:
A temperature of 25oC (298K)
Pressure of 1 atmosphere (101.325K)
Standard enthalpy changes:

Are values of enthalpy changes that are measured under standard conditions.
They are denoted by he symbol ∆H0
A subscript is also added to the symbol to indicate the type of enthalpy change
involved.
Common standard enthalpy changes

(i). ∆H0f; refers to the standard molar enthalpy change of formation.
Example:
H2(g) + ½ O2(g) → H2O(l); ∆H0f (H2O) = -286KJmol-
(ii). ∆H0c; refers to the standard molar enthalpy change of combustion;
Example:
CH4(g) + 2O2(g) → CO2(aq) + 2H2O(l); ∆H0c(CH4) = -890KJmol-
(iii). ∆H0neut; refers to the standard molar enthalpy change of neutralization.
Example:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l); ∆H0neut = -58KJmol-
(iv). ∆H0soln; refers to the standard molar enthalpy change of solution

Example:
NaNO3(s) + H2O(l) → NaNO3(aq); ∆H0soln (NaNO3) = +21KJmol-
(v). ∆H0hyd; refers to the standard molar enthalpy change of hydration.

Example:
Na+(s) + Cl-(s) + H2O(l) → Na+(aq) + Cl-(aq); ∆H0hyd (NaCl) = -774KJmol-
(vi). ∆H0latt; refers to the molar enthalpy change of lattice formation.

Example:
Na+(g) + Cl-(g) → NaCl(aq); ∆H0latt (NaCl) = -774KJmol-
(vi). ∆H0at; refers to the standard molar enthalpy change of atomization.
Example:
Na(s) → Na(g); ∆H0at (Na) = 108.4 KJmol-
Hess’s law of constant heat summation

States that the energy changes in converting reactants to products is the same
regardless of the route by which the chemical change occurs.
Worked examples:
1. Use the information below to determine the enthalpy of combustion of carbon
(formation of carbon (IV) oxide). (Ans; -392.45KJ)
C(s) + ½O2(g) → CO(g); ∆H = -110.45KJ
CO(g) + ½O(g) → CO2(g); ∆H = -282.0KJ
2. One mole of butane(C4H10) burns completely in oxygen and liberates 2877kj.

(a) Write an equation for the combustion of butane.
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l)
(b) Draw an energy cycle, hence an energy level diagram for the reactions
concerned.
3. If the following heats of combustion are given

∆Hºc (graphite) = -393kjmol-
∆Hºc (H2(g)) = -286KJmol-
∆Hºc (C4H10) = -2877kjmol-
Calculate the heat of formation of butane, C4H10 from its elements in their normal
states at S.T.P. ( Ans; -125KJ/mol)
4. Given the standard enthalpies of combustion as

C(s) + O2(g) → CO2(g); ∆H1 = -394kJmol-;
H2(g) + ½O2(g) → H2O(l); ∆H2 = -286kJmol-
C2H2(g) + 1½O2(g) → 2CO2(g) + H2O(l); ∆H = -1300kJmol-.
Find the standard enthalpy of formation of ethyne, C2H2(g). (Ans;+226kJ/mol)
RATES OF REACTION AND REVERSIBLE REACTIONS
Reaction rate:
Is the measure of how much of the reactants are consumed or how much of the
products are formed per unit time.
Measurements of reaction rates

Reaction rates are measured in terms of
i) How much product is formed in a given time.
ii) How much reactant is consumed in a given time
Collision theory and activation energy
Activation energy (EA):

Is the minimum amount of energy required by reacting particles to cause a
successful collision to form products.
Factors determining the value of activation energy:

i) Strength of the bonds in the particles of the reactants;
ii) Whether the reaction is exothermic or exothermic;
iii) Presence of catalysts;
Factors affecting the rate of reaction

a. Concentration of reactants
b. Temperature
c. Surface area (size of the particles
d. Catalyst Light
e. Pressure
(a). Concentration of reactants.
Increase in concentration of one of the reactants increases the rate of the
reaction;
Reason:
Higher concentration results in a greater probability of collision hence a
higher rate of reaction
Worked example:
In an experiment to determine the effect of concentration on the rate of a reaction,
various concentrations of sodium thiosulphate were reacted with equal volume of
hydrochloric acid and the time taken for the precipitate to obscure a cross on
paper put under the reaction beaker was determined.
The results are shown in the table below.
Volume of S2O32- Volume of H2O, Volume of HCl, Time for cross

(cm3) cm3 cm3 to disappear, (s)
50 0 10 20
40 10 10 25
30 20 10 34
20 30 10 52
10 40 10 70
(a). Plot a graph of time (vertical axis) against volume of aqueous sodium
thiosulphate.
(b). From the graph estimate the time for the cross to disappear when 10 cm 3 of
hydrochloric acid is added to a mixture of 35cm3 of aqueous thiosulphate and
15cm3 of water.
(c). What is the effect on the rate of the reaction of adding more water to the
aqueous sodium thiosulphate? Explain your answer.
(d). On the same graph, plot the curves you would obtain if the experiment were
repeated at:
(i). at 45oC;
(ii). using 10 cm3 of less concentrated hydrochloric acid.
(b). Effect of temperature
An increase in temperature increases the rate of a chemical reaction.
Reasons:
Increase in temperature increases the kinetic energy of the reacting particles;
The particles therefore move faster leading to more frequent and more effective
collisions.
The rate of reaction therefore increases;
(c). Effect of particle size (surface area).

A decrease in particle size (surface area) increases the rate of a chemical reaction;
and an increase in particle size decreases the rate of a chemical reaction.
Reason:
A smaller particle size means a larger total surface area and this offers a large
surface on which the reacting particles can collide;
This means more collisions, hence more chances of effective collisions leading to a
higher rate of reaction;
Example: Reaction between dilute HCl and marble chips

The larger CaCO3 granules undergo a slower rate of reaction than the finely
powdered CaCO3
Worked example:
3.0g of powdered carbonate of metal M of formula MCO 3 were mixed with excess
dilute hydrochloric acid. The mass of the reaction vessel and its contents were
recorded at various times. From these readings, the total loss in mass of the
reaction vessel and its contents was calculated and recorded as shown in the table
below. The experiment was carried out at room temperature.
Time (secs) 0 30 60 90 120 150 180 210

Total loss in mass (g) 0 0.08 0.37 0.90 1.19 1.28 1.32 1.32
(a) (i). Plot a graph of total loss in mass against time.

(ii). Determine the total loss in mass after 100seconds.
(b) (i). Write an equation for the reaction that occurs.
(ii). calculate the number of moles of:
Carbon (IV) oxide gas produced.
MCO3 used.
(iii). Calculate the relative atomic mass of metal M.
(c). On the same axis sketch a curve that you are likely to obtain if the
experiment was repeated:
(i) At 50oC. Explain.
(ii). Using MCO3 granules instead of the powder. Explain.
(d). Effect of catalysts

Catalysts are substances which alter the rate of a chemical reaction without being
consumed, e.g. finely divided iron in the Haber process;
They alter the rate of a chemical reaction but remain unchanged at the end of the
reaction;
They can therefore be reused at the end of the reaction;
Note: Generally, a catalyst increases the rate of a reaction by lowering

activation energy.
Worked example:
Hydrogen peroxide decomposes slowly to water and oxygen under normal
conditions.
When a little manganese (IV) oxide is added to the solution the rate of
decomposition is enhanced. The results of an experiment on the decomposition of
hydrogen peroxide in presence of manganese (IV) oxide are shown below. Study the
results and answer the questions that follow.
Volume of 0 19 27 33 36 38 39 40 40
oxygen (cm3)
Time (seconds) 0 30 60 90 120 150 180 210 240
(a). Plot a graph of volume of oxygen produced (vertical axis) against time.
(b). What is the rate of reaction:

(i). during the first 30 seconds.
(ii). between 30 seconds and 60 seconds.
(c). Explain why:
(i). the slope of the curve is steeper at the start of the reaction.
(ii). the curve goes flat at the end of the reaction. (d) (i).
Suggest the role of manganese (IV) oxide I the decomposition of hydrogen
peroxide.
(ii). Comment on change in mass of manganese (IV) oxide at the end of the
reaction. Explain,
(e). Effect of light on the rate of reaction

Examples of reactions affected by light are those involving halogens:
Examples of reactions affected by light.

i) Reaction between Cl2(g) and H2(g) does not take place in the dark but is
explosive in bright light;
bright light
Cl2(g) + H2(g → 2HCl (g)
ii) For the reaction between methane and bromine; decolourisation of bromine
only occurs in presence of light;
Light
CH4(g) + Br2(l) → CH3Br(g) + HBr(g)
Experiment: Effect of light on the decomposition of silver bromide
Procedure:
About 20cm3 of 0.1M potassium bromide is put in a glass beaker.
5cm3 of 0.05M silver nitrate solution is added.
The resulting pale yellow precipitate is divided into three portions in 3 separate test
tubes.
One of the test tubes in immediately placed in a dark cupboard; the second on a
bench and the third is placed in a direct source of light e.g. sunlight.
Observations.
Formation of a pale yellow precipitate of silver bromide when silver nitrate reacts
with potassium bromide.
Equation:
KBr (aq) + AgNO3(aq) → AgBr(s) + KNO3(aq)
Pale yellow
Test tube in light: precipitate changes colour from pale yellow to grey.
Test tube on the bench: slight change in colour from pale yellow to slight grey.
Test tube in dark cupboard: no observable (noticeable) colour change in
precipitate.
Explanation:
Light decomposes silver bromide to metallic silver (hence the grey colour) and
bromine.
Equation:
Light
2AgBr(aq) → 2Ag(s) + Br2(g)

grey
No observable change in test tube placed in darkness due to lack of light;
The degree of decomposition and hence change depends on the light intensity
falling on the test tubes;
The rate of decomposition of silver bromide increases with increase in light
intensity.
Conclusion:
Light affects the rate of some chemical reactions by energizing the particles
involved in a reaction hence increasing the chances of effective collisions per unit
time thus increasing the rate of reaction.
Application of effect of light on reaction rate.

