Senior Chem - Controlling Reactions

USING AND CONTROLLING REACTIONS
TOPIC 4: USING AND CONTROLLING REACTIONS

The use and control of chemical reactions are important tasks undertaken by chemists. This topic looks at the
energy changes that accompany chemical reactions, as well as their rates and extents. It also examines the
ways in which chemical reactions are controlled and used to make materials and generate the energy needed
by a modern industrial society.
The increased use of energy from chemical reactions has been a major factor in the evolution of the
industrialised world. In this topic students consider the ways in which this energy is produced and begin
quantitative consideration of the energy changes that accompany chemical reactions.
The production of chemicals is the main function of the chemical industry. These chemicals allow naturally
occurring materials to be modified or replaced and previously unknown materials to be developed. The
industrialised world depends on a chemical industry for the manufacture of a diverse range of materials. In
this topic students look at how chemicals are produced and how the production can be performed most
efficiently.
Knowledge of chemistry can be applied to manipulate the reaction conditions of industrial processes in order
to determine the quantity or quality of the product.
4.1 MEASURING ENERGY CHANGES

Key Ideas Intended Student Learning
Almost all chemical reactions occur with either an Identify combustion and respiration as reactions
absorption or a release of heat or light energy. Other that release energy and photosynthesis as a
forms of energy, such as electrical energy, can also be reaction that absorbs energy.
released.
Exothermic reactions release energy to the Deduce whether a reaction is exothermic or
surroundings whereas endothermic reactions absorb endothermic from information provided.
energy from the surroundings.
The measurement of the heat change in chemical Calculate the heat produced or absorbed for a
reactions is called ‘calorimetry’; the insulated reaction from experimental data, given the
apparatus used for the measurement is a calorimeter. specific heat capacity of water as 4.18 J g−1 K−1.
The heat released or absorbed in a reaction at constant Determine enthalpy changes from experimental
pressure is called the ‘enthalpy change for the data for reactions, including:
reaction’; it is given the symbol ∆ H. the combustion of alcohols;
the neutralisation of acids with bases;
solution processes.
Exothermic reactions have negative ∆ H values. Identify a reaction as exothermic or endothermic,
Endothermic reactions have positive ∆ H values. given a thermochemical equation or the value of
its enthalpy change.
Thermochemical equations express a quantitative Write thermochemical equations that correspond
relationship between the quantities of reactants and the to given molar enthalpies of combustion,
enthalpy change. neutralisation, and solution.
The magnitude of the heat absorbed or evolved for a Calculate the theoretical temperature change of a
reaction is directly proportional to the quantities of specified mass of water or solution heated or
reactants involved. cooled by a reaction, given molar enthalpies and
quantities of reactants.
Introduction
Chemical reactions are usually accompanied by the absorption or release of heat and light energy. Electrical
and sound energy may also be produced.
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Reactions that produce heat include:

• Acid-base neutralisations
• Combustion reactions
• Solution of a solute in a solvent
Exothermic and endothermic reactions
Exothermic reactions release heat energy into the surroundings and cause an increase in temperature.
Endothermic reactions absorb heat energy from the surroundings and cause a decrease in temperature.
Enthalpy changes for reactions
The quantity of heat energy released or absorbed when specific amounts of substances react is called the heat
of reaction. For reactions carried out at constant pressure, the heat of reaction is called the enthalpy change.
The symbol is ∆ H.
The molar enthalpy change for a reaction is the quantity of heat released or absorbed when 1.00 mole of a
specific substance reacts in a chemical reaction under constant pressure. Units - kilojoules per mole (kJ mol-
1
).
Example
The molar enthalpy of combustion of butane (∆ Hcomb(butane)) =2874 kJ mol-1. This means that when 1 mole
of butane undergoes complete combustion, 2874 kJ of heat energy are released to the surroundings.
Calorimetry
Calorimetry is the measurement of energy changes during a chemical reaction. The vessel used for the
measurement is called a calorimeter, which is an insulated reaction vessel. eg a foam cup.
The heat energy absorbed or released by a particular reaction is calculated using the expression.
Heat = specific heat capacity of water x the temperature change x mass
Or
H = c x∆ Txm
Where H = heat change (joules (J))
C = heat capacity (J g-1 °C-1) for water c = 4.18 J g-1 °C-1
m = mass (g)
Note -Frequently the volume of water is measured and this can easily be converted to mass since 1.0 mL ≈
1.0 g
To convert the heat change to molar enthalpy
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where is n the number of moles of the reactant.

It is necessary to divide by 1000 to convert the J to kJ and by the number of moles (n) to give kJ mol-1
Example
Given that 3.24 g of methanol was burnt and the heat used to heat 200 mL of water from 18.2°C to 38.2°C,
calculate the molar enthalpy of combustion of methanol.
m = 3.24 g H = cx∆ Txm
∆ T = 38.2 – 18.2 = 20°C = 4.18 x 20 x 200
M(CH3OH) = 12 + 3x1 + 16 + 1 = 32 g mol -1 = 16720 J
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∆H =
m (water) = 200 mL (≈ 200 g)
n(CH3OH) = m/M
= 3.24/32 oleObject2
= 0.10125 mol =
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∆ H = -165 kJ mol-1
Assumptions and approximations
It is assumed that
• the calorimeter absorbed no heat.
• Heat losses to the surroundings can be ignored.
• The specific heat of the solution is the same as distilled water.
• The mass of 1 mL of solution is 1 g.
Themochemical Equations
Thermochemical reactions are chemical equations that indicate:
• The mole ratio of the reactants
• The state of each reactant and product
• The quantity of heat energy released (-) or absorbed (+) by the mole quantities of reactants or products
indicated in the equation.
Example MgCO3(s) + 2HCl(aq) → MgCl2(aq) + O2(g) ∆ H = -90.4 kJ mol-1
Specific Cases of enthalpy changes
Molar enthalpy of combustion of a substance is the quantity of heat energy released when 1.00 mole of pure
element or compound is burnt completely in oxygen under constant pressure.
Example CH4(g) + 2O2 → CO2(g) + 2H2O(l) ∆ H = -890 kJ mol-1
EXAMPLE
The fuel used in pocket cigarette lighters is butane, C4H10. The molar enthalpy combustion value for butane
is 2874 kJ mol-1. If 1.00 g of butane in a lighter was burnt beneath a steel can containing 1000 mL of water
initially at 18.5°C, calculate the theoretical maximum temperature reached by the water. Would you expect
that the temperature is actually achieved? Discuss.
Molar enthalpy of solution of a substance is the quantity of heat energy released or absorbed when 1.00
mole of the substance dissolves in sufficient solvent so that further dilution causes no further release or
absorption of heat energy.
Example NaOH(s) + aq → Na+(aq) + OH-(aq) ∆ H = -43 kJ mol-1
EXAMPLE
In an experiment to determine the the molar enthalpy of solution of potassium hydroxide, 4.9 g of potassium
hydroxide was added to 100 mL of distilled water in a polystyrene cup. The temperature of water increased
from 18.5°C to 28.1°C. Assuming that the specific heat of the solution is 4.18 J g-1 °C-1, calculate the molar
enthalpy of solution of potassium hydroxide.
Molar enthalpy of neutralisation is the quantity of heat energy released when 1.00 mole of hydrogen ions is
transferred from an acid to a base in an acid-base reaction occurring in aqueous solution.
Example NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) ∆ H = -57 kJ mol-1
EXAMPLE
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The experiment described below was performed to determine the molar enthalpy of neutralisation for the
following neutralisation:
NH3(aq) + HCl(aq) → NH4Cl(aq)
50.0 mL of 1.0 mol L-1 ammonia solution was mixed with 50 mL of 1.0 mol L-1 hydrochloric acid is a
polystyrene cup. The temperature of both solutions was 21.4°C prior to mixing. After mixing the solutions the
maximum temperature reached was 25.6°C. Use this data to calculate the enthalpy of neutralization for this
reaction.
ASSIGNMENT 4.1: MEASURING ENERGY CHANGES
1. Many reactions involve heat being given out or taken in.
(a) Define an exothermic reaction.
(b) Define an endothermic reaction.
1. For each of the following reactions, write a balanced equation for the reaction and classify it as
exothermic or endothermic.
(a) The burning of ethanol in excess oxygen
(b) Photosynthesis
(c) Aerobic respiration
1. When sulfuric acid is mixed with water it generates a lot of heat.
(a) Is this reaction an exothermic or endothermic one?
(b) Sulfuric acid is also denser that water. Explain why sulfuric acid is added TO water during
dilution rather than the other way round.
(c) Draw an energy profile diagram for this reaction.
1. When sodium nitrate is added to water the resulting solution is colder than the water added.
(a) Write a balanced annotated equation for this reaction.
(b) What type of reaction is this? Ionization or dissociation?
(c) Explain the temperature change.
(d) Draw an energy profile diagram for this reaction.
1. Distinguish between heat of reaction and molar enthalpy of reaction.
2. Given that 2.37 g of ethanol was burnt and the heat used to heat 200 mL of water from 18.8°C to
39.6°C, calculate the molar enthalpy of combustion of methanol.
3. The calorimeter used in heat experiments is frequently a foam cup.
(a) Why is a foam cup used?
(b) Why is the reaction mixture stirred during the reaction?
(c) Why is the final temperature measured as quickly as possible?
(d) What 4 assumptions are made during the calculation of the molar enthalpy change?
1. In industry and research laboratories for the
determination of ∆ H values is the bomb
calorimeter. The combustion of a preweighed sample
is carried out in pure oxygen inside a steel ‘bomb’
which in turn is immersed in water. Combustion is
both complete and rapid. The water and other
calorimeter parts absorb the heat energy released
and the temperature increase is recorded.
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Calibration of the bomb calorimeter is achieved by burning substances of known ∆ H and recording
the increases in temperature.
(a) Explain how the systematic errors inherent in the spirit burner method for determining ∆ H are
eliminated or minimized by the use of a bomb calorimeter.
(b) Explain how the bomb calorimeter can be calibrated.
1. Define the following terms
(a) Enthalpy of combustion
(b) Enthalpy of solution
(c) Enthalpy of neutralization.
1. Glucose is used as a source of energy in the human body. The thermochemical equation for the
combustion of glucose in the body is shown below:
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l) ∆ H = -2803 kJ
(a) Calculate the amount of energy released in the body when 1.0 g of glucose undergoes
combustion.
Glucose can also undergo fermentation to produce ethanol, according to the following
equation:
C6H12O6(s) → 2C2H5OH(l) + 2CO2(g)
The ethanol produced by fermentation can be burnt as a fuel, according to the following
thermochemical equation:
C2H5OH(l) + 3O2(g) → 2CO2(g)+3H2O(1) ∆ H = -1364 kJ
(b) Use your answer to part (a) to predict whether or not the fermentation of glucose will warm the
reaction mixture. Give a reason for your answer.
1. Methane is most commonly used as a fuel. The enthalpy of combustion of methane is 890 kJ mol-1.
(a) Write a thermochemical equation for the enthalpy of combustion of methane.
(b) 25 g of methane was burnt to heat some water on a gas stove. Calculate the amount of energy
produced.
(c) Calculate the mass of water that could be heated from 25°C to 100°C by the amount of energy
produced in part (b). [4.18 J raises the temperature of 1.0 g of water by 1.0°C.]
(d) Suggest two reasons why the final temperature would have been less than 100°C when the 25 g
of methane was burnt to heat the mass of water you have calculated in part (c).
1. (a) When 2.50 g of ammonium chloride is dissolved in 100 g of water the temperature falls by 1.7 °C.
Describe, including details of the apparatus used, how this determination would have been performed
in a laboratory.
(a) From the data in (a) calculate the enthalpy of solution of ammonium chloride. State two
assumptions made in the calculation. (4.2 J changes the temperature of 1.0 g of water by 1.0
°C.)
1. A pack has been developed so that small amounts of food can be heated without the need to light a fire
or burn fuel. The researchers who designed the pack found that by mixing powdered magnesium metal
with sodium chloride and iron particles the following exothermic reaction would occur rapidly when
water was added:
Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g) ∆ H = -355 kJ
When water is poured into a porous pad containing the powdered magnesium mixture the heat that is
released warms food contained in an adjacent sealed food pouch.
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Assume that the pack contains 1.0 g of powdered magnesium.

