Redox Reactions and Electrolysis

Part VII Redox Reactions, Chemical Cells & Electrolysis (Part 2)/P.
Part VII Redox reactions, Chemial Cells and Electrolysis
IV. Electrolysis
We have discussed the production of electric current from chemical reactions by electrochemical cells.
Equally important, however, is the opposite process, electrolysis, the use of an electric current to
bring about chemical changes.
Electrolysis means decomposition by electricity. It is the process in which a redox reaction is forced to
take place by passing a direct electric current through an electrolyte.
A. The General Setup For Electrolysis
a. Direct current (d.c.) power supply / cell / battery

It provides current for electrolysis.
b. Switch
When the switch is closed, the circuit is complete.
c. Ammeter
It measures the quantity of electricity passing through the circuit.
d. Variable resistor / rheostat

It is used for varying the resistance and regulating the current.
e. Voltameter
A voltameter is a container in which electrolysis takes place.
Part VII Redox Reactions, Chemical Cells & Electrolysis (Part 2)/P.2
f. Electrolyte
It is a substance which, when or dissolved in water, conducts an electric current and is decomposed by
it.
g. Electrodes
An electrode is a pole where the electric currents enters or leaves the electrolyte.
Anode: The electrode where oxidation takes place. It is the electrode connected to the positive
terminal of d.c. supply.
Anions (negative ions) are attracted towards anode during electrolysis.
Cathode: The electrode where reduction takes place. It is the electrode connected to the negative
terminal of d.c. supply.
Cations (positive ions) are attracted towards cathode during electrolysis.
B. Comparing Electrolytic Cells and Electrochemical Cells

Electrolysis is carried out in an electrolytic cell.
Electrolytic cell Electrochemical cell

Function bring out chemical reactions by generating electricity by chemical
electricity reactions
Reaction involved redox reaction is forced to occur by spontaneous redox reaction takes
supplied current place
Polarity of anode positive (oxidation) negative (oxidation)
electrodes cathode negative (reduction) positive (reduction)
In both chemical cells and electrolytic cells, oxidation always occurs at the anode and reduction
always occurs at the cathode.
You may remember "reduction always takes places at the cathode" by red cat.
C. Explanation of Electrolysis by Ionic Theory
To explain electrolysis by ionic theory, let us consider the electrolysis of a molten electrolyte, lead(II)
bromide, PbBr2(l).
Note: Lead(II) bromide, with a relatively low melting point of 370oC, is frequently used to
demonstrate electrolysis of molten electrolyte.
a. Conduction of electric current by electrolytes

In metallic conductors/graphite, an electric current is conducted by delocalized electrons in the metals,
i.e. the connecting wire.
In electrolytes, electric current is conducted by migration of mobile ions.

b. Decomposition of electrolytes by electric current
Molten lead(II) bromide consisted of mobile cations [lead(II) ions, Pb2+(l)] and mobile anions
[bromide ions, Br-(l)].
During electrolysis, cations (Pb2+) are attracted to the negative electrode (cathode) and anions (Br-)
are attracted to the positive electrode (anode).
At cathode, cations (Pb2+) are reduced by gaining electrons and becomes discharged.
Pb2+(l) + 2e- → Pb(l) silvery [Reduction]

(from cathode)
At anode, anions (Br-) are oxidized by losing their excess electrons. (If the anode is not inert, there may
be some other possible reactions, as discuss later).
2Br-(l) → Br2(g) brown gas + 2e- [Oxidation]
(to anode)
*Question: Why does not the below reaction occur?

Br-(l) → Br(g) + e-
The overall reaction is thus,

Pb2+(l) + 2Br-(l) → Pb(l) + Br2(g) [Redox reaction]
Note:
a. During electrolysis, the number of electrons gained by cations and lost by anions must be equal.
b. Discharge of ions take place only on the surface of electrodes.
c. In electrolysis, a d.c. (direct current) power supply must be used. An a.c. (alternating current) power
supply should not be used, otherwise there would be no fixed cathode and anode.
Classwork
Predict the products formed at each graphite electrode when a d.c. is passed into
(i) molten magnesium chloride, (ii) solid magnesium chloride
D. Predicting Preferential Discharge of Ions.
1. Preferential Discharge of ions in Aqueous Electrolytes
There are only one kind of cation and anion in molten electrolyte e.g. lead(II) bromide, it has only kind
of Pb2+ as cations and only kind of Br- as anions. The discharges of the ions are simple.
But in aqueous electrolytes, since water is present, the kinds of cations and anions present may not be
so simple and the prediction of products in electrolysis of aqueous electrolytes is not so straightforward,
some kinds of ions are preferentially discharged, ie. one kind of cation is discharged before the
other kinds
Basic concepts - related to aqueous electrolytes