Processing of black and white photographic films is done in dark to prevent the
decomposition of the silver bromide that is usually used to coat photographic
plates;
(f). Pressure
Pressure has no effect on reactions involving solids and liquids. It only affects
reactions in which either the reactants or products are gases.
Increasing the pressure of reacting gases by compressing brings the gaseous
particles closer thus increasing the rate of effective collisions. This results in an
increase in the rate of a reaction.
Reversible reactions
Are reactions which can proceed in both directions (forward or backward) by
changing conditions such as temperatures, pressure etc.
Note:
Reversible reactions are of two types:
i) Reversible physical changes e.g. heating ice, iodine etc.
ii) Reversible chemical changes e.g. heating hydrated copper (II) sulphate,
Haber process, decomposition of limestone, heating blue cobalt chloride,
ammonium chloride etc.
Examples:
Reaction of nitrogen and hydrogen to give ammonia in the Haber process.
N2(g) + 3H2(g) 2NH3 (g)
The reversible sign means the reaction can reach a state of equilibrium if left
undisturbed.
Equilibrium:
Is the state at which the rate of forward reaction is equal to the rate of backward
reaction.
If a sample of ammonium chloride is heated in a closed container, both the forward
and backward reactions take place.
NH4Cl(s) NH3(g) + HCl(g)
Factors affecting the position of equilibrium

Such factors act as a strain on the state of equilibrium and the system reacts in a
way to oppose the change.
The factors are:
a. Concentration
b. Pressure
c. Temperature
d. Catalysts.
(a). Concentration
Consider the equilibrium in bromine water system:
Br2(aq) + H2O(l) OBr-(aq)+ Br-(aq) + 2H+(aq)

Yellow Colourless
State and explain the effect of addition of sodium hydroxide to the

equilibrium:
Colorlessness intensify (equilibrium shifts to the right).
Explanation:
Addition of sodium hydroxide provides hydroxyl ions into the equilibrium.
The hydroxyl ions react with the hydrogen ions (on the right of equilibrium) to form
water.
Equation:
OH-(aq) + H+(aq ) H2O(l)
State and explain the effect of addition of hydrochloric acid to the

equilibrium:
Yellow intensify (equilibrium shifts to the left).
Explanation:
Addition of hydrochloric acid introduces more hydrogen ions into the equilibrium;
The hydrogen ions react with the colourless bromide and hypobromite ions to
form yellow-orange aqueous bromine;
This shifts the equilibrium to the left hence the increase in the intensity of the
yellow colour of bromine water;
Further examples:
Given the equilibrium:
2CrO42-(aq) + 2H+(aq) 2Cr2O72-(aq) + H2O(l)

Yellow Orange
Addition of sodium hydroxide to the equilibrium:

Yellow colour intensifies
Explanation:
Addition of sodium hydroxide provides hydroxyl ions into the equilibrium.
The hydroxyl ions react with the hydrogen ions (on the left of equilibrium) to form
water.
This process removes hydrogen ions from the equilibrium mixture.
This shifts the equilibrium to the left hence formation of more reactants (chromate
and hydrogen ions);
This leads to a change in colour from orange to yellow;
Addition of hydrochloric acid:

Orange colour intensifies.
Explanation:
Addition of hydrochloric acid introduces more hydrogen ions into the equilibrium;
The hydrogen ions react with the yellow chromate solution to form orange
dichromate solution (and water);
This shifts the equilibrium to the right hence the increase in the intensity of the
orange colour of dichromate solution;
(b). Pressure
A change in pressure will only affect equilibrium in reactions involving gases. It has
no effect on those reactions in which both the reactants and products are either
solieds or liquids since they cannot be compressed or expanded.
Example:
1) N2 (g) + 3H2 (g) 2NH3 (g)
Increase in pressure favours the production of ammonia; by shifting the

equilibrium position to the right; because the volume of gaseous reactants is
higher than the volume of gaseous products.
Decrease in pressure leads to the production of less ammonia (ammonia
decomposes); by shifting the equilibrium position to the left; because the volume of
gaseous reactants is higher than the volume of gaseous products.
2) N2O4 (g) 2NO2 (g)

Pale yellow dark brown
Increase in pressure:
Shifts the equilibrium to the left; leading to formation of more N 2O4 hence mixture
turns pale yellow; because the volume of gaseous products (NO2) is higher than the
volume of gaseous reactants (N2O4).
Decrease in pressure:
Shifts the equilibrium position to the right; leading to formation of more NO 2 hence
colour turns dark brown; because the volume of gaseous reactants (N 2O4) is lower
than the volume of gaseous products (NO2);
3) N2 (g) + O2 (g) 2NO(g)
Note: -
Change in pressure has no effect on the equilibrium mixture where gaseous
molecules on the two sides are equal
Increase or decrease in pressure has no effect on position of equilibrium; because
the volume of gaseous reactants is equal to volume of gaseous products;
Note:
Generally reactions involving only solids and, or liquids are not affected by
pressure change because they are not compressible;
(c). Temperature
i) Endothermic reactions
Increase in temperature favours the endothermic reactions;
Example:
N2O4 (g) 2NO2 (g) ; ∆H = + ve
Pale yellow dark brown
Increase in temperature shifts the equilibrium to the right; since the reaction is
endothermic and hence more yield of nitrogen (IV) oxide; hence dark brown fumes
will be observed;
Decrease in temperature shifts the equilibrium to the left; since the reaction is
endothermic favoured by low temperatures; hence formation of N 2O4; and the pale
yellow colour is observed;
ii) Exothermic reactions:

Decrease in temperature favours exothermic reactions.
Example:
2 SO2(g) + O2(g) 2SO3(g); ∆H = -ve
Thus:
Decrease in temperature causes more yield of sulphur (VI) oxide; because the
equilibrium shifts to the right; since the reaction is exothermic favoured by low
temperatures;
Increase in temperature causes SO3 to decompose decreasing its yields. Increase in
temperature shifts the equilibrium to the left; because the reaction is exothermic
which is favoured by low temperatures;
(d). Effect of catalyst
Presence of a catalyst has no effect on the position of the equilibrium but alters the
rate at which the equilibrium is attained.
Catalysts usually allow the equilibrium to be reached in a shorter period of time by
increasing the rates of the reactions
ELECTROCHEMISTRY
Definition:
Electrochemistry is the chemistry of electrochemical reactions; which deal with the
relationship between electrical energy and chemical reactions.
Electrochemical reactions involve transfer of electrons and are essentially REDOX
reactions.
REDOX Reactions
A redox reaction is one in which reduction and oxidation processes occur
simultaneously. Redox reactions involve electron gain and electron loss.
Experiment :- What is observed when iron fillings are added to copper (II)
sulphate solution?
Procedure
(a). 5 cm3 of 1M CuSO4 (aq) is put in a test-tube and its temperature recorded.
In the solution, a spatula end-full of iron fillings is added.
Any observations and temperature change are determined and recorded.
The procedure is repeated with fresh samples of CuSO4 with Zn, Mg, and Cu
powders.
(b). The procedure is repeated with 1M magnesium sulphate solution instead of

CuSO4 (aq).
Observations:
Solution Copper (II) Sulphate Magnesium

Sulphate
Metal solid
Iron fillings A brown solid (Cu) is formed No reaction
The blue colour of the solution (Cu2+)
fades then changes to green (Fe2+)
Zinc powder A brown solid, copper metal is No observable
deposited. reaction (change)
The blue colour of the solution (Cu2+)
fades then turns colourless;
Copper No reaction No reaction
powder
Explanations
Reactions between metals and ions of another metal involve transfer of electrons
from the metal to the other metal ion in solution.
Examples:
Fe(s) and CuSO4 (aq)
Copper being lower in the electrochemical series accepts electrons easier (than Fe)
to form copper atoms (brown solid);
Half equations
Fe (s) → Fe2+(aq) + 2e-
Cu2+(aq) + 2e- → Cu (s)
Overall reaction
Cu2+(aq) + 2e- + Fe(s) → Fe2+(aq) + 2e- + Cu(s)
Then;
Cu2+(aq) + Fe(s) → Fe 2+
(aq) + Cu (s)
(Blue) (Green) (Brown solid)
Oxidation and reduction in terms of electron loss and gain

The loss of electrons is oxidation and the species that gains electrons (causes
electron loss); Cu2+ in this case is called oxidizing agent; and is itself reduced.
Reduction: refers to gain of electrons, and the species that donates electrons
(iron solid in this case) is called a reducing agent and is itself oxidized.
Displacement reactions generally involve reduction and oxidation simultaneously
and are thus termed Redox Reactions.
Further examples
(i). Zinc solid and CuSO4(aq)
(i). Zn(s) → Zn2+(aq) + 2e- (Oxidation)

(ii). Cu2+(aq) + 2e- → Cu(s) (Reduction)
Then: Cu2+(aq) + Zn(s) → Zn2+(aq) + Cu(s) (Redox)
(iii). Silver nitrate and copper solid.
(i). Cu(s) → Cu2+(aq) + 2e- (Oxidation)

(ii). 2Ag+(aq) + 2e- → 2Ag(s) (Reduction)
Then: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) (Redox)
Note:
Amount of heat evolved in these redox reactions depends on the position of the
metal in the activity series relative to the metal ion in solution.
The closer the metals are in the activity series; the less readily displacement
occurs and the lower the heat evolution during the displacement.
E.g.: Heat evolved Mg//Cu2+ is higher than that evolved between Fe//Cu2+.
Conclusion:
Metals displace from solutions, those metals lower than themselves in the activity
series.
Note:
The more the reactive a metal is; the stronger a reducing agent it is and the
weaker an oxidizing agent it is.
Example:
Potassium is stronger reducing agent; but weaker oxidizing agent than silver, gold
etc.
Summary on displacement reactions
Metal Mg Al Zn Fe Pb Cu
Metal ion (in

solution)
K+      
Na+      
Ca2+      
Mg2+      
Al3+     
Zn2+    
Fe2+   
Pb2+  
Cu2+ 
Ag2+
Key:
A cross (x) indicates no reaction hence no redox reaction occurs.
A tick indicates redox reaction occurs.
Oxidation numbers/ oxidation state

Is the apparent charge that an element has in a compound or the charge on an ion.
Example:
Oxidation no of Aluminium in Al3+ is +3;
Importance of oxidation numbers:
Helps in keeping track of electron movement in redox reactions; hence
determination of the reduced and oxidized species.
Oxidation and reduction in terms of oxidation numbers

Oxidation
Is an increase in oxidation number.
Reduction
Refers to a decrease in oxidation number
Rules in assigning oxidation numbers