(a) Calculate the maximum amount of heat that can be released by adding water to the powdered
magnesium mixture.
(b) Calculate the minimum mass of water that must be added to release this amount of heat.
(c) The directions on the pack specify the addition of a certain volume of water. If 50 mL of water
is added, calculate its maximum rise in temperature. (4.18 J raises the temperature of 1.0 mL of
water by 1.0 °C.)
1. The enthalpy of solution of anhydrous aluminium chloride, AlC13, is -321 kJ.mol-1.
(a) Write the thermochemical equation to which this value applies.
(b) A technician prepared a solution by dissolving 2.67 g of anhydrous aluminium chloride in
enough water to make 200 mL of solution.
Calculate the final temperature of the solution if the initial temperature of the water was 20.0
°C. Show your working and state any two assumptions you have made. (4.18 J changes the
temperature of 1.0 g of water by 1.0 °C)
4.2 FUELS

Fossil fuels provide energy and are feedstock for the Describe the advantages and disadvantages of the
chemical industry. use of fossil fuels as sources of heat energy,
compared with their use as feedstock.
Carbon dioxide and water are produced by the complete Write balanced equations for the complete
combustion of compounds containing carbon and combustion of fuels in which the only products
hydrogen. are carbon dioxide and water.
The products of the incomplete combustion of fossil Describe the undesirable consequences of
fuels include carbon (soot) and carbon monoxide. Soot incomplete combustion.
and carbon monoxide are harmful to the environment.
Fuels can be compared on the basis of the quantity of Calculate the quantities of heat evolved per mole,
heat released. per gram, and per litre (for liquids) for the
complete combustion of fuels.
Fossil Fuels
The most common fuels in use today are the fossil fuels oil, gas and coal. These materials have been formed
over millions of years by the anaerobic breakdown of plants and animals buried beneath the earth’s surface.
They are contain mainly hydrocarbons like methane, ethane etc and coal contains mainly carbon.
Advantages of fossil fuels
Coal abundant, cheap
Oil abundant, easily mined and transported because it is a liquid, many uses as fuel, raw material for
plastics
Gas easily extracted, purified and treated; burns cleanly, high energy output
Disadvantages of fossil fuels
They are all non-renewable and are a valuable feedstock for other industries like plastics.
Coal Burns giving off carbon dioxide (Greenhouse gas) impurities of sulfur produce sulfur dioxide (acid
rain) when coal is burnt, high temperature combustion can lead to the formation of nitrogen oxides
(acid rain, photochemical smog, hole in the ozone layer), releases particular matter which cause
respiratory problems.
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Oil Produces carbon dioxide, sulfur dioxide and nitrogen oxides when burning; produces soot, unburnt
hydrocarbons contribute to photochemical smog.
Gas produces carbon dioxide, nitrogen oxides.
Combustion of fuels
Complete combustion of fuels can only occur when the supply of oxygen for the combustion is not limited.
This releases the maximum amount of energy. The products are carbon dioxide and water.
If the amount of oxygen is limited, incomplete combustion occurs. This is less efficient, and releases less
oxygen. The products are carbon monoxide, carbon (soot) and water in varying proportions depending on the
available oxygen.
Complete combustion C6H12(g) + 9O2(g) → 6CO2(g) + 6H2O(l) ∆ H = -3916 kJ mol-1
Incomplete combustion C6H12(g) + 6O2(g) → 6CO(g) + 6H2O(l) ∆ H = -2224 kJ mol-1
Incomplete combustion C6H12(g) + 3O2(g) → 6C(s) + 6H2O(l) ∆ H = -1558 kJ mol-1
Harmful effects of the products of incomplete combustion.
Carbon monoxide displaces oxygen from haemoglobin in the blood. Since haemoglobin is the main
mechanism for the transport of oxygen in the blood, the absorption of carbon monoxide deprives the body of
oxygen producing symptoms varying from impairment of judgement and visual perception (at 10 ppm in air)
to death (at >750 ppm).
Soot is a microcrystalline form of carbon produced by incomplete combustion. It produces visual pollution
(smoke and soot), blocks air and fuel inlets in burners and deposits on leaves causing impaired
photosynthesis. Soot in the lungs can lead to respiratory problems like bronchitis, asthma and emphysema.
Unburnt hydrocarbons contribute to photochemical smog.
Heat energy from fuels
While the energy produced by a particular combustion reaction is usually quotes in terms of the molar
enthalpy of combustion, it can be quoted in terms of heat per gram (energy density) or heat per litre.
Example hexane (C6H14), ∆ H(Combustion) = -4158 kJ mol-1, molar mass = 86 g mol-1, density = 655 g L-1
Energy density = = 48 kJ g-1
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Energy per litre = = 31668 kJ L-1
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Fuels like methane have a high heat density, but low heat per litre, while octane has a lower heat density but
because of its greater density, it gives more heat per litre.
EXERCISE 4.2 : FUELS
1. Fossil fuels are the main energy sources used today.
(a) What is a fossil fuel?
(b) What are fossil fuels made from?
(c) What are the advantages of using
(i) Coal
(ii) Oil
(iii) Gas
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(d) What are the disadvantages of using

(i) Coal
(ii) Oil
(iii) Gas
1. Write a balanced equation for the complete combustion of butane, C4H10.
2. When using a bunsen burner the flame is controlled by the amount of gas and whether the air hole is
open.
(a) When the air hole is open,
(i) Describe the flame.
(ii) What are the likely products of combustion. Explain
(iii) Write a balanced equation for the reaction.
(b) When the air hole is closed,
(i) Describe the flame.
(ii) What are the likely products of combustion. Explain
(iii) Write a balanced equation for the reaction.
1. Describe the undesirable consequences of incomplete combustion of a fossil fuel.
2. Complete the following table
Fuel ∆ H(combustio Molecula Molar Density(g/L Heat/gra Heat/litre
n) (kJ mol-1) r mass ) m
formula
Methane -890 422
Ethane -1557 546
Propane -2220 582
Butane -2875 601
Octane -5512 685
4.3 ELECTROCHEMISTRY
Electrochemical cells are conveniently divided into Identify a cell as galvanic or electrolytic, given
galvanic cells, which produce electrical energy from sufficient information.
spontaneous redox reactions, and electrolytic cells,
which use electrical energy from an external source to
cause a non-spontaneous chemical reaction.
Redox reactions can be considered as two half- Write half-equations for half-reactions, including
reactions, one involving oxidation and the other those in acidic solution, given information about
reduction. the reactants and the products.
Galvanic and electrolytic cells involve oxidation at the Identify the anode and the cathode in a galvanic
anode and reduction at the cathode, with electrons cell or an electrolytic cell, given information
being transferred from one electrode to the other about the reactants and the products.
through an external circuit.
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Galvanic cells are commonly used as portable sources Identify the:

of electric currents. • charge on the electrodes;
• direction of electron flow;
• movement of ions in the salt bridge or
electrolyte;
given a sketch for a galvanic cell and information
about electrode reactions.
Fuel cells are galvanic cells in which the electrode State the advantages and disadvantages of fuel
reactants are available in continuous supply. cells compared with other galvanic cells.
Some galvanic cells can be recharged by using an Describe the complementary nature of the
external electrical supply to reverse the electrode charging and discharging of rechargeable
reactions. galvanic cells.
Electrolytic cells are used in the production of active Describe, with the aid of equations, the
metals. electrolytic production of active metals.
ELECTROCHEMISTRY
Electrochemical cells
An electrochemical cell comprises the following components:
• Two electrodes, one being the anode, the other the cathode. They can be made of an active metal or an
inert electrode.
• An electrolyte which can be an aqueous solution containing ions or a molten ionic compound
• Metal wire that connects the two electrodes
• An oxidizing agent in contact with the cathode and a reducing agent in contact with the anode ( it may be
the electrode itself)
There are two types of electrochemical cell
• Galvanic cells which use redox reactions to produce a direct electric current. eg dry cell “batteries”
• Electrolytic cells which use electricity in the form of a direct current to bring about electrolysis (non
spontaneous redox reaction). These are used in electroplating and making a number of chemicals (eg salt
water chlorinators in pools)
Redox terminology
Redox is a combination of the words REDuction and OXidation. They must occur simultaneously.
Oxidation is a half reaction in which a species loses electrons. Two examples are:
Mg → Mg2+ + 2
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SO2 + 2H2O → + 4H+ + 2

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Reduction is a half reaction in which a species gains electrons. Two examples are
Cu2+ + 2 → Cu
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I2 + 2 →2
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Oxidising agents (or oxidisers) cause oxidation by accepting electrons and are reduced in the process.
Reducing agents (or reducers) cause reduction by donating electrons and are oxidised in the process.
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Electrolytes are liquids that conducts electricity. Can be a molten ionic salt or aqueous solution of a. ions.
The anode is the electrode at which oxidation occurs.
The cathode is the electrode at which reduction occurs.
Redox pairs are couplings of oxidisers (or reducers) and their reduced (or oxidised) forms. Examples:
Oxidiser Reduced form
Permanganate ion (pink) → Manganese (II) ion
(colourless)
Dichromate ion (orange) → Chromium (III) ion

(Green)
Hydrogen peroxide H2O2(aq) → H2O(l) water
Hypochlorite ion → Chloride ion
Bromine (orange) Br2(aq) → Bromide ion

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Iodine (yellow/brown) I2(aq) → Iodide ion

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Reducer Oxidised form

Sulfite ion → Sulfate ion
Hydrogen sulfide H2S(g) → S(s) Sulfur

Hydrogen peroxide H2O2(aq) → O2(g) Oxygen (bubbles)
Sulfur dioxide SO2(g) → Sulfate ion
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Bromide → Br2(aq) Bromine

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(orange)
Iodide ion → I2(aq) Iodine (yellow/brown)

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Iron (II) ion → Iron (III) ion

Writing redox equations for reactions in neutral or acidic solutions

The procedure for writing redox equations involves writing equations for the oxidation half reaction and
reduction half reaction and then summing these equations to produce an equation for the overall reaction.
This is illustrated in the following example:
Sulfur dioxide gas is bubbled through an acidified solution containing dichromate ions; the latter is reduced
to chromium (III) ions and the sulfur dioxide is oxidised to sulfate ions. The equation for the overall reaction
is developed as follows:
1. Identification of the redox pairs
→
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SO2(g) →
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2 Develop each redox pair into a balanced half–equation using the following steps in the order shown:
• balance any element other than hydrogen or oxygen
→ 2
SO2(g) →
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• balance the oxygen atoms by adding an appropriate number of water molecules to the left or right
hand sides
→ 2 + 7H2O
2H2O + SO2(g) →
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• balance the hydrogen atoms by adding an appropriate number of hydrogen ions to the left or right
hand sides
+ 14 → 2 + 7H2O
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2H2O + SO2(g) → + 4
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• balance the electrical charge by adding an appropriate number of negatively charged electrons to
the left or right hand sides
+ 14 + 6 → 2 + 7H2O
2H2O + SO2(g) → + 4 + 2
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3. Combining the two half reaction equations to produce an overall equation involves the following
steps:
• if the number of electrons shown in the two half equations are not equal then the half equations
must be multiplied by an integer to make them equal
+ 14 + 6 → 2 + 7H2O
3x[2H2O + SO2(g) → + 4 + 2 ]
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• the two half equations are then added together. Electrons, water molecules and hydrogen ions
appearing on opposite sides are cancelled out
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+ 2 + 3SO2(g) → 2 + + 2H2O
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• check that all atoms and charges balance