a. Ionization of water
Ionization refers to the formation of ions from molecules. Water ionizes slightly to give hydrogen
ions H+(aq) and hydroxide ions OH-(aq).
H2O(l) H+(aq) + OH-(aq)
∴ In an aqueous solution of any electrolyte, H+ and OH- ions exist, besides those from electrolyte.
For example, in dilute solution of sodium chloride NaCl(aq), the ions present in the solution include:
Na+(aq), Cl-(aq), H+(aq) and OH-(aq).
b. Ionization of acids in water

Acids are covalent compounds. However, acid molecules ionize when dissolved in water.
ionization
e.g. HCl(g) + → H+(aq) + Cl-(aq)
water  
molecules of mobile ions
hydrogen chloride gas
ionization
H2SO4(l) + → 2H+(aq) + SO42-(aq)
water  
molecules of mobile ions
sulphuric acid
c. Indicators showing whether a solution is acidic or alkaline

Pure water contains an equal number of hydrogen ions H+(aq) and hydroxide ions OH-(aq). Pure water
is described as neutral.
Solutions [e.g. hydrochloric acid HCl(aq)] that contain more H+(aq) than OH-(aq) are describes as
acidic.
Solutions [e.g. sodium hydroxide solution NaOH(aq)] that contain more OH-(aq) than H+(aq) are
described as alkaline.
Indicators can be used to show whether a solution is acidic or alkaline. An indicator gives different
colours in acidic and alkaline solution. For example, litmus solution gives a red colour in acidic
solutions and a blue colour in alkaline solutions.
d. Concentration of solution
Concentration of a solution is usually expressed in molar concentration (or molarity), unit is M.
Thus 3M NaCl(aq) solution is more concentrated than 0.1M NaCl(aq) solution.
3M NaCl(aq), 5M NaOH(aq) and 12M H2SO4(aq) are regarded as concentrated solutions; in

comparison, 0.1M NaCl(aq), 0.5M NaOH(aq) and 2M H2SO4(aq) are dilute solutions.
Classwork
a. Give the formulae of ions present in the electrolyte below:
(i) molten sodium chloride
(ii) aqueous solution of copper(II) sulphate
b. Is dilute nitric acid acidic, neutral or alkaline?
c. Which is more concentrated, 0.1 M H2SO4 or 1M H2SO4?
2. Electrolytes of Aqueous Sodium Chloride Solution

In aqueous solution of sodium chloride, there are 4 kinds of ions:
Cations Anions
From sodium chloride NaCl: Na+(aq) Cl-(aq)
From water: H+(aq) OH-(aq)
Na+(aq) and H+(aq) both move towards the cathode. Usually, one kind of cation is discharged before
the other kinds, i.e. preferentially discharged.
Hence, which of the cations is preferentially discharged, Na+(aq) or H+(aq)?
Cl-(aq) and OH-(aq) both move towards the anode. Which of the anions is preferentially discharged,
Cl-(aq) or OH-(aq)?
We have to consider the factors affecting preferential discharge of ions.

3. Factors Affecting Preferential Discharge of Ions
a. Position of ion in the electrochemical series E.C.S.
Cations lower in the E.C.S. are more readily discharged.