1. Oxidation number of an uncombined element is zero (0)
2. The charge on a monoatomic ion is equivalent to the oxidation number of
that element;
3. The oxidation number of hydrogen in all compounds is +1 except in metal
hydrides where it’s –1;
4. The oxidation number of oxygen in all compounds is –2 except in peroxides
where it is –1 and 0F2 where it is +2.
5. In complex ions the overall charge is equal to the sum of the oxidation states of
the constituent elements.
6. In compounds, the sum of oxidation numbers of all constituent atoms is
equal to zero.
Worked examples
1. Calculate the oxidation number of nitrogen in:
(i). NO3-
Solution:
N + (-2 x 3) = -1
N = -1 + 6
= +5
Note: thus nitric acid is called nitric (V) acid since the oxidation number of
nitrogen in it is +5;
(ii). NO2;
Solution:
N + (-2 x 2) = 0
N=0+4
= +4
Note: Thus the gas NO2 is referred to as nitrogen (IV) oxide because the oxidation
umber of nitrogen in it is +4
(iii). AgNO3;
Solution:
1 + N + (-2 x 3) = 0
1 + N + (-6) = 0
N = 0 – 1 + 6;
N = +5
2. Determine the oxidation number of manganese in each of the following, and hence
give the systematic names of the compounds.
(i). MnSO4
Solution:
Mn + 6 + (-2 x 4) = 0
Mn = 0 – 6 + 8;
Mn = +2
Systematic name: Manganese (II) sulphate;
(ii). Mn2O3;
Solution:
2Mn + (3 x -2) = 0;
2Mn = 0 + 6
Mn = ½ x 6;
Mn = +3;
Systematic name: Manganese (III) oxide;
(iii). KMnO4
Solution:
1 + Mn + (-2 x 4) = 0
Mn = 0 – 1 + 8;
Mn = +7;
Systematic name: Potassium manganate (VII) oxide
(iv). MnO3-;
Solution:
Mn + (-2 x 3) = -1
Mn = -1 + 6;
Mn = +5
Systematic name: Manganese (V) ion;
Determination of redox reactions using oxidation numbers
Worked examples:
Redox reactions involving Halide ions and halogens

Experiment
(i). Procedure:
2 cm3 of chlorine gas are bubbled into each of the following solutions: - KI, KCl,
KBr, and KF.
The observations are made and recorded.
The procedure is repeated using fluorine, bromine and iodine in place of chlorine.
(ii). Observations
Halide Potassium Potassium Potassium Potassium

fluoride Chloride Bromide Iodide
Halogen
Chlorine (Cl2) Solution Solution Colourless Colourless
remains remains solution turns solution turns
colourless colourless red brown black
Bromine Solution Solution Solution remains Colourless
(Br2) remains remains colourless solution turns
colourless colourless black;
Iodine (I2) Solution Solution Solution remains Colourless
remains remains colourless solution turns
colourless colourless black;
Note: Colours of halogens in tetra – chloromethane:-
Halogen Colour in
tetrachloromethane
Chlorine Yellow
Bromine Red-brown
Iodine Purple
Explanations
Fluorine displaces all the other halogens; Cl2, Br2 and I2 because it has a greater
tendency to accept electrons than all the rest.
Chlorine displaces both Bromine and Iodine from their halide solutions
Cl2 takes electrons from the bromide and iodide ions i.e. oxidizes them, to form
bromine and iodine respectively.
Equations:
(i). Chlorine and potassium bromide:
Cl2 (g) + 2KBr (aq) → 2KCl (aq) + Br2 (l)
Cl2 (g) + 2Br-(aq) → 2Cl-(aq) + Br2 (l)
Cl2 (g) + 2Br-(aq) → 2Cl-(aq) + Br2 (l)
(ii). Chlorine and Potasium iodide:

Cl2 (g) + 2KI (aq) → 2KCl (aq) + I2 (l)
Cl2 (g) + 2I-(aq) → 2Cl-(aq) + I2 (l)
Note: oxidation number of chlorine decreases from 0 to -1 hence reduction; while

oxidation number of iodine increases from -1 to 0; hence oxidation;
Electrochemical Cell
The tendency of metals to form ions

When a metal is placed in an aqueous solution of its ions, some of the metal
dissolves;
M(s) → Mn+ (aq) + ne-
Dissolution of the metal causes electron build up on its surface; making it

negatively charged, while the surrounding solution becomes positively charged.
The positive charge of the solution increases and some of the cations start
recombining with the electrons on the metal surface to form atoms.
Mn+ (aq) + ne- → M(s)
Consequently, an electric potential difference is created between the metal rod and
the positively charged ions in solution.
This arrangement of a metal rod (electrodes) dipped in a solution of its ions
constitutes a half – cell.
Note:
The tendency of a metal to ionize when in contact with the ions differs form one
metal to another.
This difference can be measured by connecting two different Half – cells to make a
full cell.
The electrodes of the 2 half – cells are connected by a metallic conductor; while the
electrolytes (solutions) of the half cells are connected through a salt bridge.
Connection of two half cells to a full cell.
The difference between the electrode potentials of the two electrodes is called the
electromotive force (e.m.f) of the cell. The e.m.f is measured in volts using a
voltmeter.
Functions of the salt Bridge

i) Complete the circuit by making contact between the two solutions
(electrolytes)
ii) Maintains balance of charges in electrolytes by providing ions to replace
those ions that are used up or those that are formed.
Experiment: - to measure the relative tendency of metals to ionize
Example 1
Observations
The zinc rod in the zinc-zinc ions half – cell dissolves;
The blue colour of the copper (II) Sulphate solution fades/ decrease;
Brown deposits of copper appear on the copper rod. .
A voltage of 1.10 V is registered in the voltmeter.
Equations/ reactions, at each half cell

In zinc-zinc ions half cell
Zn(s) → Zn2+ (aq) + 2e-
In the copper-copper ion half cell

Cu2+ (aq) + 2e- → Cu(s);
On connecting the 2 half cells; electrons will flow form the zinc rod to the copper
rod through the external wire.
The copper rod gains the electrons lost by the Zinc rod.
The overall reaction in the cells is a Redox reaction

Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)
The voltage of 1.10 V registered in the voltmeter is a measure of the difference

between the electrode potential (Eθ) of Zinc and Copper electrodes, i.e. the
potential difference/ the Electromotive force.
Cell diagram for a voltaic cell

Rules/conventions for cell representation
1. A vertical continuous line (/); represents the metal-metal ion or metal ion-metal
interphase.
2. Two unbroken parallel lines (//).represents the salt bridge.
Example: - cell diagram for the above cell;

Zn(s) / Zn2+ (aq) // Cu2+ (aq) / Cu(s);
Electrode potential E0, values of other metal – metal ions with Cu/Cu 2+
half
cell as the reference half cell
Metal / metal ion half cell Electrode potential Eθ relative to

Cu2+ / Cu half cell
Mg(s) / Mg2+ (aq) +2.04
Zn(s) / Zn2+ (aq) +1.10
Pb(s) / Pb2+ (aq) +0.78
Cu(s) / Cu2+ (aq) +0.00
Ag(s) / Ag+ (aq) -0.46
Positive and negative E values
(i). Positive E values -

If the Eθ value for a metal / metal ion is positive then the metal undergoes
oxidation (loses electrons) while the reference electrode undergoes reduction
(accepts electrons)
Example:
The Eθ value for Zn(s) / Zn2+ (aq) relative Cu2+ (aq) / Cu(s) is positive because the zinc
metal is oxidized to zinc ions while the copper ions are reduced to copper metal.
(ii). Negative E values:

Implies that the reference half cell undergoes oxidation (donates electrons) while
the other metal ions in the other half cell undergoes reduction (accepts electrons)
Example:
The E value for Ag (s) / Ag+ (aq) is negative because Cu is more reactive than silver
and gives out electrons (oxidation); while the less reactive Ag has its ions accepting
electrons (reduction) to form Ag solid.
(iii). The 0 (Zero) E value:

Always indicate the reference electrode / half-cell; in which case there would be no
potential difference (with itself)
Example:
The 2 half cells of Cu(s) / Cu2+(aq) or Cu2+(aq) / Cu(s) have no potential difference in
between them hence a zero (0) E value.
Note:
The electrode potential of a single element is usually determined by measuring the
difference between the electrode potential of the element and a chosen standard
electrode.
This gives the standard electrode potential (E0) of the element.
The standard electrode potential (E0)

Definition
Is the potential difference for a cell comprising of a particular element in contact
with 1 molar solution of its ions and the standard hydrogen electrode.
It is denoted with the symbol E0.
The standard Hydrogen Electrode

Is the hydrogen half-cell, which has been conventionally chosen as the standard
reference electrode.
It has an electrode potential of zero at:-
A temperature of 25oC
A hydrogen pressure of 1 atmosphere
A concentration of 1M hydrogen ions
Note: The ions in the other half-cell must also be at a concentration of 1 molar.
Components of the Hydrogen half – cell;

Consist of an inert platinum electrode immersed in a 1M solution of Hydrogen ions
Hydrogen gas at 1 atmosphere is bubbled into the platinum electrode.
Platinised platinum
Is platinum loosely coated with finely-divided platinum.
This enables it to retain comparatively large quantity of hydrogen due to its porous
state.
Platinised platinum also serves as a route by which electrons leave or enter the
electrode.
The hydrogen electrode is represented as: H2 (g) / H+(aq); 1M
Negative and positive electrode potentials

(a). Negative electrode potential
If the metal electrode has a higher/ greater tendency to loose electrons than the
hydrogen electrode; then the electrode is negative with respect to hydrogen
electrode; and its electrode potential is negative.
Examples: Zinc, Magnesium etc.
(b). Positive electrode potential

If the tendency of an electrode to loose electrode is lower than the hydrogen
electrode, then the electrode is positive with respect to the hydrogen electrode; and
its potential is positive.
Examples: copper, silver etc
Reduction potentials
Is a standard electrode potential measured when the electrode in question is
gaining electrons.
The lower the tendency of an electrode to accept/ gain electrons; the lower (more
negative) the reduction potential and vise versa.
Examples:
K+ (aq) + e (aq) → K(s); E0 = -2.92V
F2 (g) + e- (aq) → 2F-(aq); E0 = +12.87V
Mg (s) + 2e- → Mg2+ (aq); Eθ = -2.71 V
Note:
The standard electrode potentials in the above table are reduction potentials.
The greater the tendency to undergo reduction, the higher (more positive) the E θ
value.
The reverse reaction (oxidation) would have a potential value equal in magnitude
but opposite in sign to the reduction potential.
Thus potassium ions with E0 = -2.92V have a lesser tendency to gain electrons than
magnesium ions.
Thus Potassium is the weakest oxidizing agent; but the strongest reducing agent,
since it has the greatest tendency to donate electrons.
Note:
Oxidation potentials will be the potentials of electrodes measured when they are
losing electrons hence undergoing oxidation.
Standard electrode potentials (reduction potentials) of some

elements
Lithium with E0 = -3.04 V has the highest tendency to lose electrons and therefore
is the strongest reducing agent. The more negative the E 0 value the greater the
reducing power. Lithium has the least tendency to accept electrons hence it is the
weakest oxidizing agent.
Fluorine with E0 = + 2.87 V has the highest tendency to accept electrons and
therefore is the strongest oxidising agent. The more positive the E 0 value the
greater the oxidising power. Conversely, fluorine is the weakest reducing agent
since it has the least tendency to lose electrons.
Uses of Standard Electrode Potentials

i) Comparing the oxidizing and reducing powers of substances.
ii) Determining the e.m.f of a cell
iii) Predicting whether or not a reaction will take place
The E0 value for a REDOX reaction