Galvanic cells
Galvanic cells are electrochemical cells which produce electrical energy in the form of a direct electric
current from spontaneous redox reactions. In these cells, the reducing agent and oxidising agent are not in
direct contact with each other. They are connected via a metal wire and a salt bridge.
A galvanic cell is made of two half cells:
• An oxidation half cell called the anode
• A reduction half cell called the cathode
The half cells are connected via an external metal wire through which electrons flow
A salt bridge connects the solutions in the two half cells. The salt bridge contains free ions which conduct
ions to complete the circuit. Positive ions migrate towards the reduction half cell, while negative ions
migrate towards the oxidation half cell. Example of the Zn| Zn2+| | Cu2+| Cu cell
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When a cell composed of two metal half–cells is operating, the more reactive of the two metals (in this case
zinc) is oxidised. The zinc electrode is eaten away:
Zn(s) → +2
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The electrons that are lost flow through the metal wire to the cathode where they are accepted by copper ions
in the solution. The copper ions are reduced to copper metal which deposits on the surface of the electrode:
+ 2 → Cu(s)
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The equation for the overall cell reaction is obtained by adding the oxidation and reduction half equations:
Zn(s) + → Cu(s) +
The positive ions in the salt bridge move into the copper half cell to counter the negative charge of the
electrons moving into this half-cell via the conducting wire. The negative ions in the salt bridge move into
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the zinc half cell to replace the negative charge of the electrons moving out of this half-cell via the
conducting wire. This movement of ions constitutes an electric current that completes the electrical circuit.
A salt bridge consists of a concentrated solution of a salt, the ions of which should not react with the ions
present in the solutions in the half–cells. The ions should also not be easily oxidised or reduced. A suitable
salt for the salt bridge of the above cell is sodium chloride. In solution, sodium ions cannot be reduced and
chloride ions can only be oxidised if they are present in very high concentration. Neither ion forms a
precipitate with the ions in the halfcells.
From knowledge of the relative reactivity of metals it is possible to predict the reactions that occur in any
galvanic cell consisting of metal half–cells:
• the more reactive metal will be oxidised to its ions
• the ions of the less reactive metal will be reduced to the metal
Having established the half reactions occurring in each half-cell, it is possible to deduce other features of the
cell:
• the more reactive metal will be become the anode
• the less reactive metal will become the cathode
• the direction of electron flow in the external metal wire will be from anode to cathode
• the direction of movement of positive ions in the salt bridge will be towards to cathode
• the direction of movement of negative ions in the salt bridge will be towards to anode
Solution half cells
Galvanic cells can be constructed using inert electrodes in contact with oxidising and reducing solutions.
Inert electrodes (usually platinum or graphite) are used as the electrodes. Example below.
Electron flow
electr
graphite
Graphite
Reducer and Oxidiser and

oxidised form reduced form
( Fe2+ /Fe3+ ) Salt bridge ( MnO−4 /H + )/Mn2+
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Fuel Cells
In a typical fuel cell, gaseous fuels are fed continuously to an anode (negative electrode) compartment and an
oxidant (such as oxygen from the air) is fed continuously to the cathode (positive electrode) compartment.
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Oxidation and reduction half reactions take place at the anode and cathode respectively to produce an electric
current. eg
Anode : H2 → 2H+ + 2e-
Cathode : O2 + 2H2O + 4e- → 4OH-
The electrodes are porous to increase the surface area and often impregnated with a catalyst.
In the galvanic cells studied so far, the main limitation is that when the chemicals are all used up, the cell
stops producing electricity, eg a battery becomes flat. In fuel cells, there is a continuous flow of reactants
over the electrodes and theoretically it will continue to produce electricity as long as the supply of gases
continues.
The diagram below represents an alkaline hydrogen-oxygen fuel cell, one of the first fuel cells developed.
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In this cell:
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The electrolyte is aqueous potassium hydroxide. The electrode reactions take place under alkaline
conditions. Operating temperature is in the range 50 to 200°C.
Hydrogen gas flows over the anode (the negative electrode) where it undergoes oxidation as follows:
H2 + 2OH- → 2H2O + 2e-
The electrons lost flow through the anode and the external circuit to the cathode thereby creating an electric
current.
Oxygen molecules flowing over the cathode accept the electrons that have come from the anode and are
reduced. The hydroxide ions that are produced migrate through the electrolyte towards the anode:
O2 + 2H2O + 4e- → 4OH-
The overall cell reaction is:
O2 + 2H2 → 2H2O∆ H = -286 kJ mol-1
The total output of this cell is electrical energy, heat energy and water.
Advantages and disadvantages of fuel cells
Advantages
Fuel cells have several advantages over conventional galvanic cells and over electricity generators that use
steam driven turbines. These advantages include:
• they continuously produce an electric current so long as fuel and oxidant is continuously supplied;
• they have high operating efficiency (between 70 and 80%);
• they offer a better mass to power output ratio than conventional galvanic cells;
• they use readily available fuels and oxidants;
• they do not produce pollutant gases such as sulfur dioxide and the oxides of nitrogen;
• the electrodes and electrolyte are not consumed during operation;
• electrode reaction products are removed as they are formed and do not remain inside the cell;
• they require minimal maintenance;
• they are silent during operation as there are no moving parts;
• in different versions they can be used for small to large scale applications and for stationary or mobile
(particularly transport) power generation.
Disadvantages
The following disadvantages are the focal points for much of the current research being undertaken on fuel
cells:
• impurities in the fuel or oxidant can 'poison' the electrode catalysts and/or contaminate the electrolyte.
For example, any carbon dioxide present in the oxidant can react with a potassium hydroxide electrolyte
forming potassium carbonate solid that can clog the porous electrodes. This restricts the use of air as an
oxidant.
• high purity fuels and oxidants are costly;
• medium to high temperatures are needed for the cells to function most effectively;
• metal electrode catalysts such as platinum and palladium are very costly;
• some of the electrolytes are very corrosive.
Similarities and differences between conventional galvanic cells and fuel cells
The table below summarises the main similarities and differences between conventional galvanic cells
(Commonly called batteries) and fuel cells.
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Similarities between Differences between conventional cells and fuel cells

conventional cells and fuel cells Conventional galvanic cells Fuel cells
redox reactions used to produce limited quantities of reactants continuous external supply of
direct current stored in cell reactants
electrolyte exists between When fully discharged must be never discharged or run down
electrodes discarded or recharged.
No emission of pollutants during Discarding presents some
operation environmental problems.
Recharging is time consuming.
cathode positively charged limited 'life' virtually unlimited 'life'
anode negatively charged
energy output decreases as cell waste products are removed
runs down continuously
Rechargeable galvanic cells
Rechargeable galvanic cells are also called storage cells. During discharge of these cells, electrode reactions
produce an electric current in an external circuit. At the same time, the oxidiser and reducer inside the cell
are both used up.
During recharge, an external power source provides an electric current to the electrodes. The discharge
reactions are reversed and the original oxidiser and reducer are regenerated. This can be repeated many
times.
The lead-acid cell
The typical lead-acid car battery consists of 6 (2V) lead-acid cells connected in series to give 12 V.
Structure
• Anode is spongy lead.
• Cathode is lead (IV) oxide, PbO2, packed onto lead plates.
• Electrolyte is 38% sulfuric acid (density 1.25 g mL-1)
• Separators of polymer sheets separate the cells
During discharge
• At the anode (-) : Pb(s) + → PbSO4(s) + 2e-
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• At the cathode (+) : PbO2(s) + + 4H+ + 2e- → PbSO4(s) + 2e-
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Sulfuric acid is consumed during the reaction and the density decreases (at 1.1 g mL-1 the battery is flat).
During charging the above reactions are reversed (and sulfuric acid is regenerated).
The nickel-cadmium cell
Structure
• Anode is cadmium
• Cathode is solid nickel (III) hydroxide, Ni(OH)3, mixed with graphite to improve conductivity.
• Electrolyte is potassium hydroxide.
• Separators of polymer sheets separate the cells
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During discharge
• At the anode (-): Cd(s) + 2 → Cd(OH)2(s) + 2e-
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• At the cathode (+) : 2Ni(OH)3(s) + 2e- → 2Ni(OH)2(s) + 2
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During recharge these reactions are reversed.

Electrolytic cells
An electrolytic cell is an electrochemical cell in which an external source of electrical energy is used to
bring about a non-spontaneous redox reaction. This process is called electrolysis.
Uses of electrolytic cells:
• Producing pure metals from from their compounds;
• Recharging batteries;
• Electroplating;
• Refining metals such as copper;
• Producing non-metallic elements like chlorine.
The basic components of an electrolytic cell are:
• an external source of electrons such as a battery;
• an electrolyte
• two electrodes (can be active or inert)
• an external conductor
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e- Cathode
Power
Negatively
Positively
Anode (+)
(-)
supply
charged ions
Electrons are
(cations)
(anions)
supplied
drawn away
to the
are cathode
from attracted
the anodeto
the
the cathode
anode (+)(-)
During the operation of an electrolytic cell:

• The power supply pumps electrons through the external circuit;
• In the electrolyte, the positive ions (cations) are attracted to the cathode (-) and negative ions (anions) are
attracted to the anode (+). This constitutes an electric current.
• An oxidation half reaction occurs at the anode. This can either be the anions in the solution or water,
depending on which is more easily oxidised.
• A reduction half reaction occurs at the cathode. This can either be the cations or water depending on
which is more easily reduced.
Reduction Oxidation
These metal ions are more easily reduced than These non-metal ions are more easily oxidised than
water Cu2+, Ag+, Ni2+, Zn2+,Pb2+ water Cl-, Br-, I-
If water is reduced, the following reaction occurs If water is oxidised, the following reaction occurs
H2O + 2e- → 2OH- + H2(g) 2H2O → 4H+ + O2(g)+ 4e-
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Production of highly reactive metals

Highly reactive metals like sodium and potassium, can only be produced by electrolysis of molten chloride
salts.
-
Power
eMolten salt(-)
Cathode
Anode (eg
(+) NaCl)
Na2Cl+ →
supply
+ -
e→ ClNa
2
+ 2e
A Comparison of galvanic and electrolytic cells
Type Electrode Type of reaction Charge on electrode

Galvanic Anode Oxidation Negative (-)
Cathode Reduction Positive (+)
Electrolytic Anode Oxidation Positive (+)
Cathode Reduction Negative (-)
EXERCISE 4.3 : ELECTROCHEMISTRY
1. The diagram below represents an electrochemical cell.
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(a) Is it a galvanic or electrolytic cell?

(b) What energy change occurs in this cell?
(c) What is the role of -(V)-, (A), (B), (C)
(d) Which metal is more reactive?
(e) Write half equations for the reactions at each electrode
(f) Write an equation for the overall reaction
(g) Which electrode is the anode? Why?
(h) Which electrode is positive? Why?
(i) If A contains KCl(aq), which way will the potassium ions move?
(j) Which electrode loses weight? Why?
(k) What happens to an iron nail placed in zinc sulfate solution?
1. Write equations for the half reactions and the overall reaction for (a) and (b) below. Identify each half
reaction as oxidation or reduction.
(a) An acidified solution of potassium dichromate is added to an aqueous solution of sulfite ions.
The dichromate is converted to green chromium (III) ions, Cr3+, while at the same time the
sulfite ion is converted to sulfate ions.
(a) An acidified solution of hydrogen peroxide is added to an aqueous solution of potassium iodide.
The iodide is converted to yellow/brown iodine.
1. For the following combinations of metal half-cells, predict the direction of electron flow and identify
the anode and cathode.
metal half-cell combinations direction of electron flow anode cathode
Zn| Zn2+| | Fe2+| Fe
Ag| Ag+| | Pb2+| Pb
Fe| Fe2+| | Cu2+| Cu
2. Suggest a common use for galvanic/voltaic cells.
3. Fuel cells are become popular energy sources.
(a) What is a fuel cell? Give an example of the reactants used.
(b) What are the electrodes often made from?
(c) What are the advantages of fuel cells?
(d) What are the disadvantages of fuel cells?
1. The lead-acid battery is rechargeable.
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(a) What is the anode made of?