Anions higher in the E.C.S. are more readily discharged.
Question:
In the electrolysis of dilute sodium chloride solution,
(i) which ion, Na+(aq) or H+(aq), is preferentially discharged at the cathode?
(ii) which ion, Cl-(aq) or OH-(aq), is preferentially discharged at the anode?
Note: NO3-(aq) and SO42-(aq) ions are so weak reducing agents that they are never discharged in
aqueous solution, even though their concentration are high.
b. Concentration of ions
An ion is more readily discharged if it is present at a higher concentration.
For example, in electrolysis of very dilute sodium chloride solution, OH-(aq) ions are preferentially
discharged rather than Cl-(aq) ions (as predicted from positions of ions in the E.C.S.).
However, in electrolysis of concentrated sodium chloride solution, Cl-(aq) ions are preferentially
discharged, not OH-(aq) ions. This is because the concentration of Cl-(aq) is much greater than that of
OH-(aq). This is known as "concentration effect".
c. Nature of electrode
In most cases of electrolysis, inert electrodes (graphite or platinum) are used. They do not affect the
order of discharge of ions. Other electrodes may affect the preferential discharge of ions and hence the
products formed.
For example, in the electrolysis of concentrated sodium chloride solution, sodium ions are discharged if
mercury cathode is used.
Note: Strictly speaking, the graphite and platinum electrodes are not completely "inert" after all.
When oxygen is liberated at graphite anode, the anode product is contaminated with carbon
dioxide due to oxidation of carbon. Also chlorine gas attacks platinum slightly.
E. Examples Of Electrolysis
1. Electrolysis of Acidified Water
The figures above show a Hofmann voltameter which is useful for electrolysis in which gases are to be
collected.
In acidified water e.g. adding of dilute sulphuric acid to water, there are 3 kinds of ions:
Cations Anions
From sulphuric acid H2SO4: H+(aq) SO42-(aq)
Water ionizes slightly to give hydrogen ions, H+(aq) and hydroxide ions, OH-(aq).
At cathode: Hydrogen ions are discharged (reduced). Hydrogen ions pick up electrons to form
hydrogen gas.
2H+(aq) + 2e- → H2(g)
At anode: Hydroxide ions are discharged (oxidized). Hydroxide ions give up electrons to form
oxygen gas.
2OH-(aq) → 1/2 O2(g) + H2O(l) + 2e-
The sulphate ions SO42- are more difficult to oxidize than hydroxide ions.
i.e. hydroxide ions are preferentially discharged.
Note that, volume of hydrogen : volume of oxygen = 2 : 1
This can be shown by combining the two half equations:

2H+(aq) + 2OH-(aq) → H2(g) + 1/2 O2(g) + H2O(l)
2H2O(l) → H2(g) + 1/2 O2(g) + H2O(l)
H2O(l) → H2(g) + 1/2 O2(g)
i.e. 2H2O(l) → 2H2(g) + O2(g)
Changes in solution:
As electrolysis goes on, water molecules ionize continuously to replace the H+(aq) and OH-(aq) ions
discharged.
Thus the ions discharged come from water. The number of H+(aq) and SO42-(aq) ions from sulphuric
acid remains unchanged. The electrolysis of dilute sulphuric acid is therefore actually the electrolysis of
water.
As electrolysis goes on, water is decomposed and its volume of decrease. Thus the concentration of
sulphuric acid increases.
Example
A little sodium hydroxide solution NaOH(aq) is added to water. The resulting solution is added to a
Hofmann voltameter and electrolyzed, using platinum electrodes.
a. Name the product liberated at (i) cathode (ii) anode.

b. What is the volume ratio of the products in (a)?
2. Electrolysis of very dilute sodium chloride solution
In dilute sodium chloride solution, there are 4 kinds of ions:
Cations Anions
At cathode: Hydrogen ions are preferentially discharged (reduced), giving hydrogen gas.
2H+(aq) + 2e- → H2(g)
Water ionizes continuously to replace the hydrogen ions H+(aq) discharged.

Thus there is an excess of hydroxide ions OH-(aq) near the cathode and the solution
there becomes alkaline.
At anode: Hydroxide ions are preferentially discharged (oxidized), giving oxygen gas.
2OH-(aq) → 1/2 O2(g) + H2O(l) + 2e-
Water ionizes continuously to replace the hydroxide ions OH-(aq) discharged. Thus
there is an excess of hydrogen ions H+ near the anode and the solution there becomes
acidic.
Universal indicator can show whether a solution is acidic or alkaline. It gives a red colour in acidic
solutions and a blue colour in alkaline solution.
If a few drops of universal indicator are added into the sodium chloride solution, the solution near the
cathode would turn blue and that near the anode would turn red during the electrolysis.
Overall reaction: Combining the two half-equations, we get

2H+(aq) + 2OH-(aq) → H2(g) + 1/2 O2(g) + H2O(l)
i.e. 2H2O(l) → 2H2(g) + O2(g)
This is essentially the electrolysis of water. As electrolysis goes on, amount of water decreases, making
the sodium chloride more concentrated.
Classwork
Describe what will be observed at both electrodes when the following substances are electrolyzed (using
graphite electrodes).
(i) dil. sodium bromide NaBr(aq)
(ii) dil. sodium iodide NaI(aq)
3. Electrolysis of dilute or concentrated sodium chloride solution (brine)
a. Using graphite electrode
In concentrated sodium chloride solution, there are 4 kinds of ions:
Cations Anions
At cathode:
Hydrogen ions are preferentially discharged (reduced), giving hydrogen gas.
2H+(aq) + 2e- → H2(g)
At anode:
The number of chloride ions is much greater than that of hydroxide ions. Chloride ions Cl-(aq)
are preferentially discharged (oxidized), giving chlorine gas.
2Cl-(aq) → Cl2(g) + 2e-
Overall reaction: Combining the two half-equations, we get:

2H+(aq) + 2Cl-(aq) → H2(g) + Cl2(g)
As electrolysis goes on, water molecules ionize continuously to replace the H+(aq) ions discharged.
OH- (aq) ions accumulate and the solution gradually changes to sodium hydroxide solution.
Question: What is the ratio of the volume of hydrogen gas and chlorine gas produced?
b. Using mercury cathode and graphite anode
If mercury is used as the cathode in the electrolysis of concentrated sodium chloride solution, sodium
will be formed at the cathode instead of hydrogen.
Cations Anions
At cathode: Sodium ions are preferentially discharged (reduced), giving sodium metal.
The sodium metal dissolved in the mercury to form a sodium amalgam (an alloy of
sodium and mercury). This moves towards the water and reacts with the water.
Hydrogen gas and sodium hydroxide are formed.
Na+(aq) + e- + Hg(l) → Na/Hg(l) sodium amalgam
2Na/Hg(l) + 2H2O(l) → 2NaOH(aq) + H2(g) + 2Hg(l)
At anode: Chloride ions are preferentially discharged (oxidized), giving chlorine gas.
2Cl-(aq) → Cl2(g) + 2e-
Overall reaction: Combing the two half-equations, we get,

2Na+(aq) + 2Cl-(aq) → 2Na(s) + Cl2(g)
As electrolysis goes on, the number of Na+(aq) ions and Cl-(aq) ions decreases; the sodium chloride
solution thus becomes more and more dilute.
4. Electrolysis of dilute copper(II) sulphate solution
a. Using graphite electrode
In dilute copper(II) sulphate solution, there are 4 kinds of ions.
Cations Anions
From copper(II) sulphate CuSO4: Cu2+(aq) SO42-(aq)
At cathode: Copper(II) ions are preferentially discharged (reduced), giving a deposit of copper on
the cathode.
Cu2+(aq) + 2e- → Cu(s)
At anode: Hydroxide ions are preferentially discharged (oxidized), giving oxygen gas.
4OH-(aq) → O2(g) + 2H2O(l) + 4e-
The blue colour of the solution fades out because the concentration of copper(II) ions decreases. As
hydrogen ions H+(aq) and sulphate ions SO42-(aq) remain, the solution becomes sulphuric acid
eventually.
b. Using copper electrodes
Cations Anions
From copper(II) sulphate CuSO4: Cu2+(aq) SO42-(aq)
At cathode: Copper(II) ions are preferentially discharged (reduced), giving a deposit of copper on
cathode.
Cu2+(aq) + 2e- → Cu(s)
At anode: Copper loses electrons more readily than hydroxide and sulphate ions, because Cu(s)
is a stronger reducing agent than OH-(aq) or SO42-(aq) ions. Copper anode dissolves
to form copper(II) ions (oxidized).
Cu(s) → Cu2+(aq) + 2e-
The cathode gets bigger and heavier as copper is deposited on it. The anode becomes smaller and
lighter as it dissolves to form Cu2+(aq) ions. The increase in mass of cathode is equal to decrease in
mass of anode.
For every Cu2+(aq) ion discharged at cathode, one is formed at anode. Therefore the concentration of
copper(II) sulphate solution does not change. The intensity of blue color of solution also remains
unchanged.
Classwork
Suggest what happens in the electrolysis of dilute copper(II) sulphate solution using copper anode and
carbon cathode.
Products of electrolysis of some aqueous solution
Electrodes Main product at

Solution
Cathode Anode Cathode Anode
dil. sulphuric acid platinum platinum H2 O2
conc. hydrochloric acid graphite graphite H2 Cl2
dil. sodium hydroxide graphite graphite H2 O2
dil. sodium nitrate graphite graphite H2 O2
dil. sodium chloride graphite graphite H2 O2
conc. sodium chloride graphite graphite H2 Cl2
conc. sodium chloride mercury graphite Na Cl2
conc. potassium bromide graphite graphite H2 Br2
conc. potassium iodide graphite graphite H2 I2
dil. copper(II) chloride graphite graphite Cu O2
dil. copper(II) sulphate graphite graphite Cu O2
dil. copper(II) sulphate copper copper Cu Cu2+
dil. zinc nitrate platinum zinc H2 Zn2+
Classwork
1. In the following diagram, electrodes A and B are made of carbon while electrodes C and D are made of
copper.
a. (i) What are the gases produced at electrodes A and B respectively?