Is usually calculated as the sum of the E0 value for the half cells involved.
Note:
If the sum is positive then the reaction can occur simultaneously;
If the value of the sum is negative the reaction cannot occur;
Examples;
1. The reduction potentials of Mg(s)/Mg2+(aq) and Zn(s)/Zn2+(aq) half cells are;
Mg2+ (aq) + 2e- → Mgs) E0 = - 2.37 V
Zn2+ (aq) + 2e- → Zn(s) E0 = - 0.76 V
Using the electrode potential, answer the following questions.

i) Write an ionic equation for the cell made by combining the two half cells.
ii) Calculate the e.m.f of the cell formed in part (i).
iii) Write the cell notation/cell diagram for the cell.
Answers;
i) Mgs) + Zn2+ (aq) → Mg2+ (aq) + Zn(s) ; E0 = + 1.61 V
ii) - 0.76 – (- 2.37) = + 1.61 V
iii) Mg(s)/Mg2+(aq)// Zn2+(aq) /Zn(s) ; E0 = + 1.61 V
2. Use electrode potentials above to calculate the e.m.f for the electrochemical cell
represented below:
Al(s)/Al3+(aq)// Zn2+(aq) /Zn(s)
Answer;
- 0.76 – (- 1.16) = + 0.90 V
3. Use the cell representation below to answer the question that follows;
Cu(s)/Cu2+(aq)// Ag+(aq) /Ag(s) ; E0 = + 0.46 V
Given that the E0 value for Ag+(aq) /Ag(s) is + 0.80 V, calculate the E0 value for
Cu(s)/Cu2+(aq)
Answer; E0cell = E0R.H.S - E0L.H.S
+ 0.46 = + 0.80 - E0L.H.S
E0L.H.S = + 0.46 - 0.80

= + 0.34 V
4. Use the standard electrode potentials for the elements A, B, C, D and E given
below to answer the questions that follow. The letters do not represent the
actual symbals of the elements.
E 0 (volts)
A2+ (aq) + 2e- → A(s); - 2.37
B2+ (aq) + 2e- → B(s); - 0.76
C+ (aq) + e- → ½ C2(g); 0.00
D2+ (aq) + 2e- → D2(s); + 0.34
½ E2(g) + e- → E-(aq); + 1.36
i) What is the E0 value for the strongest oxidizing agent? Explain.

Answer: = 1.36 V i.e most positive
ii) Which two of the above element7s would produce the largest e.m.f or potential
difference in an electrochemical cell? Explain.
A and E; the elements with the most positive E 0 and the most negative E0
iii) What would be the initial potential difference of the cell chosen in (ii) above?
Answer; + 1.36 – (- 2.37) = + 3.73 V
iv) Write the cell represenitation for the electrochemical cell formed.
A(s)/A2+(aq)// ½ E2(g)/E-(aq), pt E0 = + 3.73 V
Note: pt represents platinum electrode.
Using standard Electrode potential to predict if a reaction will take place
Example;
Predict whether a reaction will occur between iodine and chloride ions
I2 (aq) + 2e- → 2I(aq); + 1.36 V
Cl2(aq) + 2e- → 2Cl-(aq); + 1.51 V
Answer;
I2 (aq) + 2e- → 2I(aq); + 1.36 V
2Cl-(aq) → Cl2(aq) + 2e- - 1.51 V
Overall E0 = ( +1.36) + (-1.51)

= -0.15 V
The overall E0 of the cell is negative. Therefore iodine cannot displace chlorine from
a chloride solution.
Use of Electrochemical cells

Electrochemical cells are used as a source of energy.
VOLTAIC CELLS
Are also called electrochemical cells.
Are cells in which electrical energy is generated from chemical reactions.
Types of electrochemical cells
(i). Primary cells -
Electrochemical cells which are not rechargeable
(ii). secondary cells-

Voltaic/electrochemical cells which are rechargeable.
1. Primary cells/dry cells:

Are of various types and an example is the Le’ clanche dry cell.
The Le’clanche dry cell
i) Structure
Consist of a Zinc can with carbon rod at the centre.

The central graphite/carbon rod is surrounded by powdered Manganese (IV) oxide
and carbon; which are in turn surrounded by a paste of NH 4Cl (s) and Zinc
Chloride.
The protruding portion of the carbon rod is covered with a brass cap; and the zinc
can covered with a sealing material.
Chemical reactions
The Zinc can is the negative terminal; while the carbon/graphite rod is the positive
terminal;
At the Negative terminal
Zn(s) → Zn2+ (aq) + 2e-
At the Negative terminal

2NH4+(aq) + 2e- → 2NH3(g) + H2(g)
Note: These gases (NH3 (aq) and H2 (g) ) are NOT used immediately but are used in
more complex reactions.
The ammonia gas forms a complex with the zinc chloride in the paste.
The hydrogen gas is oxidised to water by the Manganese (IV) oxide.
Functions of the various components
a) Brass cap - Functions as the positive terminal where the reduction reaction
occurs.
b) Zinc can - Is the Negative terminal; where the oxidation reaction occurs.
c) Carbon rod - It serves as the positive electrode.

Acts as the connecting rod between the positive and negative terminal through it
electron flow form the Zinc can to the brass cap.
d) Manganese (IV) Oxide - To oxidise the Hydrogen gas produced at the
anode/positive terminal/brass cap to water.
Note: Dry ammonium chloride does not conduct electric current. This explains
why a paste, which is a conductor, is used.
The dry cells cannot provide a continuous supply of electricity for a long period of
time.
Reason - The reactants (electrolytes) are used up and cannot be replaced.
2. Secondary cells
Are voltaic/electrochemical cells that are rechargeable.

A common example is the lead – acid accumulator.
The lead – acid accumulator
Lead plate acts as the negative terminal while lead (IV) oxide plate acts as the
positive terminal.
Both of these electrodes are dipped into an aqu9eous solution of sulphuric (VI)
acid.
At the negative terminal;
Pb(s) → Pb2+ (aq) + 2e-
At the positive terminal;
PbO2(s) + 4H+(aq) + 2e- → Pb2+ (aq) + 2H2O(l)
The lead (II) ions formed react instantly with the sulphate ions to form lead (II)
sulphate which is i0nsoluble and adheres to the electrodes.
Pb2+(aq) + SO42-(aq) → PbSO4(s)
Net reaction;
Discharging
+ 2-
Pb(s) + PbO2(s) + 4H (aq) + 2SO4 (aq) → 2PbSO4(s) + 2H2O(l)
During recharging;
Recharging
2PbSO4(s) + 2H2O(l) → Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq)
Fuel Cells
Are electrochemical cells which convert the chemical energy of a fuel directly to
electrical energy. An example is the hydrogen oxygen cell.
At the negative terminal;

2H2(g) + 4OH-(aq) → 4H2O(l) + 4e-
At the positive terminal;

O2(g) + H2O(l) + 4e- → 4OH- (aq)
Overall equation;
2H2(g) + O2(g) → 2H2O(l)
The cell goes on producing electricity as long as hydrogen and oxygen are fed into
it, so that it does not become exhausted like a primary cell. The fuel cell unlike
secondary cell does not store energy.
The electrode, other than completing the circuit also catalyzes the reactions which
increase the output of the cell.
ELECTROLYSIS
Defination
Electrolysis is the process in which electrical energy is used to cause non
spontaneous chemical reactions to occur.
Terminologies used in electrolysis

i) Electrolyte
Is an aqueous solution or a melt which allows electric current to pass through it as
it gets decomposed.
Electric current transfer in electrolyte occur through ions.
Electrolyte with many ions are called strong electrolyte; while those with few ions
are called weak electrolytes.
ii) An electrode is defined as a solid conductor dipped in an electrolyte and allows
current to enter or leave the electrolyte.
a) Anode – Is the electrode connected to the positive terminal of a battery/cell

b) Cathode- Is the electrode connected to the negative terminal of the battery/cell.
Note: Graphite rods are commonly preferred as electrodes in most access.

Reasons: i) They are inert/unreactive
ii) Are cheap
Platinum is also inert; but less preferred because its expensive.
ELECTROLYSIS OF VARIOUS SUBSTANCES
1. Electrolysis of Dilute Sodium Chloride Solution
Anode: Attracts OH- , Cl- ions
Oxidation (loss of electrons) occurs at the anode.
OH- ions are preferentially discharged. This is because it has lower E 0 value
of + 0.04 V than Cl- ions with E0 value of +1.36 V.
4OH- (aq) → 2H2O(l) + O2(g) + 4e-
Observation made at Anode; Bubbles of a colourless gas that relights a glowing

splint. This is due to formation of oxygen gas.
Cathode: Attracts Na+, H+ ions

Reduction (gain of electrons) occurs at the cathode.
H+ ions are preferentially discharged. This is because it has higher E 0 value
of 0.00 V than Na+ ions with E0 value of +2.71 V. Hence hydrogen ions have
greater tendency to gain electrons.
2H+(aq) + 2e- → H2(g)
Observation made at Cathode; Bubbles of a colourless gas that produces a pop

sound when burned in air. Hydrogen gas is produced.
Other Observations
Concentration of sodium chloride increases. This is because OH - and H+ ions are
discharged. This decreases the amount of water in the electrolyte, hence increase
in concentration.
2. Electrolysis of Concentrated Sodium Chloride Solution
Anode: Attracts OH- , Cl- ions

Cl- ions are preferentially discharged. This is because of its relatively higher
concentration.
2Cl- (aq) → 2Cl2(g) + 2e-
Observation made at Anode; Bubbles of a green yellow. This is due to formation of

chlorine gas.
Cathode: Attracts Na+, H+ ions

H+ ions are preferentially discharged. This is because it has greater tendency to
gain electrons.
2H+(aq) + 2e- → H2(g)

Other Observations
The discharge of hydrogen ions leads to accumulation of hydroxide ions (OH -)
The concentration of hydroxide ions increases this results in an increase in pH
hence solution becomes alkaline.
As the electrolysis process continues, the concentration of chloride ions decrease
and eventually hydroxide ions are oxidized to water and oxygen gas.
3. Electrolysis of Dilute Sulphuric (VI) Acid
Anode: Attracts OH- , SO42- ions
OH- ions are preferentially discharged.
4OH- (aq) → 2H2O(l) + O2(g) + 4e-

Cathode: Attracts H+ ions
2H+(aq) + 2e- → H2(g)

Other Observations
i) Concentration of sulphuric (VI) acid increases. This is because OH - and H+ ions
are discharged. This decreases the amount of water in the electrolyte, hence
increase in concentration.
ii) 4OH- (aq) → 2H2O(l) + O2(g) + 4e-
4H+(aq) + 4e- → 2H2(g)
After balancing the electrons, the ratio of O2 : H2 is 2:1
The volume of hydrogen is therefore twice that of oxygen.
4. Electrolysis of aqueous magnesium sulphate
Anode: Attracts OH- , SO42-ions
4OH- (aq) → 2H2O(l) + O2(g) + 4e-