(b) Write an equation for the reaction occurring at the anode.
(c) What is the cathode made from?
(d) Write an equation for the reaction occurring at the cathode.
(e) Write an equation for the overall reaction.
(f) When testing a battery to see if it flat, the density is sometimes measured. Why?
(g) What happens during recharging?
1. One common use of electrolytic cells in the production of metals.
(a) What is an electrolytic cell?
(b) What are some of the other uses of electrolytic cells?
(c) Zinc is prepared by electrolysis of a zinc sulfate solution.
(i) At which electrode is zinc deposited?
(ii) Write a half reaction for the reaction where zinc is deposited.
(iii) Why does the sulfate ion not react at the other electrode?
(iv) Write a half equation for the reaction occurring at this electrode.
1. Elements like sodium and potassium cannot be produced by electrolysis of aqueous solutions of their
ions.
(a) Why?
(b) But they are produced by electrolysis. What is the electrolyte?
4.4 RATE OF REACTION
The time taken for a reaction to reach a specified point Determine the effect of varying conditions on the
is an indication of the rate of the reaction. rate of a given reaction, using experimental data.
The rates of a reaction at different times can be Draw and interpret graphs representing changes
compared by considering the slope of a graph of in quantities or concentration of reactants or
quantity (or molar concentration) of reactant or product products against time.
against time.
The rates of a reaction are affected by changes in the: Predict and explain the effect that changes in
concentration of reactants; condition have on rates of reactions in terms of
the:
temperature of the reaction mixture;
frequency of collisions between reactant
pressure of the reaction mixture (for systems involving
particles;
gases);
orientation of colliding particles;
state of subdivision of reactants;
energy of colliding particles;
presence of catalysts (including enzymes);
activation energy.
intensity of light (for photochemical reactions).
The energy changes in a reaction can be represented by Draw and interpret energy profile diagrams that
an energy profile diagram. show the relative enthalpies of reactants and
products, the activation energy, and the enthalpy
change for the reaction.
Introduction
One of the prime factors to consider when making chemicals is the speed at which chemical reactions occur
and to know how these speeds can be changed. The speed at which reactions occur is known as the rate of
reaction.
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If ways can be found to increase the speed of commercially important reactions without a corresponding
increase in the energy requirements, a considerable saving in an already increasing energy bill would result.
An example of this can be found in the research for a more efficient conversion of solid fuels, e.g. coal, into
liquid or gaseous fuels.
Not only must the chemist consider how to increase the reaction rate, but also find ways of decreasing very
fast reactions to a more manageable rate. Some desirable commercial reactions are too fast to be useful.
Control is important.
In chemical reactions, chemical bonds are broken and new bonds form. Studies of the speed at which
reactions occur provide a further understanding of, and theoretical support for, the chemists' ideas of how
atoms bond together.
The rates observed for different reactions vary greatly. Reactions between acids and bases in solution are so
fast that the rate is difficult to measure. Other reactions such as the rusting of iron are slow. At a further
extreme, reactions involving the weathering of rocks are so slow that change may not be observed in a
lifetime.
Measuring Reaction Rate
The rate of a reaction is measured by the change in amount of substance, either reactions or products, divided
by the time taken for that change to occur. If solutions are used, the change in concentration of a species can
be used.
Rate = =
Rate = =
Consequently, if one monitors the amount of a reactant over a period of time and draws a graph of the
results, the following graph may depict a typical outcome. This graph shows the decrease in the
concentration of a reactant, A, against time. The straight lines show the rate at three points during the
subsequent reaction. The slope of these tangents gives a measure of the rate
Conditions Affecting Reaction Rates

From experiment, it has been found that the rate of a chemical reaction is
determined by a number of factors. These factors are:
• the nature of the reactants,
• the concentrations of the reactants,
• the temperature of the reactants,
• the pressure of the reaction mixture for gaseous systems,
• the state of subdivision of the reactants, ie the particle size,
• Reactions, which are affected by light, are called photochemical reactions.
• the amount (intensity) of light falling on the reactants, for reactions affected by light, and
• catalysts (including enzymes).
The study of factors that affect rate of reaction is called reaction kinetics.
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Collision theory of chemical reactions

The effects of these factors can be explained in terms of The Collision Theory Of Chemical Reactions. This
theory is base on the premise that, for a reaction to occur
• the particles (atoms, ions or molecules) are in constant random motion.
• The particles must collide.
• The colliding particles must have enough energy to start a reaction.
The rate of the reaction is dependent on
• The magnitude of the activation energy.
• The frequency of the collisions
• The energy of the particles.
• The orientation of the particles.
Energy Profile diagrams
The course of a chemical reaction can be represented as an energy profile diagram which shows the relative
potential energy values for the reactants, products and the activation complex. In order to form the activation
complex, the kinetic energy of the colliding particles must exceed the activation energy or the particles just
bounce off.
Energy profile diagram for an exothermic reaction Energy profile diagram for an endothermic
reaction
Factors that affect reaction rate.
Factor Effect on rate Explanation Example
Concentration Increases with More particles per unit volume Concentrated acids react faster
concentration. gives more collisions than dilute ones
Temperature Increases with Particles have more kinetic Food deteriorates faster in
temperature energy hence a collision is warm weather, hence the need
more likely to produce an for refrigeration
activated species.
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Factor Effect on rate Explanation Example

Pressure (gases) Increases with Pressure compresses the gas The Haber processes forces
pressure and so the particles are closer hydrogen and nitrogen
together hence more collisions. molecules together under 200
atmospheres of pressure to
increase the yield
Surface Area Increases with Increased surface area exposes Explosions occur in flour mills
surface area more particles to collisions or coal mines if flames come in
contact with fine dust
Catalysts Catalysts can Catalysts can provide an Platinum catalyses the
increase or alternative pathway for a decomposition of pollutants in
decrease the rate reaction. It may provide a the catalytic converter of a car.
of a reaction surface for the reaction or
without being orientate molecules correctly.
used up in the Basically it changes the
process. activation energy.
Intensity of light Increased Light increases the energy of Photosynthesis.
intensity of light the particles.
increases the rate
of photochemical
reactions
Time Reactions slow The chemicals are used up and Reactions slow down and stop.
with time. so concentration drops
EXERCISE 4.4 : REACTION RATES

1. Hydrogen peroxide solution can be used as a bleaching agent. It decomposes as shown by the
equation:
2H2O2 → 2H2O + O2
An experiment carried out to monitor the decomposition of hydrogen peroxide gave the following data
for the concentration of hydrogen peroxide remaining at the end of each time interval shown.
[H2O2] mol L-1 Time (min)
2.32 0
1.86 5
1.49 10
0.98 20
0.62 30
0.25 50
(a) Draw a graph of hydrogen peroxide remaining against time.
(b) Name the dependent and independent variables in this experiment
(c) Use the graph to calculate the instantaneous rate of the reaction:
(i) At 5 minutes
(ii) At 25 minutes
(d) Calculate the average rate of reaction over the first 20 minutes.
(e) On the same set of axes sketch two graphs:
(i) The graph expected if the experiment was conducted at a higher temperature.
(ii) The graph expected if a catalyst had been added before the experiment was started.
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(f) Use the collision theory to explain why the concentration of hydrogen peroxide fell more
rapidly in the first 5 minutes than it did in the 5-minute intervals between 25 and 30 minutes.
1. List the 6 factors that affect reaction rates, how changes in that variable affect the rate and explain it
in terms of collision theory. A table may be a good way to display your answer.
2. Sketch generalized energy profile diagrams for exothermic and endothermic reactions showing the
relative enthalpies of the reactants, the products, the activation energy and the enthalpy change for
the reaction.
4.5 CHEMICAL EQUILIBRIUM
All chemical reactions carried out in a closed system at Describe the dynamic nature of a chemical
a fixed temperature eventually reach a state of dynamic system at equilibrium.
equilibrium in which the concentrations of all the
reactants and products cease to change with time. The
total mass of reactants and products in a closed system
remains constant.
The position of equilibrium in a chemical system at a Write Kc expressions that correspond to given
given temperature can be indicated by a constant, Kc, reaction equations, and perform calculations
related to the concentrations of reactants and products. involving Kc and equilibrium concentrations in
which all reacting species are included in the
expression.
The changes in concentrations of reactants and Draw and interpret graphs representing changes
products as a system reaches equilibrium can be in concentration of reactants and products against
represented graphically. time.
The final equilibrium concentrations for a given Calculate the initial and/or equilibrium
reaction depend on the: concentrations or quantities of reactants and
• initial concentrations of the reactants and products; products, given sufficient information about
a particular system initially and/or at equilibrium.
• temperature;
• value of Kc;
• pressure (for systems involving gases).
If a change is made to a system at equilibrium so that it Predict, using Le Châtelier’s principle, the effect
is no longer at equilibrium, a net reaction will occur (if on the equilibrium position of a system of a
possible) in the direction that counteracts the change. change in the:
This is a statement of Le Châtelier’s principle. concentration of a reactant or product;
overall pressure of a gaseous mixture;
temperature of an equilibrium mixture for which
the ∆ H value for the forward or back reaction is
specified.
CHEMICAL EQUILIBRIUM
Most chemical reactions are reversible. By convention, in a chemical equation, the reactants are placed on
the left and the reactants on the right:
Reactants → products
This is called the forward reaction. When the products of a reaction react to for the original reactants, the
following representation is use:
Reactants ← products
This is called the back reaction.
When forward and back reactions occur at the same time, the following convention is used:
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Reactants products
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If a reversible reaction is carried out in a closed system and at constant pressure, then the concentrations of
reactants and products eventually reach constant values. The system is said to have reached a position of
equilibrium. At equilibrium, the measurable or observable properties of the system, such as colour intensity,
pressure and pH are constant.
Note: A closed system is one where no chemicals enter or leave the system.
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Before equilibrium, the forward reaction is faster than the reverse reaction, but as the concentration of
products increases, so the rate of the reverse reaction increases until the forward and backwards reactions are
equal. Equilibrium has been achieved. Note that at equilibrium reactions are still occurring – it is a dynamic
equilibrium.
The equilibrium constant
Consider the equilibrium reaction below:
aA + bB cC + dD
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At equilibrium, the expression below has a constant value called the equilibrium constant, Kc.
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Where [C], [D] etc represent the molar concentrations at equilibrium. We don’t worry about units for Kc.
Examples
Reaction equation Kc expression
2SO2 + O2 2SO3
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N2 + 3H2 2NH3
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The magnitude of the equilibrium constant, Kc, provides an indication of the yield of products.
Large Kc values (>10), indicate a high yield at equilibrium position, whereas small value (<0.1) indicate low
yields.
Calculations involving the equilibrium constant
Example
The conversion of sulfur dioxide to sulfur trioxide is an important step in the Contact Process used to make
sulfuric acid.
2SO2 + O2 2SO3
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For one such equilibrium mixture, the concentrations at 727°C were determined to be:
[O2] = 0.0150 mol L-1, [SO2] = 0.0223 mol L-1, [SO3] = 0.0360 mol L-1
Therefore the Kc value can be calculated from the Kc expression as below:
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Given that there was no SO3 present initially, the initial concentrations of SO2 and O2 can be calculated as
below:
In 1 litre SO2 O2 SO3
At equilibrium 0.0223 0.0150 0.0360
Changes in attaining -0.0360 -0.0180 +0.0360
equilibrium
Therefore initially 0.0223 + 0.0360 = 0.0150 + 0.180 = 0
0.0583 0.0330
Changing the extent of a reaction – le Châtelier’s Principle
If the conditions of a system at equilibrium are changed, then the system adjusts to form a new equilibrium
system with a different equilibrium position. The system can be changed by changing concentration,
temperature and/or pressure (for gaseous systems). The conditions can be manipulated to maximise the yield
of a particular reaction
Le Châtelier’s Principle can be used to predict how changes affect the equilibrium position.
If an external change is made to the reaction conditions of a system at equilibrium so that it is no longer at
equilibrium, a net reaction will occur (if possible) in the direction that counteracts the change: the internal
change will oppose the external change.
Changes to concentration
When a concentration change is brought about by adding or removing some reactant or product from a
system, then a shift in the equilibrium position will occur to minimise the change.
External change Internal change
Increasing the concentration of a reactant The extra reactant is consumed.
The equilibrium moves to the right.
Decreasing the concentration of a reactant The removed reactant is partially replaced by
products forming more reactants.
The equilibrium moves to the left.
Increasing the concentration of a product The extra product is consumed.
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The equilibrium moves to the left.

Decreasing the concentration of a product The removed product is partially replaced by
reactants forming more products.
The equilibrium moves to the right.
Example
Consider the following equilibrium:
N2O4(g) 2NO2(g)
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If extra N2O4(g) is added to the system, the equilibrium shifts to the right to consume the extra N2O4(g) this
results in the formation of more NO2(g) (at constant temperature and pressure). The concentration changes
with time are illustrated in the diagram below.
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Changes to pressure
Pressure changes can cause a shift in the position of an equilibrium if at least one of the reactants or products
is a gas. When the pressure is increased, the volume decreases and a change to the equilibrium position is
possible. In a closed container at a fixed temperature, the pressure is proportional to the total number of
molecules. A reduction of the total number of particles reduces the pressure.

Increasing the pressure (by decreasing the volume) The equilibrium position is shifted to produce a
smaller number of molecules
Decreasing the pressure of a system (by increasing The equilibrium position is shifted to produce a
the volume) greater number of molecules
Note:
If an inert gas is added to an equilibrium system to increase the pressure but without increasing the volume,
no change to the position of the equilibrium occurs (since there is no change in concentration).
If there are equal numbers of molecules on the left and right side of the reaction, the eqilibrium position is
not affected by pressure changes.
Example
28
N2O4(g) 2NO2(g)
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If the pressure is increased, by decreasing the volume, the equilibrium position is shifted to produce a
smaller number of molecules in the gas phase. The back reaction will be favoured because it converts two
molecules (2xNO2) into one (1xN2O4). At the new equilibrium position, the concentrations of NO2 and N2O4,
are both greater at the new equilibrium position.
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Changes to the temperature of a system at equilibrium

If the forward reaction of an equilibrium is exothermic, then the back reaction is endothermic to the same
magnitude.
According to Le Châtelier’s Principle, if the temperature of a system is increased, the equilibrium shifts in
the direction that absorbs the heat gained from the surroundings. Thus it shifts in the endothermic direction.
Increasing the temperature The equilibrium shifts in endothermic direction
Decreasing the temperature The equilibrium shifts in exothermic direction
Example
N2O4(g) 2NO2(g) ∆ H = +58 kJ mol-1
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Note: The quoted ∆ H value always refers to the forward reaction.