Cathode: Attracts Mg2+, H+ ions

Reduction (gain of electrons) occurs at the cathode.
H+ ions are preferentially discharged.
2H+(aq) + 2e- → H2(g)

Other Observations
Concentration of Magnesium sulphate increases. This is because OH - and H+ ions
are discharged. This decreases the amount of water in the electrolyte, hence
increase in concentration.
5. a) Electrolysis of aqueous copper (II) sulphate using carbon electrodes
4OH- (aq) → 2H2O(l) + O2(g) + 4e-

Cathode: Attracts Cu2+, H+ ions

Cu2+ ions are preferentially discharged because they have greater tendency to gain
electrons.
Cu2+(aq) + 2e- → Cu(s)
Observation made at Cathode; Brown solid deposited. Copper is formed.
Other Observations
i) Concentration of copper (II) ions in solution decreases and blue colour of
copper (II) sulphate becomes pale and finally colourless.
Cu2+(aq) + 2e- → Cu(s)
ii) pH of the solution decreases. Hydrogen ions accumulate in the solution and
therefore the solution becomes acidic.
b) Electrolysis of aqueous copper (II) sulphate using copper electrodes

When copper electrodes are used in the electrolysis of copper (II) sulphate
solution, the mass of the anode decreases, while that of the cathode increases.
However copper anode dissolves;
Cu(s) → Cu2+(aq) + 2e-
Observation made at Anode; Copper anode dissolves.
Cathode: Attracts Cu2+, H+ ions

Cu2+ ions are preferentially discharged because they have greater tendency to gain
electrons.
Cu2+(aq) + 2e- → Cu(s)
Observation made at Cathode; Brown solid deposited. Copper is formed.
Other Observations
i) Concentration of of the solution remains the same. This is because the amount of
copper oxidized at the anode is equal to the amount of copper deposited at
cathode and therefore the concentration remains the same.
ii) The colour of the solution does not fade.
Factors Affecting Preferential Discharge During Electrolysis

1. Position in the electrochemical series
2. The concentration of the electrolyte

A cation or anion whose concentration is high is preferentially discharged if the
ions are close in the electrochemical series.
3. The product obtained at the electrode depends on the nature of the electrode
used.
APPLICATIONS OF ELECTROLYSIS
1. Extraction of reactive metals

Reactive metals/elements like sodium, magnesium, aluminum are extracted
form their compounds by electrolysis.
2. Purification of metals e.g refining copper
The impure copper is made of the anode.
Strips of copper are used as the cathode
Copper (II) Sulphate is used as the electrolyte.
During the electrolysis the anode dissolves and pure copper is deposited on the
cathode.
The impurities (including valuable amounts of silver and gold) from the crude
copper collect as sludge become the anode.
3. Electroplating: Is the process of coating one metal with another, using

electrolysis so as to reduce corrosion or to improve its appearance.
During electrolysis:
i) the item to be electroplated is made the cathode
ii) the metal to be used in electroplating is used as the anode
iii) the electrolyte is made from a solution containing the ions of the metal
to be sued in electroplating.
Examples
iv) Gold-plated watches; silver – plated utensils
v) Steel utensils marked EPNS. I.e. Electroplated Nickel Silver.
4. Anodizing Aluminum
Is the reinforcement of the oxide coating on Aluminum utensils/articles
Is done by electrolysis of dilute sulphuric acid using Aluminum articles as anode.
This prevents arrosion of Aluminum articles
Manufacture of sodium hydroxide and chlorine from Electrolysis

of Concentrated Sodium Chloride (Brine)
The mercury cathode cell

Is an electrolytic arrangement commonly used for the large scale manufacture of
chlorine and sodium hydroxide.
Electrolyte in the mercury cell is Brine (concentrated NaCl)

Anode is carbon or titanium, this is because they do not react with chlorine gas.
Cathode is a moving mercury film.
a) Reactions at the Anode

Both Chloride (Cl-) and Hydroxide(OH-) ions are attracted.
Due to their high concentrations the chloride ions are preferentially discharged.
2Cl-(aq) → Cl2(g) + 2e-
b) Reactions at the Cathode (moving mercury)

The Na+ (aq) and H+ (aq) are attracted
The discharge of H+ (aq) is more difficult. This is because hydrogen has a high over
voltage at the moving mercury electrode and so sodium is discharged.
2Na+(aq) + 2e- → 2Na(l)
The sodium atoms formed dissolve in the hot mercury to form sodium
amalgam(NaHg)
Na(l) + Hg(l) → NaHg(l)
The sodium amalgam reacts with water to form sodium hydroxide, hydrogen and
mercury.
2NaHg(l) + 2H2O(l) → 2NaOH(aq) + 2Hg(l) + H2(g)
Hydrogen is pumped out while the Mercury is recycled.

The resultant NaOH is about 50% pure.
Pure sodium hydroxide is obtained by evaporating the water in the aqueous
sodium hydroxide solution to get pellets or flakes.
The process is expensive due to the high cost of mercury and the safety measures
applied since mercury is poisonous.
QUANTITATIVE TREATMENT OF ELECTROLYSIS
An electric current is measured in amperes. The quantity of electric charge(Q) is

measured in coulombs (C).
A coulomb is the quantity of electricity passed when a current (I) of one ampere
flows for a time (t) of one second.
Example
Copper (II) sulphate solution was electrolyzed using carbon electrodes. Use the
results below to determine the quantity of electricity required to deposit one
mole of copper atoms at the cathode.
Time taken = 15 minutes

Current = 2 amperes
Mass of copper deposited at cathode = 0.6 g
Answer
Quantity of electricity = It; Where I is current in amperes and t is time in seconds.
Q = It = 2 X 15 X 60
= 1800 coulombs
0.6
Moles of copper deposited = = 0.00945
63.5
0.00945 moles = 1800 coulombs

1 x 1800
1 mole = = 190,476 coulombs
0.00945
Faraday’s Law of Electrolysis

States that the mass of a substance produced during electrolysis is directly
proportional to the quantity of electricity passed.
From the example above; Cu2+(aq) + 2e- → Cu(s)

Two moles of electron requires190,476 coulombs
190,476
Therefore one mole of electron would require = 95,238 coulombs
2
Note; The quantity of electricity carried by one mole of electrons is a constant

called a Faraday (F) and is equivalent to 96,487 coulombs. The experimental value
is lower due to experimental errors.
¿ X RFM
Generally; Mass deposited = where;
nX F
¿
Moles of substance produced = n X F where;
I is current in amperes
T is time in seconds
n is the number of moles of electrons( or charge on a metallic ion)
F is faraday’s constant
Worked examples
1. What mass of copper would be coated (deposited) on the cathode from a solution
of copper (II) Sulphate by a current of 1 ampere flowing for 30 minutes.
(Cu = 63.5; Faraday constant = 96487 C)
Answer;
1 X 30 X 60 X 63.5
Mass deposited = = 0.5923 g
2 X 96,487
2. An element x has relative atomic mass of 88g. When a current of 0.5 amperes
was passed through a solution of x chloride for 32 minutes, 10 seconds; 0.44 g
of x was deposited at the cathode. (1 faraday = 96500 C)
Calculate the charge on the ion of x.
¿ X RFM
Mass =
nX F
0.5 X 1930 X 88 0.5 X 1930 X 88

0.44 =
n X 96500
; n=
0.44 X 96500
= +2
3. In the electrolysis of dilute CuSO4 solution, a steady current of 0.20 Amperes

was passed for 20 minutes. (1 Faraday = 96, 500 C Mol-, Cu = 64)
Calculate
a) The number of Coulombs of electricity used
b) The mass of the substance formed at the cathode.
4. What volume of oxygen will be liberated at the anode when a current of 3

amperes is passed through magnesium sulphate solution for 45 minutes and 30
seconds?
(Molar gas volume at r.t.p = 24.0 litres, F = 96,500 coulombs).
3 X 1380
Moles of oxygen produced = = 0.0107 moles
4 X 96,500
1 mole = 24000 cm3
0.0107 X 24000
0.0107 moles = = 2568 cm3
1
METALS: EXTRACTION PROPERTIES AND USES
Chief Ores of Metals
An ore is a compound in which a metal can be extracted.
Metal Ores of the Metal Formula of Ores

Sodium Sodium chloride NaCl
Aluminium Bauxite Al2O3.2H2O
Zinc Zinc blende ZnS/PbS
Calamine ZnCO3
Zinc oxide ZnO
Lead Galena PbS
Zinc blende ZnS/PbS
Iron Haematite Fe2O3
Magnetite Fe3O4
Siderite FeCO3
Pyrite FeS2
Copper Copper pyrites CuFeS2
Methods of Extraction
Depend on position of the metal in the reactivity series.
Main methods are:

1. Electrolytic Method:
Used for metals high up in the reactivity series
E.g. Sodium
Aluminium.
2. Reduction method:
For less reactive metals.
E.g. Iron, Zinc, Lead and Copper.
1. Sodium
Main ores is sodium chloride; NaCl
Sodium metal is extracted by the Down’s process where the molten sodium
chloride is electrolyzed.
Extraction; The Down’s Cell
The Down’s cell consists of an iron shell lined with heat bricks on the outside. The
heat resistant wall is meant to maintain the high temperature so that the
electrolyte does not crystalise.
At the centre of the cell is the carbon anode surrounded by a steel cathode.
Sodium is obtained by the electrolysis of fused sodium chloride in the electrolytic
cell.
Calcium chloride is added to the electrolyte to lower the melting point of sodium
chloride from 800oC to 600oC; This is economical because it saves on electricity
used in heating.
Steel or iron is used as the cathode, while carbon/graphite is used as the anode.
Steel is not used as the anode. This is because at high temperatures, steel would
react with chlorine formed at the anode, but graphite is inert even at high
temperatures.
Steel wire gauze (diaphragm) separates the electrodes to prevent products of

electrolysis (sodium and chlorine) from recombining.
At the Anode
2Cl- (l) → Cl2(g) + 2e-
At the Cathode
2Na+(l) + 2e- → 2Na(l)
Molten sodium is lighter than fused sodium chloride and floats on the surface
where it is removed.
Reasons;
Sodium is less dense than molten sodium chloride
Sodium has a low melting point.
Liquid calcium metal may also be produced at the cathode. However calcium liquid
does not mix with sodium liquid as it is much denser. In addition, calcium has
higher melting point than sodium. During cooling, calcium crystallizes first leaving
liquid sodium which is tapped.
Uses of sodium;
1. Is alloyed with lead in the preparation tetraethyl (IV) lead, which is added to
petrol as an anti-knock.
2. Used in sodium vapours lamps, for street lighting (orange-yellow street lights).
3. Used in nuclear reactors to conduct away heat.
4. Manufacture of sodium peroxide, and sodium cyanide used in the extraction of
silver and gold.
2. Aluminium
Forms 7% of the earth’s crust and is the most common metal.
Its chief ore is Bauxite; Al2O3.H2O
Chemical test to confirm presence of the ore;

Crush the ore into a fine powder;
Add dilute nitric (V) acid to the powder
Filter to obtain a solution of the ore;
To a solution of the ore add NaOH(aq) dropwise till in excess, and then repeat the
same procedure using Ammonia solution, NH4OH.
Observations:
 With NaOH(aq):
White precipitate in soluble in excess;
 With NH4OH(aq):
White precipitate insoluble in excess;
Extraction from Bauxite;
Involves two main processes;-
 Purification of Bauxite.
 Electrolysis of purified bauxite (alumina)
i. Purification of bauxite
Bauxite is ground into a fine powder and then dissolved in hot concentrated
sodium hydroxide under pressure. The amphoteric aluminium oxide and acidic
silicon (IV) oxide dissolves in the base while iron (III) oxide which is insoluble in the
base is filtered out as red mud.
2NaOH(aq) + Al2O3.3H2O(s) → 2NaAl(OH)4(aq).
Ionically:
Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2[Al(OH)4]-(aq);
SiO2(s) + 2OH-(aq) → SiO32-(aq) + H2O(g)

The iron impurities (mainly iron (III) oxide) DO NOT dissolve.
This mixture is then filtered, during which iron (III) oxide remain as residue of red
mud while a filterate of sodium aluminate and sodium silicate is collected.
Carbon (IV) oxide is bubbled through the filtrate to precipitate the aluminium
hydroxide.
2[Al(OH)4]-(aq) + CO2(g) → 2Al(OH)3(s) + CO32-(aq) + H2O(l);
Alternatively:
Aluminium hydroxide may be precipitated by seeding process using pure
aluminium hydroxide crystals.
Al(OH)3(aq)
-
Al(OH) 4 (aq) Al(OH)3(s) + OH-(aq);
seed
The aluminium hydroxide is then heated to obtain aluminium oxide. (Al 2O3)
2Al(OH)3(s) → Al2O3(s) + 3H2O(l)
ii. Electrolysis of purified bauxite

The Alumina (Al2O3), has a high melting point, 2015oC and a lot of heat would be
required to melt it.
Additionally the molten compound is a very poor conductor of electricity.
Consequently, cryolite (Na3AlF6) is mixed with the oxide to lower the melting
temperature of Al2O3 from 2015oC to around 800oC;
At this lower temperature the molten oxide also conducts well.
The molten alumina mixed with bauxite is then electrolysed in a steel cell lined
with carbon graphite as the cathode.
Note;
Other than being an electrolyte the graphite cathode lining also prevents alloy
formation, as it ensures no contact between the resultant aluminium and the steel
tank;
The anodes also made of Graphite dip into the steel tank at intervals.
At the anode;
Observation;
Effervescence of a colourless gas.
Explanations:
Oxygen ions migrate to the anode and get oxidized to form oxygen gas.
The resultant oxygen gas reacts further with the graphite anode to form carbon (IV)
oxide.
This is due to the high temperatures involved during the process. Consequently the
carbon anode should be replaced from time to time.
6O2-(l) → 3O2(g) + 12e-
Then;
C(s) + O2(g) → CO2(g)
At the cathode;
Observation;
A silvery white metal which quickly becomes dulled.
Explanation:
Aluminium ions move to the cathode and are reduced to form aluminium metal.
Equation;
4Al3+(l) + 12e- → 4Al(l)
Note:
Cryolite usually adds Na+; and F- ions into the electrolyte.
Thus the anions are O2- and F- ions into the electrolyte.
However oxygen is discharged in preference to Fluorine.
Reason;
Fluorine is a stronger oxidizing agent than oxygen. Thus oxygen easily gives
electrons than fluorine, hence discharge.
Aluminium is discharged in preference to sodium.
Uses of aluminium
1. Making parts of airplanes, railway, trucks, buses, tankers, furniture, and car.
This is because aluminium is very light due to a very low density.
2. Making cooking vessels/ utensils such as sufurias because it is a good
conductor of heat and electricity.
It is also not easily corroded by cooking liquids due to the unreactive coating of
aluminium oxide.
3. Making overhead cables because it is a good conductor of electricity.
It is also light hence can easily be supported by poles.
It is also ductile to be rolled into wires (cables).
4. Aluminium powder mixed with oil is used as a protective paint.
5. Making Aluminium foils due to its high malleability. The foil is used in cooking;
packaging and for milk bottle tops.
6. Making alloys, which have high tensile strength and yet light.
Examples:
Alloy Component
Duralumin Aluminium, copper, manganese and
magnesium
Magnalium Aluminium (70%) and magnesium (30%)
7. As a reducing agent in the Thermite process in the production of some

elements such as chromium, cobalt manganese and titanium.
3. Extraction of Iron
Is the second most abundant metal after aluminium, forming about 7% of the
earth’s crust.
Main ores
Haematite, Fe2O3;
Magnetite, Fe3O4;
Siderite, FeCO3;
Qualitative analysis for presence copper in an ore sample.

Crush the ore into fine powder;
Add dilute nitric (V) acid to the ore, to dissolve the oxide filter to obtain the filtrate.
To the filtrate add aqueous sodium hydroxide / ammonium hydroxide dropwise till
in excess.
Formation of a brown precipitate in both cases indicates presence of Fe 3+
Extraction from haematite (Fe2O3).

However if the ore is siderite, the ore is fiorst roasted in air to convert it to iron (III)
oxide.
Raw materials.
Iron ore; i.e. haematite
Coke; C
Limestone; CaCO3;
Hot air;
In the blast furnace three important reactions take place.
1. At the bottom of the furnace, coke(carbon) is oxidized to carbon(IV)oxide. The
reaction is exothermic and the temperature rises to 1600 oC.
C(s) + O2(g) → CO2(g) ∆H = -393 kJmol-1
2. In the middle of the furnace, carbon(IV)oxide is reduced by coke to

carbon(II)oxide and the temperature drops to about 1000oC since the reaction is
endothermic.
CO2(g) + C(s) → 2CO(g) ∆H = +283 kJmol-1
3. At the upper part of the furnace where the temperature has fallen to about
700oC, iron(III)oxide is reduced to iron metal. Both carbon and carbon(IV)oxide
act as reducing agents.
2Fe2O3(s) + 3C(s) → 4Fe(l) + 3CO2(g)
Fe2O3(s) + 3CO(s) → 2Fe(l) + 3CO2(g)
Carbon(II)oxide is the main reducing agent because of the large surface that is in
contact with the iron(III)oxide.
The iron produced falls to the lower part of the furnace where the temperatures are
high enough to keep it molten. The carbon(IV)oxide produced is recycled.
The limestone fed into the furnace alongside coke and iron(III)oxide is decomposed
by heat in the furnace to form calcium oxide and carbon(IV)oxide.
CaCO3(s) → CaO(s) + CO2(g)
Calcium oxide being basic reacts with acidic and amphoteric oxide in the furnace
to form slag.
CaO(s) + SiO2(s) → CaSiO3(l)
CaO(s) + Al2O3(s) → CaAl2O4(l)
The slag formed is tapped off at a higher level of the furnace because of its lower
density. The iron obtained from the blast furnace is 90 – 95% pure and it is called
‘’pig Iron’’. The main impurities in pig iron are carbon, silicon, manganese, sulphur
and phosphorus, depending on the composition of the original ore.
These impurities considerably affect the properties of iron by making it less hard
and brittle as well as lowering the melting point of the iron.
Uses/application of the slag

1. Light-weight building material.
2. Manufacture of cement.
3. Road building material.
Uses of iron.
Iron exists in different types and alloys, depending on percentage composition of
iron, and other elements.
Each type of alloy of iron has different uses depending on properties.
Iron alloy or Properties. Uses

type
Cast iron Refers to iron just after it has Making:
been produced in the blast  Furnaces;
furnace;  Grates;
Contains 3-5% carbon, 1%  Railings;
silicon, and 2% phosphorus;  Drainage pipes;
Disadvantage: very brittle  Engine blocks;
hence easily breaks;  Iron boxes;
Advantage: It is extremely very Note: This is due to its very
hard; hard nature;
Manufacture of wrought iron
and steel;
Wrought iron Refers to cast iron with 0.1% making iron nails; horse shoes;
carbon. agricultural implements like
It is malleable hence can easily pangas;
be moulded or welded; Note:
Its use is declining due to
increased use of mild steel
Steel Are alloys whose main Mild steel is used for making:
component is iron;  Nails; Car bodies;
Other components may be  Railway lines; Ship
carbon; vanadium; manganese; bodies;
tungsten; nickel and chromium;  Rods for reinforced
Examples: concrete, pipes;
Mild steel: has about 0.3%
carbon, 99.75% iron;
Stainless steel: Stainless steel: Is used in

Contains 74% iron, 18% making cutlery; sinks; vats;
chromium, and 8% nickel;
Cobalt steel: Cobalt steel: is used for

Contains about 97.5% iron and making electromagnets;
2.5% cobalt;
Very tough and hard;
Slightly magnetic;
4. Extraction of Zinc
Main ores;
(i). Zinc blende; ZnS (Zinc blende is often found mixed with galena- PbS)
(ii). Calamine; ZnCO3.
It is extracted by electrolysis or reduction of its oxide using carbon.
Preliminary steps:
The ore is first concentrated by froth floatation.
The concentrated ore is then roasted in air to convert it to the oxide.
In the case of calamine, the carbonate decomposes to zinc oxide and
carbon(IV)oxide.
ZnCO3(s) → ZnO(s) + CO2(g)
2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)
The impurity PbS in the ore produces lead(II)oxide and sulphur(IV)oxide
2PbS(s) + 3O2(g) → 2PbO(s) + 2SO2(g)
After obtaining the oxide zinc metal is extracted by either reduction using carbon
or carbon(II)oxiode or it may be converted to zinc sulphate and electrolyzed.
(a). The reduction method.

The oxide is mixed with coke and limestone and heated in a blast furnace where it
is reduced to zinc.
ZnO(s) + C(s) → Zn (g) + CO (g)
ZnO(s) + CO(s) → Zn (g) + CO2 (g)
The limestone (CaCO3) decomposes to liberate CO2 which is then reduced by coke
to form carbon (II) oxide.
Heat
CaCO3(s) → CaO(s) + CO2 (g)
Then:
CO2 (g) + C(s) → 2CO (g)
The resultant carbon (II) oxide and coke are the reducing agents in the furnace, at
about 1400oC.
They reduce the oxide to the metal; which is liberated in vapour form.
At the furnace temperatures zinc exists in vapour form, and leaves at the top of the
furnace.
Liquid zinc being lighter settles above molten lead and is run off;
The vapour is condensed in a spray of molten lead to prevent re-oxidation of zinc.
The resultant zinc is 98-99% pure and can be further purified by distillation.
SO2 is a by-product and is the main source of pollution in the extraction of zinc.
Usually it is channeled to a contact process plant for the manufacture of sulphuric
acid.
Alternatively it can be scrubbed off to prevent pollution of the environment.
Less volatile impurities remain in the furnace.
The silica impurities combine with the quicklime/ calcium oxide (CaO) from
limestone to form calcium silicate.
CaO(s) + SiO2(s) → CaSiO3(s)

The silicates together with other less volatile impurities form slag, at the bottom of
the furnace from where it is run off.
Sulphur (IV) oxide Coke and limestone CO2 and excess CO(g)
ZnO(s)
ZnO, C, CaCO3
Roaster Mixer Reaction chamber
ZnS (ore) →
Zinc + impurities
Separation chamber Slag

Air
Zinc liquid (pure)
Pure zinc solid Cooling chamber
(b). Electrolytic extraction of zinc.