When the temperature is increased at constant at constant volume, the equilibrium is shifted in the forward
(endothermic) direction. The number of moles and concentration of N2O4 decreases while NO2 increases.
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Catalysts
Catalysts increase the rate of attainment of equilibrium, they do not affect the equilibrium position because
they affect both forward and backward reactions equally.
EXERCISE 4.5 : EQUILIBRIUM
1. Write expression for the equilibrium constants for the following equilibria:
(a) PCl5 PCl3 + Cl2
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(b) N2 + O2 2NO
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(c) 4NH3 + 5O2 4NO + 6H2O

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(d) N2 + 3H2 2NH3

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2. A mixture of dinitrogen tetroxide, N2O4, and nitrogen dioxide was at equilibrium at 100°C.
The equation for the equilibrium is: N2O4 2NO2
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The equilibrium concentrations were measured to be

[N2O4] = 0.485 mol L-1, [NO2] = 0.320 molL-1
(a) Calculate Kc to this reaction.
(b) In another investigation of the same reaction, equilibrium was again established at 100°C. The
concentration of NO2 was found to be 0.0540 mol L-1.
Calculate:
(i) The equilibrium concentration (in mol L-1) of N2O4.
(ii) The concentration (in mol L-1) of NO2 initially admitted to the vessel, given that there was
no N2O4 initially present.
(iii) Using the answers from (i) and (ii) draw a semi-quantitative graph of concentration
versus time from the initial time until sometime after equilibrium has been reached.
1. Changing the conditions of the reaction can change the extent of a reaction.
30
(a) State le Châtelier’s Principle.

(b) What is the effect on the position of an equilibrium if:
(i) The concentration of the reactants is increased?
(ii) The concentration of the products is decreased?
(c) Soft drinks contain carbon dioxide dissolved in water under pressure, so equilibrium exists
between gas dissolved and gas under pressure above the water.
Explain, in terms of le Châtelier’s principle why an open bottle of soft drink goes flat.
(d) What is the effect on the position of an equilibrium if there is an increase in temperature:
(i) To an exothermic forward reaction.
(ii) To an endothermic backwards reaction.
1. Consider the equilibrium below:
N2(g) + O2(g) 2NO(g)
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(a) What effect would an increase in pressure have on this equilibrium?

(b) Draw a sketch graph to show the changes in concentrations with time, from the time nitrogen
and oxygen were mixed and the initial equilibrium was established, until after extra oxygen had
been added and a new equilibrium had been established.
H2 + I2 2HI ∆ H = +10.9 kJ mol-1
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Predict and explain the effect on the position of the equilibrium of an increase in temperature.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
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Predict and explain the effect on the position of the equilibrium of a decrease in pressure.
N2(g) + O2(g) 2NO(g)
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Predict and explain the effect on the position of the equilibrium of the addition of oxygen at constant
volume and temperature.
4. Fuel-grade ethanol can be produced synthetically by a reaction between ethylene and steam. The
reaction is carried out at 300°C and 60 atmospheres pressure, in the presence of a catalyst, as shown
by the equation below:
C2H4(g) + H2O(g) C2H5OH(g) ∆ H = -46 kJ mol-1
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(a) Explain the effect of the high pressure on the yield of ethanol produced by this reaction.
(b) Methanol, another synthetic fuel, is produced industrially by a reaction between carbon
monoxide and hydrogen, as shown by the equation below:
CO(g) + 2H2(g) CH3OH(g)
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The graph below shows the effect of temperature on the yield of methanol produced by this reaction:
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(i) Write the expression for Kc for the reaction given above.
(ii) State what the graph above shows about the yield of methanol as the temperature is
increased.
(iii) Using your answer to part (ii), and giving reasons, state whether the production of
methanol is endothermic or exothermic.
(iv) T2 is the preferred operating temperature for this industrial process. Suggest why T2 is
chosen in preference to either T1 or T3.
1. Sulfur dioxide is added to white wines as an antioxidant and bactericide. It reacts with water to give
the hydrogensulfite anion, as shown by the equations below:
SO2(aq)+ H2O H2SO3(aq)
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H2SO3(aq) +
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Explain why the amount of sulfur dioxide decreases as the pH of the wine is increased.
2. Exhaust pollutants can be passed through catalytic converters that remove carbon monoxide, nitrogen
dioxide, and hydrocarbons by redox processes.
(a) Nitrogen dioxide may be converted into nitrogen by reduction with carbon monoxide. Write a
balanced equation for this reaction.
(b) Suggest why, in a catalytic converter, the catalyst is supported on a porous material.
(c) Write the equation for the reaction taking place in the catalytic converter which reduces the
nitric oxide concentration
(d) Draw energy profile diagram to show how a catalyst affects the exothermic reaction between
nitrogen dioxide and carbon monoxide.
(e) Nitric oxide (NO) is formed at high temperatures in internal-combustion engines, according to
the following equation:
N2(g) + O2(g) 2NO(g) ∆ H= +181 kJ mol-1
(i) State the effect of the high temperature on the rate of the reaction.
(ii) Write the equilibrium expression for this reaction.
(iii) Calculate the value of Kc for the reaction if an equilibrium mixture contains 0.035 mol L-1
of nitrogen, 8.9 x 10-3 mol L-1 of oxygen, and 1.4 x 10-3 mol L-1 of nitric oxide.
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(iv) Suggest why exhaust gases from internal-combustion engines are not equilibrium
mixtures.
4.6 CHEMICAL INDUSTRY
In any industrial chemical process, it is necessary to Explain the reaction conditions that will
select conditions that will give maximum yield in a maximise yield.
short time. This will often involve compromises
between conditions that produce the maximum rate,
conditions that produce the maximum yield, and costs.
The steps in industrial chemical processes can be Interpret flow charts and use them for such
conveniently displayed in flow charts. purposes as identifying raw materials, chemicals
present at different steps in the process, waste
products, and by-products.
The siting of a chemical plant will depend upon factors Identify the factors that influence the siting of a
such as: access to raw material; waste products; by- chemical plant and apply this knowledge to
products; access to markets for the product; costs of justify a site for an industrial chemical process,
energy, labour, transport, and land; regulatory given relevant information.
restrictions.
Chemical Industry
The chemical industry uses chemical reactions on a large scale to convert raw materials into useful products.
The chemical plant is a complex network of components and structures such as reaction vessels, pipes,
pumps, storage tanks, valves and heat exchangers.
The industry employs a range of personel including chemists, technicians, engineers, sales personnel,
accountants, transport workers etc.
For a particular process, the conditions of the reactions are controlled to produce the best yield of product
possible, at an economic rate of formation of products. Conditions that give the best yield may not be the
fastest reactions, and so there is a need for compromise between the conflicting factors.
Chemical yield
The yield of a product from a chemical reaction is the quantity obtained.
Percentage yield =
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The theoretical yield is the quantity of product predicted by the stoichiometry of the chemical reaction.
Haber Process
The Haber process is the industrial process used throughout the world to produce ammonia.
It involves the reaction of nitrogen and hydrogen at about 400°C and 250 atmospheres in the presence of an
iron catalyst. Under these conditions a 45% yield is obtained.
N2(g) + 3H2(g) 2NH3(g) ∆ H = -46kJ mol-1
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Using le Châtelier’s principles the following conditions would be expected

• High pressure because there are more atoms on the left hand side of the equation.
• Low temperatures because it is an exothermic reaction.
While the pressure use is high, the temperature used is moderate because while a low temperature would
give a higher yield, the reaction would be too slow.
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The graph below shows the effects of different temperatures and pressures on the yield.
Contact Process
Most sulfuric acid is produced via the Contact Process.
The first step involves producing sulfur dioxide by either burning sulfur or a metal sulfide:
S(s) + O2(g) → SO2(g)
2ZnS(s) + 3O2(g) → 2ZnO(s) + SO2(g)
The sulfur dioxide is then mixed with oxygen (in air) and passed over the catalyst, vanadium pentoxide
(V2O5), at 450°C and atmospheric pressure. The sulfur dioxide is oxidised to sulfur trioxide.
2SO2(g) + O2(g) 2SO3(g) ∆ H = -99 kJ mol-1
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The sulfur trioxide is absorbed into concentrated sufuric acid solution, forming oleum, H2S2O7, which is
diluted as required to make sufuric acid. This gives a yield of about 90%.
SO3(g) + H2SO4(l) → H2S2O7(l)
H2S2O7 + H2O(l) → 2H2SO4(l)
The key step is the production of sulfur trioxide. Le Châtelier’s principle would suggest that the highest yield
would be produced using:
• High pressure - because there are less molecules on the right hand side.
• Low temperature – because the reaction is exothermic
The actual conditions used are:
• atmospheric pressure – because higher pressure only increases the yield slightly and doesn’t warrant the
expense.
• relatively high temperature – this is a compromise between the yield of sulfur trioxide (higher at low
temperature) and the rate of formation of sulfur dioxide (faster at high temperature).
The effect of different temperatures on the yield of sulfur trioxide at different temperatures is shown in the
diagram below.
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Flow charts
A flow chart is often used to represent the movement of materials through various components of the plant.
These materials are classified as follows:
Raw materials are the materials converted into useful products.
Waste materials are those for which there are no use or market. If they are produced in large quantities
and/or they are toxic, then their disposal can present problems to the operators of the plant.
By-products are products of the process that are not the main products, but have some value or can be used
within the plant.
A flow chart is usually represented in the form of a line and block diagram.
Siting of a chemical plant

A number of factors need to be considered when selecting the site for a chemical plant:
• Land cost
• Availability of labour
• Access to energy and raw materials
• Availability of cooling water
• Access to markets
• Availability of equipment
• Regulatory restrictions
• Safety
Energy Costs
Energy costs are often a major cost in chemical processes. The can be minimised by:
Reuse of energy - heat from an exothermic reaction can be transferred to other processes
Using lower temperatures – catalysts can often be used for this.
Running processes continuously – this saves on heating up and cooling down costs
EXERCISE 4.6 : The Chemical Industry
1. Sulfuric acid is made by the Contact Process. A flow diagram for the process is shown below:
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An important step in the commercial manufacture of sulfuric acid is the preparation of sulfur
trioxide from the sulfur dioxide which involves the following equilibrium reaction.
2SO2(g) + O2(g) 2SO3(g); ∆ H = -198 kJ
In this industrial process a mixture of air and sulfur dioxide is passed is passed over a finely divided
catalyst bed of V2O5 (vanadium pentoxide) at 450 oC to form sulfur trioxide.
(a) State and explain the effect of an increase in pressure on the equilibrium yield of sulfur trioxide.
(b) (i) State whether this formation of sulfur trioxide is an endothermic process.
(i) Explain why the equilibrium yield of sulfur trioxide increases as the temperature is
lowered.
(i) Explain why the reaction is carried out at 450oC despite the fact that the yield of SO3
increases as the temperature is lowered.
(b) The gas issuing from a reaction vessel in the industrial process is found to have the following
equilibrium composition at 450oC.
[SO2] = 3 x 10-4 molL-1 [O2] = 5 x 10-3 molL-1 [SO3] = 2 x 10-3 molL-1
With reference to the chemical equation:
2SO2(g) + O2(g) 2SO3(g),
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calculate the equilibrium constant for the reaction at 450oC.

(c) Vanadium (V) oxide is a catalyst for the industrial process described in the introduction.
(i) Explain how the catalyst increases the rate of formation of sulfur trioxide.
(ii) What effect, if any, does the presence of the catalyst have upon the value of the
equilibrium constant? Explain your answer.
(iii) Explain why it is preferable to have the catalyst in a finely divided state.
1. A flow diagram for the preparation of ammonia is shown below.
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The following thermochemical equation outlines the industrial production of ammonia.