Step I: Preparation of electrolyte:
The ZnO is converted to zinc sulphate by reacting it with dilute sulphuric (VI) acid.
ZnO(s) + H2SO4(aq) → ZnSO4(aq) + H2O(l)
Any lead (II) oxide impurity present in the zinc oxide reacts with the acid to form
lead (II) sulphate.
PbO(s) + H2SO4(aq) → PbSO4(s) + H2O(l)
The insoluble lead (II) sulphate is then precipitated and separated by filtration;
The zinc sulphate is then dissolved in water and the solution electrolysed.
Cathode:
Is made of lead containing 1% silver.
Observations:
Deposits of a grey solid.
Explanations:
Zn2+ and H+ migrate to the cathode.
The Zn2+ are discharged in preference to H+;
Reason:
The cathode is relatively reactive. Thus since zinc is more reactive than hydrogen,
its ions undergo reduction faster;
Zn2+(aq) + 2e- → Zn(s);
Note:
If graphite electrodes were used, hydrogen gas would have been evolved instead;
Anode:
Is made of Aluminium sheets;
Observations:
Evolution of a colourless gas that relights a glowing splint;
Explanations:
OH- and SO42- migrate to the cathode.
The OH- are discharged in preference to SO42-; giving off oxygen gas
Reason:
The OH- ions have a higher oxidation potential than SO42- and therefore easily
giving electrons for reduction at the cathode
4OH-(aq) → 2H2O(l) + O2(g) + 4e-
Note:
Over 80% of zinc is extracted by the electrolytic method.
Zinc extracted by the electrolytic method is much more pure.
Note: - Industrial plants that can be set up near the zinc extraction plant.
i. Contact process plant, to make use of the SO2 by-product.
ii. Lead accumulators factories, to utilize the zinc produced.
iii. Paper factory using, SO3 and hence SO2 in bleaching.
iv. Brass factory for alloying zinc and copper.
v. Steel factory to use zinc in galvanization.
Properties of zinc
Physical properties
Is a blue-grey lustrous metal with:
 Density of 7.1gcm-3
 Melting point of 420oC
 Boiling point of 907oC
Uses of zinc:
1. Galvanization of iron sheets to prevent corrosion and rusting.
Note:
Rusting does not occur even when galvanized iron sheets are scratched and
exposed.
Reason:
The rest of the zinc protects the iron from rusting. This is because zinc being more
reactive gets oxidized in preference to iron, and is hence “sacrificed” in the
protection of iron.
This method is referred to as cathodic or sacrificial protection.
2. Making brass; an alloy of copper and zinc.
3. Making outer casings of dry batteries;
4. Die-castings contain zinc and aluminium, and are used for making radio and
car parts;
5. Zinc cyanide is used for refining silver and gold;
5. Extraction of Lead
Is a transition element that combines with other elements to form compounds with
2 oxidation states, lead(II) and lead(IV) compounds.
Chief ore is Galena, PbS (lead sulphide).
Extraction of lead:
Occur in three main steps:
 Ore concentration;
 Extraction by reduction;
 Purification (refining) by electrolysis;
1. Ore concentration:
Is done by selective froth floatation;
The ore is ground into a fine powder, then water and a suitable oil added;
Air is then blown into the mixture; facilitating formation of a low density froth that
floats on top;
Additionally, chemicals such as sodium cyanide and zinc sulphate are added to
facilitate separation of zinc sulphide present in the ore.
The separated PbS is then dried and broken into smaller pieces, then subjected to
reduction;
2. Reduction:
Step I: Roasting the ore:
The crushed and concentrated ore is roasted in a furnace to convert it to lead (II)
oxide;
2PbS(s) + 3O2 (g) → 2PbO(s) + 2SO2 (g)
Step II: Ore reduction:

The lead oxide obtained is mixed with coke, limestone and silica and some scrap
iron;
The mixture is fed into the top of the Imperial smelting furnace (ISF); where it is
melted using hot air blasts introduced near the bottom of the furnace;
Main reactions:
(i). The lead (II) oxide is reduced to lead by the coke.
2PbO(s) + C(s) → Pb(s) + CO2(s);
(ii). The scrap iron is added so as to react with any lead sulphide that may be
present.
Fe(s) + PbS(s) → Pb(s) + FeS(s)
(iii). The limestone undergoes decomposition to give calcium oxide and liberate
carbon (IV) oxide;
CaCO3(s) → CaO(s) + CO2 (g);
The carbon (IV) oxide gets reduced by coke to form more carbon (II) oxide for
reduction as in reaction (ii);
CO2 (g) + C(s) → 2CO (g);
(v). The calcium oxide reacts with silica in form of SiO 2 to form calcium silicate;
CaO(s) + SiO2 (g) → CaSiO3 (l);

The iron(II)sulpphide and calcium silicate form slag which is tapped off separately
from the lead. The lead produced by the method is not pure. Pure lead is obtained
by blowing a blast of air through the molten impure lead. Oxygen in the air
oxidises the impurities into compounds which are less dense than lead. The
compounds float on the molten lead and are skimmed off. More pure lead can be
obtained by electrolysis.
The cathode is made of a pure strip of lead while the impure lead is made the
anode. At the cathode, lead is deposited while at the anode lead dissolves.
Pollution effects:
Main pollutant is sulphur (IV) oxide from roasting of the ore.
Pollution control:
It is directly fed into a contact process plant or scrubbed using calcium hydroxide
forming calcium sulphite;
Uses of lead:
1. It is used in several alloys e.g. solder and also added to bronze alloys to make
them stronger;
2. Lead is used in the manufacture of accumulators;
3. Making lead pipes for water supply; this is also discouraged particularly in soft
water areas due to threat of lead poisoning;
5. Making tetraethyl lead (IV) which for many years was used as a fuel additive to
increase octane rating of fuels;
6. Used in weights, clock pendulums, plumb bobs etc; due to its high density;
7. It absorbs X-rays and hence lead aprons and lead glass are used to shield
hospital radiographers;
8. Used for safe disposal or storage of radioactive substances since no radioactive
emission has been known to pass through thick lead blocks;
6. Extraction of Copper
Is a red brown metal.
Found in Canada, USA, Zambia, and Tanzania.
Main ore is copper pyrites, CuFeS2;
Extraction- from copper pyrites.

1. Crushing the ore
The ore is crushed to increase the surface area for the succeeding chemical
reactions.
The ore is then concentrated.
2. Concentration of the ore.

The ore is concentrated by froth floatation.
The fine ore powder is mixed with water and oil, after which air is blown into the
mixture, usually from below.
Bubbles of the air forms froth, resulting to concentration of the ore.
The lighter oil floats on top of the water, with the ore floating on top of the oil.
The denser water sediments the earthy impurities like soil particles.
The concentrated ore is then tapped off.
This process involves formation of an oil froth onto which the ore floats hence the
name froth formation.
3. First Roasting
The concentrated copper pyrite, CuFeS2 is then roasted in air to remove some of
the sulphur impurities as sulphur (IV) oxide.
2CuFeS2(s) + 4O2 (g) → Cu2S(s) + 2FeO(S) + 3SO2 (g);
Silica(SiO2) is then added and the mixture is heated in the absence of air. The silica
reacts with iron(II)oxide to form iron(II)silicate which separates out as a slag leaving
behind the copper(I)sulphide.
FeO(s) + SiO2(g) → FeSiO3(s)
The Cu2S is heated in a regulated supply of air where some of it is converted to

Cu2O
2Cu2S(s) + 3O2(g) → 2Cu2O(s) + 2SO2(g)
The copper(I)oxide then reacts with the remaining copper(I)sulphide to form copper
metal and sulphur(VI)oxide.
Cu2S(s) + 2Cu2O(s) → 6Cu(s) + SO2 (g);
The sulphur(IV)oxide produced is either fed into adjacent sulphuric(VI) acid plant
or scrubbed using calcium hydroxide.
SO2(g) + Ca(OH)2(aq) → CaSO3(s) + H2O(l)
The copper metal obtained is about 97.5% pure copper. This is called blister
copper. It is refined by electrolysis to obtain 99.8% pure copper.
Main impurities
Traces of gold
Traces of silver
Iron
Sulphur
At the cathode.
Observations:
Deposition of a brown solid.
Explanations:
The copper (II) ions, Cu2+ move to the cathode, where they accept electrons and
undergo reduction.
Cations in the electrolyte are Cu2+ and H+ but Cu2+ are preferentially discharged
due to their easy tendency to undergo reduction.
Equation:
Cu2+(aq) + 2e- → Cu(s);
At the anode
Observations:
Dissolution of the anode, hence the impure copper rod decreases in size.
Explanation
Since the metal rod is dipped into a solution of its ions, the copper solid undergoes
oxidation, losing electrons to form copper ions, Cu2+
Consequently as more copper ions, Cu2+ get reduced at the cathode; more are
released by the dissolving anode.
Cu(s) → Cu2+(aq) + 2e-
Overall reaction
Cu(s) + Cu2+(aq) → Cu2+(aq) + Cu(s)
Where copper(II)carbonate is the chief ore, it is roasted first to obtain
copper(II)oxide.
CuCO3(s) → CuO(s) + CO2(g)
The copper(II)oxide is then reduced to copper metal using coke and carbon(II)oxide
as reducing agents.
2CUO(s) + C(s) → Cu(s) + CO2(g)
CUO(s) + CO(s) → Cu(s) + CO2(g)
Uses of copper
1. Making copper wires and contacts in switches, plugs and sockets
2. Making soldering instruments.
3. Manufacture of alloys.
Examples
Alloy Components
Brass Copper and zinc
Bronze Copper and tin
German silver Copper, zinc and nickel;
4. Making coins and ornaments.

Reason:-it is durable and aesthetic.
Effects of Extraction of Metals on the Environment

1. Mining of the ores from the ground may lead to gaping holes being left in the
ground if not refilled with earth. If undesired earthly material accompanying the
ores are carelessly disposed of, it may lead to serious land pollution.
2. Gaseous by products such as SO2, CO2 and Cl2 cause air pollution.
3. Solid by-products such as slag causes land pollution. Conversely, solid by-
products can be disposed off carefully by either burning them or making other
uses of them. For example, slag may be used in carpeting roads.
RADIOACTIVITY
Is the process where an unstable nuclide breaks up to yield another nuclide of
different composition with emission of particles and energy.
Substances, which undergo radioactivity are said to be radioactive.
Isotopes which are radioactive are known as radioisotopes.
The spontaneous disintegration of radioactive nuclides is known as radioactive
decay.
Radioactivity is a nuclear process and not a chemical reaction.
Differences between chemical and nuclear reactions
Nuclear Reaction Chemical Reaction

Takes place within the nucleus Takes place on the outer energy
and involves neutrons and levels containing valence
protons electrons. Does not involve
neutrons and protons
Releases large amounts of energy Releases much less amounts of
energy
Not affected by environmental Affected by environmental factors
factors such as temperature and such as temperature and pressure
pressure
Stability of Isotopes of elements

A particular nucleus of an atom characterized by its protons and neutrons is
known as a nuclide.
Nuclides can either be stable or unstable. Most nuclides have a neutron to

proton(n/p) ratio of 1:1.
1.6
However a nuclide with n/p ratio of more than 1.6:1 i.e are said to be unstable.
1
The unstable nuclides normally undergoes some changes by emitting radiation in
form of particles and energy.
Types of Radiactivity
i) Natural Radioactivity – Radioactive nuclei split spontaneously yielding a
new nuclide with the emission of radiation and energy.
ii) Artificial radioactivity – large stable nuclides are bombarded with fast
moving high-energy particles. The nuclides split into relatively smaller
nuclei with emission of radiation and energy.
Types of Radiations
i) Alpha particles -  Are positively charged and represented as
ii) Beta particles – β Are negatively charged and represented as
iii) Gamma rays – are high energy rays. They do not have an electrical charge.
They are not emitted on their own but normally accompany the emission of
alpha or beta particles
Properties of Radiations
1. Penetrating Power
Alpha particles have very low penetrating power. They do not pass through a sheet
of paper.
Beta particles have higher penetrating power. They can pass through a sheet of
paper but are stopped by a sheet of aluminium foil.
Gamma rays have highest penetrating power. They can pass through a sheet of
paper and a sheet of aluminium foil. They are however stopped by a thick lead
block.
2. Deflection in an Electric Field

Alpha particles are positively charged. They are therefore attracted to the negative
plate in an electric field. Since they are heavy they are only slightly deflected.
Alpha particles are negatively charged. They are therefore attracted to the positive
plate in an electric field. Since they have a much smaller mass, their deflection is
greater than that of alpha particles.
Gamma rays do not have a charge and are therefore unaffected by an electric field.
4. Ionising Effect
Alpha particles have very high ionizing power. They produce a large number of
ions as they pass through gases due to their slow speed and high charge. Their
slow speed enables the alpha particles to be in contact with target atoms for a
longer time.
Beta particles have lower ionizing power and produce fewer ions in gases.
Gamma rayshave very low ionizing power.
Radioactive Decay and Half Life

When a radioactive nuclide decays, a new nuclide is formed.
Table below shows the radioactive decay for a sample of 400 g of iodine – 131
Time (days) Mass (g) of radioactive iodine

remaining
0 400
8.1 200
16.2 100
24.3 50
32.4 25
A graph of the data
From the graph it can be noted that after every 8.1 days the amount of substance
remaining is half the previous amount.
The half life of a radioisotope is the time taken for a given mass or number of
nuclides to decay to half its original mass or number.
Example
Radioactive isotope Lr-257 has half life of 8 seconds. Determine the mass
remaining when 48g of the radioisotope is allowed to decay for 32 seconds.
Answer
32
Number of half lives = = 4 half lives
8
1st half-life 2nd half-life 3rd half-life 4th half-life

48 g → 24 g → 12 g → 6g → 3g
Hence mass remaining = 3 g.
Alternatively;
Remaining amount = ( ½ )n x original amount; where n is the number of half lives.
Mass remaining = ( ½ )4 x 48 = 3 g.
Each radioactive isotope decays at its own rate and therefore has its own half life.
Nuclear Reactions
When an alpha particle is emitted from the nucleus, both the atomic number and
the mass number of the nuclide decrease. A new nuclide is formed.
Examples;
Beta particle emission
Gamma rays are not shown when writing nuclear equations because they have no
effect on mass number and atomic number of a nuclide.
Example;
Radioactive Decay Series
A radioactive decay series represents the sequential and continuous disintegration
of unstable nuclide until a stable nuclide is formed.
Example;
In this decay series, natural decay ends when stable lead-202 with n/p ratio of
about 1.5:1 is formed.
Nuclear Fission
Is the process in which a heavy nuclide undergoes splitting when bombarded by a
fast moving neutron.
Energy is liberated due to the fact that the total mass of the products is slightly
less than the mass of the initial nuclides. This difference in mass is radiated as
energy. A very small loss in mass results in an enormous amount of energy being
released.
The energy can be tapped and used to generate electrical energy.
Nuclear Fusion
Is the process in which light nuclei combine together when they are made to collide
at high velocity resulting in the formation of heavy nucleus. The process is
accompanied by liberation of large quantities of energy. Some sub-atomic particles
such as neutrons are also released during nuclear fusion.
Similarities between Nuclear Fission and Nuclear Fusion
1. In both cases a large quantity of energy is released.
2. Both processes results in chain reactions.
3. In both cases sub-atomic particles such as neutrons accompany the process.
4. The energy released can be harnessed and converted into other forms of useful
energy such as electrical energy.
5. The large amount of energy produced in both reactions can be very destructive
when missed such as in nuclear warfare.
Applications of Radioactivity
Uses of Radioactive Isotopes
Medical Applications
1. Cobalt-60 and Caesium-137 are used to destroy cancerous tissue.
2. Sterilisation of surgical instruments using gamma radiation.
3. Radioactive iodine-131 is used in patients with defective thyroid to enable
doctors to follow the path of iodine through the body.
4. Used to monitor growth in bones and healing of fractures.
5. Detecting leakages in underground water or oil pipes without digging them out.
Agricultural Applications
1. Carbon(IV)oxide containing radioactive carbon-14 is used in monitoring
photosynthesis and related processes.
2. Radioactive phosphorus is used in monitoring absorption of phosphate
fertilizers.
Other Uses
1. Gamma radiation is used in preservation of food.
2. Gauging the thickness of thin metal and paper sheets.
3. Measuring the level of food in canned and packed food.
4. Determining the age of archeological materials in fossils from carbon-14 dating.
5. Manufacture of nuclear weapons and atomic bombs.
Dangers of Radioactivity
1. Environmental pollution; radioactive materials emit radiation into the
atmosphere. The radiations cause cancer.
2. Testing of nuclear weapons in the oceans causes environmental pollution since
plants and other living organisms may take in the radioactive materials released
in the water.
3. When not put into proper use, radioisotopes can be used as weapons of mass
destruction.
Control of Environmental Pollution; Can be achieved by proper use, storage and

disposal of radioactive materials as well as regular checks of equipment which emit
radiations.


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ACIDS, BASES AND SALTS

HCl (aq) → H+(aq) + Cl- (aq)

CH3COOH(aq) → H+ (aq) + CH3COO-(aq)

OR: - An acid is a proton donor i.e. a substance which provides protons or

(b) Weak acids

H2CO3(aq) → H+(aq) + HCO3-(aq)

CH3COOH (aq) → H+(aq) + CH3COO-(aq)

(ii). Using electrical conductivity

Diagram: Electrolytic circuit

CuO(s) + 2H+ (aq) → Cu 2+(aq) + H2O(l)

(a). Strong alkalis

(b). Weak alkalis

QUESTION: Why is calcium hydroxide a weak base?

Measuring the strength of alkalis

(ii). Using pH values

EFFECT OF A SOLVENT ON A SOLUTE

Experiment: - To find out if solutions of HCl in different solvents

Test. Solution of HCl in Solution of HCl in

1. Add magnesium ribbon Evolution of hydrogen No reaction

2. Add small marble CO2 evolved No reaction

The presence of hydrogen ions in aqueous solution of hydrogen chloride explains

In methylbenzene hydrogen chloride remains as molecules. The solution therefore

It is the hydroxide ions that cause alkaline properties.

Amphoteric oxides and hydroxides

(i). Basic oxides

(ii). Acidic oxides

(iii). Amphoteric oxides

Aluminium hydroxide Hydroxide dissolves Hydroxide dissolves

(ii). Al2O3(s) + 6HNO3(aq) → 2Al(NO3)3(aq) + 3H2O(l)

(iii). ZnO(s) + 2HCl(aq) → ZnCl2(aq) + H2O(l)

(ii). Zn(OH)2(s) + 2HCl(aq) → ZnCl2(aq) + 2H2O(l)

(iii). Al(OH)3(s) + 3HCl(aq) → AlCl3(aq) + H2O(l)

Note: In these reactions the metal oxides are reacting as bases.

Reaction with alkalis

(ii). Al2O3(s) + 2NaOH(aq) → 2NaAlO3(aq) + H2O(l)

(iii). ZnO(s) + 2NaOH(aq) → Na2ZnO2(aq) + H2O(l)

(ii). Zn(OH)2(s) + 2NaOH(aq) → Na2Zn(OH)4(aq)

(iii). Pb(OH)2(s) + 2NaOH(aq) → Na2Pb(OH)4(aq)

SOLUBILITY AND SOLUBILITY CURVES

Thus the solubility of the salt is 25 g/100g H2O

If 100g (100 cm3 of water) dissolves 25g of KNO3

Experiment: to determine the effect of temperature on solubility

Total volume of water added 5 10 15 20 25

When solubility is plotted against temperature, the following graph is obtained.

The Solubility curves for various salts

If a saturated solution of KClO3 at 70oC is cooled to 30oC, crystallization occurs.

Solubility at various temperatures

If the mixture is cooled from 50 oC to 20 oC mass of potassium chlorate that

Temperature (oC) 0 20 40 60 80 100

If 100 cm3 of a saturated solution of KNO3 and Pb(NO3)2 is cooled from 70 oC to 40

At 70 oC the mass of;

Mass of potassium nitrate deposited = 138 – 64 = 74 g

2C17H35COO-Na+(aq) + Ca2+(aq) → (C17H35COO-)2Ca(s) + 2Na+(aq)

Types of water hardness

Methods of Removing Hardness of Water

(i). Boiling: This method removes temporary hardness only

(ii). Distillation: This method removes both types of hardness.

Ca2+(aq) + CO32-(aq) CaCO3(s)

Na2X(aq) + Ca2+(aq) CaX(s) + 2Na+(aq)

Na2X(aq) + Mg2+(aq) MgX(s) + 2Na+(aq)