N2(g) + 3H2(g) 2NH3(g) ∆ H = -92 kJmol-1
(a) (i) What temperature and pressure conditions would you select to maximise the yield of ammonia?
(i) State two other conditions shown in the flow diagram which aid ammonia formation
(a) What is the name given to this industrial process?
(b) Ammonia is readily separated from the equilibrium mixture by rapidly lowering the
temperature. Briefly explain why this technique is so effective.
(c) State two important uses of ammonia.
1. Ammonia is manufactured in large quantities by the Haber process. The chemical equation which
represents the synthesis of ammonia is given below:
N2(g) + 3H2(g) 2NH3(g)
The position of equilibrium is affected by both the temperature and the pressure at which the process
is carried out. The following graph shows how the percentage yield of ammonia at equilibrium varies
with temperature and pressure.
(a) (i) Use the graphical information to deduce whether the forward reaction is exo or endothermic
giving reasons.
(i) Using Le Chatelier’s principle, explain the effect that increasing the pressure has on the
yield of ammonia.
(a) In the chemical plant the conditions commonly used are 80-110 atmospheres pressure and a
temperature of 650-720 K. In view of the above graphical data:
(i) Explain why such a relatively high temperature is used in industry.
(ii) Suggest two reasons why a relatively low pressure is actually used.
(b) Write a balanced equation for the formation of ammonia in the Haber process.
(c) What catalyst is used in the Haber process?
(d) Use the graphs to suggest what conditions produce the highest percentage of ammonia at
equilibrium when the catalyst is used effectively.
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(e) Suggest why the normal working temperature of many Haber process plants is over 350°C.
1. Water gas is a mixture of hydrogen and carbon monoxide. It is made by passing steam over heated
coke.
H2O(g) + C(s) H2(g) + CO(g)
It was used for many years as a commercial fuel.
(a) This reaction was carried out at normal atmospheric pressure. Suggest and explain how
increasing the pressure affects:
(i) The time taken to reach equilibrium.
(ii) The equilibrium yield of water gas.
(b) Write the expression for the equilibrium constant, Kc , for this reaction.
(c) During the conversion of steam into water gas, it was found that 30% of the steam had been
converted. Calculate the value of Kc under these conditions.
1. Explain with examples, the meaning of the following industrial terms:
(a) raw materials
(b) waste products
(c) by-products
(d) plant yield
1. The costs of manufacturing a chemical, the environmental impact, the types of energy required, the
market, the returns and the safety of both workers and residents are some of the factors which must be
considered before a chemical plant can be set up. Argue a case for and against setting up a small
pharmaceutical plant in your area. What is your conclusion?
4.7 METAL PRODUCTION
The likelihood that an uncombined metal will occur Predict whether a metal is likely to occur in
naturally increases with lack of reactivity. nature uncombined or combined with other
elements, given the relative position of the metal
in a table of metal reactivities.
The stages in the production of metals from their ores Identify the stages in the production of a metal
include: concentration of the mineral; conversion of the from its ore, and explain why not all stages are
mineral into a compound suitable for reduction; necessary in the production of some metals.
reduction; refinement of the metal.
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The stages in the electrolytic production of zinc from Describe, with the aid of equations, the
its ore are: concentration of the zinc mineral; production of zinc from its ore.
conversion of the zinc mineral into a form suitable for
reduction; electrolytic reduction.
Electrolysis of molten electrolyte is used in the Explain why the production of aluminium
reduction stage for the production of more reactive requires a molten non-aqueous electrolyte.
metals.
Reduction of the oxide using carbon can be used for Explain why zinc and iron can be obtained by
the production of less active metals. reduction using carbon whereas this is not
possible for aluminium.
The method used in the reduction stage in the Predict the likely method of reduction of a metal
production of a metal is related to the reactivity of the compound to the metal, given the position of the
metal. metal in the activity series of metals.
Energy cost is a factor taken into account in the Explain why reduction using electrolysis of an
production of all metals. aqueous solution is preferable to electrolysis of a
melt.
Metal reactivity
Reactive metals can easily be oxidised (losing electrons) eg
Ca → Ca2+ + 2e
To make metals from their ores (metal compounds), they have to reduced (by accepting electrons). However
metals that are easily oxidised, are hard to reduce back to their metallic state.
Metals can be ranked in order of reactivity according to the ease with which they displace hydrogen from
water or acids or to displace one another from an aqueous solution.
The reactivity series below lists metals in order of decreased reactivity.
Metal Reaction with acid Reaction with water Metal ion

Most K react violently with react vigorously with K+ Most
reactive Ca dilute acids to produce liquid water to produce Ca2+ difficult to
metal salts and metal hydroxide and reduce
Na Na
hydrogen hydrogen
Mg Mg2+
Al A13+
Zn react with dilute acids react readily with steam to Zn2+
Fe to produce metal salts produce metal oxides and Fe3+
Ni and hydrogen hydrogen Ni2+
Sn Sn2+
Pb Pb2+
Cu Cu2+
Hg do not react with dilute Hg2+
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do not react with liquid

Ag acids to produce Ag+ oleObject118
Least water or steam.

Au hydrogen Au3+ Ions easily
reactive
reduced
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The natural occurrence of metals

Metals occur in the earth’s crust as compounds called minerals. Some common economically important
minerals are listed below.
metal mineral forms metal mineral forms

K KCl Ni NiS
Ca CaCO3, CaSO4, CaF2 Sn SnO2
Na NaCl, Na2CO3 Pb PbS, PbSO4
Mg MgCO3, MgSO4 Cu CuFeS2, Cu2S
Al Al2O3 Hg HgS
Zn ZnS, ZnCO3 Ag Ag, Ag2S
Fe Fe2O3, Fe3O4 Au Au
Metals ores
A metallic ore is a mineral that can be mined at a profit
The production of metals from their ores
• The first stage in the process is mining. This can be by open cut or underground mining. This produces
an ore which is a mixture of the metal mineral and waste minerals called gangue.
• After mining it is usual to concentrate the ore. Techniques used to produce the concentrate include:
• Crushing
• Grinding to powder
• Froth flotation or chemical leaching
• The concentrate often needs to be converted to a substance suitable for treatment.
• Reduction of the metal by smelting or electrolysis
• Refining of the metal
Not all these steps need be followed however. eg Some ores are quite concentrated and need no further
treatment.
Zinc
Zinc is mined as a sulfide, sphalerite (ZnS). One place where this is commonly done is Broken Hill.
Crushing and Grinding
The first stage in the treatment of the ore is to crush it (to about 2 cm) and then grind it to particles that are
small enough (200 microns) to be separated by froth flotation.
Froth flotation
The powder is mixed with water, frothing agents (oil or detergent) and collecting agents are added, then air is
blown into the mixture. The zinc sticks to the air bubbles and floats to the top where it can be skimmed off.
Roasting the zinc sulfite
The concentrate is roasted in air to make zinc oxide.
ZnS(s) + 3O2(g) → 2ZnO(s) + SO2(g)
Leaching of the zinc oxide
The sulfur dioxide from the roasting step can be used to make sulfuric acid which can then be used to
convert the zinc oxide to zinc sulfate solution.
ZnO(s) + H2SO4(aq) → ZnSO4(aq) + H2O(l)
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Zinc powder is added to the solution to displace any least reactive metal ion impurities like Ag+, Cd2+ or
Cu2+.
Zn(s) + → + Cd(s)
Electrolysis of the zinc sulfate solution

Zinc is extracted from the final solution by electrolysis. The anode is lead the cathode is aluminium.
Anode reaction: 2H2O(aq) → O2(g) + 2H+ + 4e
+ 2e → Zn(s)
Cathode reaction:
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Aluminium
Aluminium is mined as the mineral bauxite (Al2O3) in northern Australia eg Weipa.
Bauxite contains iron oxide and silica as impurities and these need to be removed before refining.
The bauxite is mixed with hot concentrated sodium hydroxide solution.
The aluminium oxide dissolves (Note: aluminium is amphoteric)
Al2O3(s) + 2 + 2H2O→ 2
The silica also dissolves

SiO2(s) + 2 →2 + 2H2O
The basic iron oxide does not dissolve and is filtered off.
The aluminium oxide is then crystallised out of the solution with seed crystals.
Because aluminium is so reactive, it cannot be extracted by electrolysis of an aqueous solution. Water would
be reduced first.
The final stage in the industrial production of aluminium involves electrolysis of molten alumina, Al2O3. As
the melting point of alumina is very high (2030°C), it is mixed with cryolite (Na3AlF6) and other ionic
compounds to form a mixture of lower melting point (just less than 1000°C). This still consumes a lot of
energy, a lot more than would be used if an aqueous solution could be used.
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Electrolysis is carried out in a carbon-lined steel cathode vessel using carbon anodes. Fresh alumina is added
continuously.
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Anode reaction: Oxide ions are oxidised, but at this temperaure, they burn the carbon electrodes
away and need to be replaced periopdically.
→ O2(g) + 4e
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then C(s) + O2(g) → CO2(g)

Cathode reaction: Aluminium ions are reduced to aluminium metal
+ 3e → Al(l)
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Chemical reduction of metals oxides to metals

Metals below aluminium on the reactivity series can be produced industrially by the reaction of the metal
oxides with carbon. Carbon is a strong enough reducer to take oxygen from the ore.
3C(s) + 2Fe2O3(s) → 4Fe(l) + 3CO2(g)
C(s) + 2ZnO(s) → 2Zn(l) + CO2(g)
Carbon monoxide also reduces metal oxides.
3CO(g) + Fe2O3(s) → 2Fe(l) + 3CO2(g)
CO(g) + ZnO(s) → Zn(l) + CO2(g)
Summary of reduction methods
Metal Most common method of reduction used to Metal ion

obtain the metal
Most K KCl Most
reactive Ca CaCl2 difficult to
Electrolysis of molten chloride or molten reduce
Na NaCl
oxide
Mg MgCl2
Al Al2O3
Zn Reduction of metal oxide by carbon or carbon ZnO
monoxide.
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Fe Fe2O3
Ni NiO
(note about 50% of zinc is produced this way)
Sn SnO2
Pb PbO
Cu Roasting metal sulfide in oxygen Cu2S
Hg HgS + O2 → Hg + SO2 HgS
Ag
Au
Native metals – no reduction required

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Ions easily
Least
reduced
reactive
EXERCISE 4.7 : Metal Production
1. The reactivity of metals can be determined by the reaction of metals with water, dilute acids and by
displacement reactions. Write balanced annotated equations for the following reactions.
(a) Sodium and water
(b) Calcium and hydrochloric acid
(c) Zinc and steam
(d) Iron and copper sulfate
(e) Copper and silver nitrate Na
2. The metals opposite are arranged in a metal reactivity series. Ca
(a) List the metal(s) likely to occur in nature in the uncombined state. Al
(b) Explain the difference between the terms ore and mineral. Zn
(c) Complete a table for the metals (except Hg) listed in activity series with the following Pb
headings, Metal, Metal Ion, Method of Production of Metal
Hg
(d) Which metal ion would require the most energy to be reduced to the metal?
(e) In chemical reactions what do metals act as?
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3. This table shows the stages involved in production of a metal from its ore.
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(a) Explain why not all stages are necessary in the production of some metals.
(b) Draw a similar diagram to show the production of zinc from its ore. Include equations for the
chemical reactions.
1. Copper occurs naturally as a mineral, malachite, CuCO3.Cu(OH)2, iron as haematite, Fe2O3 and
aluminium as bauxite, Al2O3.
(a) What is the oxidation state of the metal in each of the above minerals?
(b) How is iron extracted from its mineral haematite?
(c) To extract aluminium from purified bauxite a molten electrolyte is required. Explain why.
1. Magnesium is a reactive metal.
(a) (i) State two metals which can be displaced from solutions of their salts by Mg.
State one metal which cannot be displaced from solution of its salt by Mg.
Magnesium is obtained industrially by electrolysing molten magnesium chloride. Magnesium is
formed at the cathode and chlorine at the anode.
(b) (i) Write the half equation for the formation of chlorine and explain why this is classified as
oxidation.
(i) Write the half equation for the formation of magnesium at the cathode.
1. By observing the reactions of metals with water and dilute sulfuric acid it is possible to put metals in
order of their reactivity.
A, B, C and D represent four metals.
Metal Reaction with water Reaction with dilute sulfuric acid
A No reaction Reacts slowly at first
B No reaction No reaction
C Little or no reaction Reacts quickly
D Vigorous reaction Violent – dangerous reaction
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(a) Put the metals A, B, C and D in decreasing order of their reactivity.

(b) The metals used were copper, magnesium, sodium and zinc. Identify A, B, C and D.
1. (a) Aluminium is extracted by the electrolysis of a 5% solution of aluminium oxide in molten cryolite,
Na2AlF6. The temperature of the electrolyte is maintained at around 1200 K.
(i) Why is pure molten aluminium oxide not used as the electrolyte?
(ii) Write an equation for the reaction that occurs at the anode. Explain why, if carbon
anodes are used, they have to be replaced regularly.
(iii) Suggest two reasons why the extraction of aluminium requires a lot of energy.
(iv) Suggest two different properties of aluminium that have resulted in its economic
importance.
(b) Zinc is a metal which can be reduced using a molten electrolyte, or an aqueous electrolyte or
by using carbon.
(i) Arrange these reduction processes in increasing order of energy requirement.
(ii) Why then is electrolysis of a solution containing Zn2+(aq) the preferred reduction process.
1. Electrodes were placed in solid lead bromide, PbBr2. The bulb in the circuit did not light up. The lead
bromide was heated until molten. The bulb then lit up. A red-brown vapour was seen at the anode and
silver coloured drops of lead formed at the cathode.
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(a) Molten lead bromide is an electrolyte. Explain the term electrolyte.

(b) Give the name of the red-brown vapour.
(c) (i) Write a balanced ionic equation to show the formation of lead at the cathode.
(i) Name and explain the type of reaction that occurs in i).
(a) Lead is extracted from its ores by reduction using coke. Why not use electrolysis?
ASSIGNMENT 4.1 ANSWERS : MEASURING ENERGY CHANGES
1. (a) Exothermic – gives out heat (surroundings get hotter)
(a) Endothermic – takes in heat (surroundings get colder)
1. (a) C2H5OH + 3O2 → 2CO2 + 3H2O (exothermic)
(a) 6CO2 + 6H2O → C6H12O6 + 6O2 (endothermic – absorbs light energy)
(a) C6H12O6 + 6O2 → 6CO2 + 6H2O (exothermic)
1. (a) Exothermic
(a) The sulfuric acid sinks and mixes with the water dispersing the heat. If water is added to the acid it sits on
top, generating heating and probably boiling spitting out acid..
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(a)
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1. (a) NaNO3(s) + aq → +
(a) Dissociation
(a) Heat is absorbed from the surroundings to break the bond in the sodium nitrate crystals.
(a)
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1. Heat of reaction is the heat given of by a particular reaction, molar enthalpy is the heat given off (or taken
in) per mol at constant pressure.
2.
m(ethanol) = 2.37 g
M(ethanol) = 2x12 + 6x1+16 = 46 g mol-1
n(ethanol) = 0.05152 mol
m(water) = 200 g (≈ 200 mL)
∆ T = 39.6-18.8 = 20.8°C oleObject138
3. (a) A foam cup is a good insulator.

(a) To thoroughly mix the chemicals and the heat
(a) To prevent inaccuracy due to heat losses to the surroundings
(b) Assumptions
There are no heat losses to or from the surroundings
The specific heat is 4.2
The solution behaves the same as water (c =4.2)
the density of the solution is 1g mL-1
1. (a) Much better insulated.
(a) Burn a known amount of a substance of known enthalpy of combustion, measure the temperature increase
and calculate the heat evolved and work out the % error.
1. (a) Molar enthalpy of combustion of a substance is the quantity of heat energy released when 1.00 mole of
pure element or compound is burnt completely in oxygen under constant pressure.
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(a) Molar enthalpy of solution of a substance is the quantity of heat energy released or absorbed when 1.00
mole of the substance dissolves in sufficient solvent so that further dilution causes no further release or
absorption of heat energy.
(a) Molar enthalpy of neutralisation is the quantity of heat energy released when 1.00 mole of hydrogen ions is
transferred from an acid to a base in an acid-base reaction occurring in aqueous solution.
1. (a)
m(glucose) = 1 g
M(glucose) = 6x12 + 12x1+6x16 = 180 g mol-1
n(glucose) = mol
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(a) Fermentation is likely to be to exothermic. Fermentation of 1 mol of glucose produces 2 mol of ethanol
which gives off (2 x 1364) 2728 kJ of energy, therefore the fermentation must make up the difference ie
(2803-2728) 75 kJ (Hess’s Law or the Law of Conservation of energy)
1. (a) CH4(g) + 2O2(g) → CO2(g) + 2H2O(g); ∆ H = -890 kJ mol-1
(a)
m(methane) = 25 g
M(methane) = 12 + 4 x 1= 16 g mol-1
n(methane) = mol
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(a)
∆ T = 100-25 = 75°C
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(b) Not all the heat will heat the water. Some heat will escape the water.
1. (a) 100 mL of water is added to a foam cup and the temperature is measured. The ammonium chloride is
added, stirred in, with a cardboard lid and the lowest temperature reached is measured.
(a)
m(NH4Cl) = 2.50 g
M(NH4Cl) = 14 + 4x1+35.5 = 53.5 g mol-1
n(NH4Cl) = mol
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m(water) = 100 g (≈ 100 mL)

∆ T = -1.7°C
(a) This assumes that the specific heat of the solution is the same as that of water and its density is the same as
that of water.
1. (a) Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g) ∆ H = -355 kJ
m(Mg) = 1.0 g
M(Mg) = 24 g mol-1
n(Mg) = mol
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(a) Mole ratio 1:2, therefore 2/24 mole of water. Mass = 2/24 x 18 = 1.5 g.
(a)
m(H2O) = 50 g
H = 14.79 kJ = 14790 J
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1. (a) AlCl3(s) + aq → + 3 ; ∆H(solution) = -321 kJ.mol-1
(a)
m(H2O) = 200 g (≈ 200 mL)
Ti = 20°C
m(AlCl3) = 2.67 g
M(AlCl3) = 27 + 3 x 35.5 = 133.5
n(AlCl3) = = 0.0200 mol
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Tf = 20 + 7.68 = 27.7°C
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ASSIGNMENT 4.2 ANSWERS : FUELS

1. (a) A fossil fuel is a carbon or hydrocarbon based fuel that is derived from the fossilized remain of living
things.
(a) Coal is made from the fossilized remains of plants formed in swamps and oil and gas from preserved marine
organisms.
(a) (i) Coal is abundant, cheap
(i) Oil is abundant, easily mined and transported because it is a liquid, many uses as fuel, raw material for
plastics
(i) Gas is easily extracted, purified and treated; burns cleanly, high energy output
(b) (i) Coal burns giving off carbon dioxide (Greenhouse gas), impurities of sulfur produce sulfur dioxide (acid
rain) when coal is burnt, high temperature combustion can lead to the formation of nitrogen oxides (acid
rain, photochemical smog, hole in the ozone layer), releases particular matter which cause respiratory
problems.
(i) Oil produces carbon dioxide, sulfur dioxide and nitrogen oxides when burning, produces soot and
unburnt hydrocarbons contribute to photochemical smog.
(i) Gas produces carbon dioxide, nitrogen oxides.
1. 2C4H10 + 13O2 → 8CO2 + 10H2O
2. (a) (i) Blue
(i) Carbon dioxide and water because complete combustion is occurring.
(i) CH4 + 2O2 → CO2 + 2H2O
(a) (i) yellow
(i) water, carbon monoxide and/or carbon
(i) 2CH4 + 3O2 → 2CO + 4H2O OR
CH4 + O2 → C + 2H2O
1. Incomplete combustion of a fossil fuel produces:
Carbon monoxide which displaces oxygen from haemoglobin in the blood. Since haemoglobin is the main
mechanism for the transport of oxygen in the blood, the absorption of carbon monoxide deprives the body of
oxygen producing symptoms varying from impairment of judgement and visual perception (at 10 ppm in air)
to death (at >750 ppm).
Soot is a microcrystalline form of carbon produced by incomplete combustion. It produces visual pollution
48
(smoke and soot), blocks air and fuel inlets in burners and deposits on leaves causing impaired
photosynthesis. Soot in the lungs can lead to respiratory problems like bronchitis, asthma and emphysema.
2.
Fuel ∆ H(combustion) Molecula Molar Density(g/L) Heat/gram Heat/litre

(kJ mol-1) r mass
formula
Methane -890 CH4 16 422 56 23500
Ethane -1557 C2H6 30 546 52 28300
Propane -2220 C3H8 44 582 50 29400
Butane -2875 C4H10 58 601 50 29800
Octane -5512 C8H18 114 685 48 33120
ASSIGNMENT 4.3 : ELECTROCHEMISTRY ANSWERS
1. (a) Galvanic
(a) Chemical →Electrical
(a) V - To detect the flow of electrons and the direction of flow.
A – salt (or electrolyte) bridge to complete the circuit.
B – electrolyte to conduct charge and may react at the electrode.
C – Electrode to make electrical contact with the solution and may react.
(b) Zinc
(c) Zn → Zn2+ + 2e-
Fe2+ + 2e- → Fe
(d) Zn + Fe2+ → Zn2+ + Fe
(e) Zinc is the anode because it is oxidized.
(f) Fe is positive, because electrons are flowing towards it.
(g) K+ will flow towards Fe half cell to replace Fe2+ ions or to complete the circuit by flowing in the opposite
direction to negative charges.
(h) The zinc electrode loses weight, because Zn is converted to Zn ions in solution.
(i) No reaction
1. (a)
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(a)
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1. For the following combinations of metal half-cells, predict the direction of electron flow and identify the
anode and cathode.
metal half-cell combinations direction of electron flow anode cathode

Zn| Zn2+| | Fe2+| Fe Zn→Fe Zn Fe
Ag| Ag+| | Pb2+| Pb Pb→Ag Pb Ag
Fe| Fe2+| | Cu2+| Cu Fe→Cu Fe Cu
2. Voltaic (or galvanic) cells can be used to make electricity.
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1. (a) A fuel cell is a voltaic cell that is powered by a continuous supply of fuel and oxygen. Hydrogen and
oxygen can be used.
(a) Inert materials like graphite or platinium.
(a) Advantages of fuel cells.
• they continuously produce an electric current so long as fuel and oxidant is continuously supplied;
• they have high operating efficiency (between 70 and 80%);
• they offer a better mass to power output ratio than conventional galvanic cells;
• they use readily available fuels and oxidants;
• they do not produce pollutant gases such as sulfur dioxide and the oxides of nitrogen;
• the electrodes and electrolyte are not consumed during operation;
• electrode reaction products are removed as they are formed and do not remain inside the cell;
• they require minimal maintenance;
• they are silent during operation as there are no moving parts;
• in different versions they can be used for small to large scale applications and for stationary or mobile
(particularly transport) power generation.
(a) Disadvantages
• impurities in the fuel or oxidant can 'poison' the electrode catalysts and/or contaminate the electrolyte.
For example, any carbon dioxide present in the oxidant can react with a potassium hydroxide electrolyte
forming potassium carbonate solid that can clog the porous electrodes. This restricts the use of air as an
oxidant.
• high purity fuels and oxidants are costly;
• medium to high temperatures are needed for the cells to function most effectively;
• metal electrode catalysts such as platinum and palladium are very costly;
• some of the electrolytes are very corrosive.
1. (a) Lead
(a) Pb + H SO → PbSO + 2H+ + 2e-
2 4 4
(a) Lead dioxide

(b) PbO2 + H2SO4 + 2e- → 2H+ → PbSO4 + 2H2O
(c) Pb + PbO2 + 2H2SO4 → 2PbSO4 + 2H2O
(d) The reaction consumes sulfuric acid and this lowers the density of the electrolyte.
(e) The above reactions are reversed.
1. (a) Uses an electric current to get a chemical reaction to occur.
(a) Cathodic protection, making chlorine and other nonmetals, electroplating
(a) (i) cathode
(i) Zn2+ + 2e- → Zn
(i) Too stable
(ii) 2H2O → O2 + 4H+ + 4e-
1. (a) They are too reactive to be easily reduced. Water is reduced first.
(a) A molten sodium or potassium salt.
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ASSIGNMENT 4.4 : REACTION RATES ANSWERS

1. (a)
Decomposition Of hydrogen peroxide vs time
2.5
2
[H2O2] (mol L-1)
1.5 B
1
Higher A
temperature
0.5 &
Catalyst
0
0 10 20 30 40 50 60
Time (min)
(a) Dependent variable - [H2O2], independent variable - time

(a) (i) At 5 minutes
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(i) At 25 minutes
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(a)
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(b) see (a) above

(c) In the first 5 minutes there was a higher concentration and therefore more particles and a higher probability
of a reaction.
1.
Factor Effect on rate (v) Explanation
Concentration v α c Higher concentration→more particles per volume→higher
(c) probability of a successful collision.
Temperature v α T Higher temperature→particles moving faster→more collisions
(T) also more likely to have enough (activation) energy to start a
reaction.
Surface area v α A More surface area→more atoms exposed to reaction
(A)
Light (I) v α I (photochemical More light→ provides energy to atoms that can use light to
reactions) provide activation energy
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Factor Effect on rate (v) Explanation

Pressure (P) v α P (gases only) More pressure forces atoms closer together increasing the
number of collisions
Time (t) v α The longer the reaction has been going, the more particles have
been used up, so the less chance there is of a collision between
particles and so the reaction is slower.
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Catalysts Catalysts provide alternative pathways usually of lower energy

to speed up reactions, but they can slow down reactions too
(inhibitors).
2.
Energy profile diagram for an exothermic reaction Energy profile diagram for an endothermic reaction
ASSIGNMENT 4.5 ANSWERS : EQUILIBRIUM
1. (a)
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(a)
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1.
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2.
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1. (a) N2O4 2NO2 : [N2O4] = 0.485 mol L-1, [NO2] = 0.320 molL-1
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(a) (i) [NO2] = 0.0540 mol L-1
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(i)
In 1 litre N2O4 2NO2
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At equilibrium (mol) 0.0138 0.0540

In attaining eq (mol)
m
+0.0138 1:2 ratio→ -0.0276
Initially (mol) 0 0.0816
Initial concentration of NO2 = 0.0816 mol L -1
(i)
1. (a) le Châtelier’s Principle - If a dynamic equilibrium is disturbed by changing the conditions, the position
of equilibrium moves to counteract the change.
(a) (i) If the concentration of the reactants is increased the equilibrium will move to the right to reduce the
concentration of the reactants, ie increase the concentration of products. Kc doesn’t change.
(i) If the concentration of the products is decreased the equilibrium will favour the right to increase the
concentration of the products. Kc doesn’t change.
(a) Once the bottle is opened, the concentration of carbon dioxide in the gas will decrease and the equilibrium
will move to replace this. But since the gas continues to escape because it is not a closed system, it will
eventually go flat.
(a) (i) An increase in temperature favours the reaction that removes heat and in the case of an exothermic
forward reaction this will the reverse reaction. ie equilibrium moves to the left.
(i) To an endothermic backwards reaction - same as above.
1. N2(g) + O2(g) 2NO(g)
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(a) Pressure has no effect on this equilibrium, because there are equal numbers of molecules of gas on each
side.
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(b)
1. H2 + I2 2HI : ∆ H = +10.9 kJ mol-1

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An increase in temperature would cause the equilibrium to shift to the side which causes a decrease in
temperature. This is an endothermic reaction, therefore the forward reaction is favoured.
2. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
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Decreasing the pressure would favour the side that increases the pressure. Since the forward reaction has slightly
more molecules it is the slightly favoured reaction. Since the increase is from 9 to 10 molecules, the change would
be minor.
3. N2(g) + O2(g) 2NO(g)
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The addition of oxygen at constant volume, means an increase in concentration, therefore the reaction moves to
the right to minimise this change. At constant temperature, there is no change in the equilibrium constant.
4. C2H4(g) + H2O(g) C2H5OH(g) : ∆ H = -46 kJ mol-1
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(a) High pressure favours the side with the least number of gas molecules hence high pressure favours the
production of ethanol.
(b) CO(g) + 2H2(g) CH3OH(g)
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(i)
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(ii) The yield increases with temperature.
54
(iii) This is an endothermic reaction, because the yield increases with temperature. Increased temperature
favours the reaction that absorbs heat (endothermic), ie the forward reaction.
(iv) T2 gives optimal output, giving the ideal compromise between yield and time taken to reach
equilibrium.
1. SO2(aq)+ H2O H2SO3(aq) ⇒ H2SO3(aq) +
As the pH increases, the H ions are removed, pulling the second reaction to the right. This then pulls the first
+
reaction to the right, hence decreasing the amount of sulfur dioxide.

2. Exhaust pollutants can be passed through catalytic converters that remove carbon monoxide, nitrogen
dioxide, and hydrocarbons by redox processes.
(a) 2NO2 + 4CO → N2 + 4CO2
(b) The catalyst is porous to increase the surface area and hence increase the reaction rate.
(c) 2NO + 2CO → N2 + 2CO2
(d)
(e) N2(g) + O2(g) 2NO(g) ∆ H= +181 kJ mol-1

(i) High temperature favours the reaction that removes heat (endothermic), which favours the formation of
nitric oxide.
(ii)
(iii) .
(iv) Exhaust gases are not an equilibrium mixture because it is an open system, gases can escape.
ASSIGNMENT 4.6 : THE CHEMICAL INDUSTRY ANSWERS
1. (a) Increasing the pressure favours the side the producing the least pressure, which is the side with the least
number of molecules, ie SO3. Thus increasing the pressure increases the yield of SO3.
(a) (i) This is an exothermic reaction.
(i) A decrease in temperature favours the side that increases the temperature, ie the exothermic reaction.
1. The reaction is carried out at a high temperature despite the lower yield because the higher
temperature allows the equilibrium to be reached faster. The reaction can be repeated many
times before the reaction at a lower temperature (and higher yield) reaches equilibrium.
2.
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3. (i) A catalyst increases the rate of a reaction by providing an alternative pathway which lowers the
activation energy for the reaction.
(i) A catalyst doesn’t affect the equilibrium constant. It increases the rate of the forward and backward
reactions so equilibrium is reached faster.
1. A finely divided catalyst works faster by increasing the surface area, which also increases
the rate of the reaction
1. (a) (i) High pressure and moderately high temperatures would maximise the yield
(i) The use of a catalyst and recycling unused gases increases the yield.
1. Haber process
2. Condensing the ammonia as it forms removes ammonia as it forms which favours the right hand side
of the equation.
3. Ammonia is used to make fertilisers and nitric acid.
1. (a) (i) The reaction is exothermic, because low temperatures increase the yield. When the temperature increases,
the equilibrium favours the reaction that removes heat, ie endothermic. Thus the given reaction must be
exothermic..
(i) Increasing pressure, favours the side that reduces the pressure. This is the side with the least number of
gaseous particles. Thus increasing the pressure force the equilibrium to the right.
1. (i) The high temperature may give a smaller yield, but equilibrium is reached faster and the cycle can
be repeated many times before equilibrium is reached at a lower temperature.
(i) A lower pressure is a compromise between yield and the expense and danger associated with high
pressure.
1. H2 + 3N2 2NH3
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2. Fe
3. Maximum yield occurs at 400 atm. and 290°C
4. A higher temperature makes the reactions faster and so equilibrium can be reached faster.
1. (a) (i) Increasing the pressure has no effect on the time taken to reach equilibrium.
(i) Increasing the pressure favours the side with the least number of gaseous particles which is the left
hand side. Therefore increasing the pressure reduces the yield.
1.
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2.
Assume 1 mole initially H2O(g) C(s) oleObject185
H2(g) CO(g)
Initially 1 1 0 0
Attaining eqm -0.3 -0.3 → 0.3 0.3
At eqm 0.7 0.7 0.3 0.3
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1. (a) Raw materials – chemicals put into the plant.

(a) Waste products – chemicals produced by reaction that can’t be used for anything else.
1. By-products – chemicals produced that can be used for something else.
2. Plant Yield - =
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1.
ADVANTAGES DISADVANTAGES
Available labour Expensive land
Available markets Environmental problems
Access to equipment Dangerous
No abundant cheap electricity
No good heavy transport system
No abundant available water
Unlikely to get council approval
On Balance – it is unlikely
ASSIGNMENT 4.7 : METAL PRODUCTION ANSWERS
1. (a) 2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
(a) Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g)
1. Zn(s) + 2H2O(g) → Zn(OH)2(aq) + H2(g)
2. Fe(s) + CuSO4(aq) → FeSO4(aq) + Cu(s)
3. Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)
1. (a) Pb
(a) A mineral in a compound found in rocks.
An ore is a mineral deposit that can be mined at a profit
(b)
Metal Metal ion Method of production of metal

Na Na+ Electolysis of molten salt
Ca Ca2+ Electolysis of molten salt
Al Al 3+
Electolysis of molten salt
Zn Zn2+ Electrolysis of an aqueous solution or reduction by carbon monoxide or carbon
(c) Na or Ca (calcium is slightly less reactive, but needs two electrons)
(d) Reducers
1. (a) Depend on the technique used. Smelting needs all steps, but electrolysis doesn’t.
(a)
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1. (a) Cu (+2), Fe (+3), Al (+3)

(a) Reduction by carbon monoxide in a blast furnace.
1. Aluminium is too stable to be reduced by aqueous electrolysis or in a blast furnace.
1. (a) (i) Anything less reactive than magnesium. Zinc, iron, copper, silver etc.
(i) Anything more reactive than magnesium eg sodium, potassium or calcium.
1. (i) 2Cl- → Cl2 + 2e (oxidation loss of electrons OR increase in oxidation Number -1 → 0)
(i) Mg2+ + 2e →Mg
1. (a) (i) D→C→A→B
(i) A (zinc), B (copper), C (magnesium), D (sodium)
1. (a) (i) Very high melting point, uses too much energy.
(i) 2O2- → O2 + 4e ⇒ C + O2 → CO2 The graphite electrodes burn away. And have to be replaced.
1. The high temperature of the reaction and the high demand for electrical energy for
electrolysis cause large energy demands..
2. Aluminium is a good structural material. Strong and light. Resistant to corrosion.
2. (i) Molten electrolyte > aqueous electrolyte > carbon
(i) Electrolysis of a aqueous electrolyte is preferred because of the high purity of the product.
1. (a) An electrolyte is liquid that conducts electricity.
(a) Bromine
1. (i) Pb2+ + 2e → Pb
(i) Reduction because it involves accepting electrons. And a decrease in oxidation number.
1. It is cheaper in a blast furnace. No electricity requirement. Lead not very soluble.
58

Senior Chem - Controlling Reactions

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Senior Chem - Controlling Reactions

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USING AND CONTROLLING REACTIONS

TOPIC 4: USING AND CONTROLLING REACTIONS

4.1 MEASURING ENERGY CHANGES

Reactions that produce heat include:

where is n the number of moles of the reactant.

Assume that the pack contains 1.0 g of powdered magnesium.

Key Ideas Intended Student Learning

Energy per litre = = 31668 kJ L-1

(d) What are the disadvantages of using

Galvanic cells are commonly used as portable sources Identify the:

SO2 + 2H2O → + 4H+ + 2

Dichromate ion (orange) → Chromium (III) ion

Bromine (orange) Br2(aq) → Bromide ion

Iodine (yellow/brown) I2(aq) → Iodide ion

Reducer Oxidised form

Hydrogen sulfide H2S(g) → S(s) Sulfur

Bromide → Br2(aq) Bromine

Iodide ion → I2(aq) Iodine (yellow/brown)

Iron (II) ion → Iron (III) ion

Writing redox equations for reactions in neutral or acidic solutions

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• check that all atoms and charges balance

Reducer and Oxidiser and

Similarities between Differences between conventional cells and fuel cells

• At the cathode (+) : PbO2(s) + + 4H+ + 2e- → PbSO4(s) + 2e-

• At the cathode (+) : 2Ni(OH)3(s) + 2e- → 2Ni(OH)2(s) + 2

During recharge these reactions are reversed.

During the operation of an electrolytic cell:

Production of highly reactive metals

A Comparison of galvanic and electrolytic cells

Type Electrode Type of reaction Charge on electrode

(a) Is it a galvanic or electrolytic cell?

(a) What is the anode made of?

Conditions Affecting Reaction Rates

Collision theory of chemical reactions

Factor Effect on rate Explanation Example

EXERCISE 4.4 : REACTION RATES

The equilibrium moves to the left.

External change Internal change

Changes to the temperature of a system at equilibrium

Note: The quoted ∆ H value always refers to the forward reaction.

(c) 4NH3 + 5O2 4NO + 6H2O

(d) N2 + 3H2 2NH3

The equilibrium concentrations were measured to be

(a) State le Châtelier’s Principle.

(a) What effect would an increase in pressure have on this equilibrium?

Using le Châtelier’s principles the following conditions would be expected

Siting of a chemical plant

calculate the equilibrium constant for the reaction at 450oC.

The following thermochemical equation outlines the industrial production of ammonia.

Key Ideas Intended Student Learning

Metal Reaction with acid Reaction with water Metal ion

do not react with liquid

Least water or steam.

The natural occurrence of metals

metal mineral forms metal mineral forms

Electrolysis of the zinc sulfate solution

The silica also dissolves

then C(s) + O2(g) → CO2(g)

Chemical reduction of metals oxides to metals

Metal Most common method of reduction used to Metal ion

Native metals – no reduction required

(a) Put the metals A, B, C and D in decreasing order of their reactivity.