(ii) Write ionic equations representing the reactions at electrodes A and B.
(iii) What are the colours of the universal indicator around electrodes A and B?
b. (i) Write ionic equations representing the reactions at electrodes C and D.
(ii) State the change in mass of electrodes C and D.
2. In the following diagram, electrodes A and B are made of silver while electrodes C and D are made of
platinum. On completion of the circuit, silver metal begins to deposit on electrode A.
a. Which one of the terminals, X or Y, is the negative terminal of the battery?

b. Write ionic equations for the reactions occurring at electrodes A, B and C respectively.
3. The diagram below shows the apparatus for the electrolysis of two solutions. Electrode A is made of
metal X. The formula of the nitrate of metal X is X(NO3)2. Electrode B is made of carbon. Electrodes C
and D are made of platinum. On completion of the circuit, metal X starts to deposit on electrode B.
a. Write an ionic equation for the reaction occurring at electrode A. Name the type of reaction
occurring at electrode A.
b. Name the gases collected at electrodes C and D respectively.
F. Applications of Electrolysis
Electrolysis is used commercially in various ways:
• Extracting reactive metals.
• Aluminium anodization.
• Manufacture of chlorine and sodium hydroxide.
• Purification of metals.
• Electroplating.
1. Extracting of reactive metals

Metals high in the E.C.S. are very reactive. They form stable compounds. To obtain these metals from
their ores, electrolysis has to be used. Potassium, sodium, calcium and magnesium, for example, are
obtained by electrolyzing their molten chlorides.
2. Anodizing aluminium
Aluminium can be anodized by electrolysis. The aluminium piece to be treated is made the anode in an
electrolytic cell. During electrolysis, the aluminium anode is oxidized. A thicker layer of aluminium
oxide is formed on the surface.
3. The Manufacture of Chlorine and Sodium Hydroxide
We can obtain chlorine and sodium hydroxide industrially by the electrolysis of saturated sodium
chloride solution (brine).
During electrolysis, chlorine gas is given out at the carbon anodes and sodium at the mercury cathode.
The sodium dissolves in mercury to form sodium amalgam.
At anode: 2Cl-(aq) → Cl2(g) + 2e-
At cathode: Na+(aq) + e- + Hg(l) → Na/Hg(l) sodium amalgam
The amalgam then flows into a second cell and reacts with water to form hydrogen and a solution of
sodium hydroxide. Mercury is recovered.
2Na/Hg(l) + 2H2O(l) → 2NaOH(aq) + H2(g) + 2Hg(l)
The net reaction is a commercial source of three important chemicals: hydrogen, chlorine and sodium
hydroxide.
Hydrogen is used to make ammonia and hydrogenated vegetable oils.

Chlorine is used to purify drinking water and to make plastics and solvents.
Sodium hydroxide is mainly used to make soap and paper.
Unfortunately, this process also produces waste products which contain poisonous mercury
compounds. These waste products will cause serious pollution problems when they are discharged into
rivers and seas.
4. Electroplating
Metal objects can be coated with a thin, even layer of another metal be electrolysis. This process is
called electroplating. A metal is electroplated to protect against corrosion or to improve its appearance.
The process of electroplating:

a. The object to be plated should be cleaned by removing grease and dust on it.
b. The object is connected to the cathode of the electrolytic cell and the plating metal is connected
to the anode. The whole setup is immersed into an aqueous solution of plating metal ion.
c. At anode: Copper loses electrons to form copper(II) ions. (Oxidation)

Cu(s) → Cu2+(aq) + 2e-
d. At cathode: Copper deposits on the surface of the object (e.g. key) as Cu2+ ions gain
electrons (reduction) to from Cu atoms.
Cu2+(aq) + 2e- → Cu(s)
e. In laboratory, the plated surface is not shining. However, the objects we bought from shops are
usually shiny and attractive. It is because in industrial electroplating many additives such as
brightener are added to the plating bath.
5. Purification of metals
Metals such as copper and lead are purified by electrolysis. The process is called electrolytic refining.
The impure copper is used as the anode in an electrolytic cell that contains a solution of copper(II)
sulphate and sulphuric acid as the electrolyte.
The cathode is a thin sheet of very pure copper.
When the cell is operated at the correct voltage, only copper and impurities more easily oxidized than
copper (e.g. iron and zinc) dissolve at the anode as the ions. The less reactive metals simply settle at
the bottom of the container.
At the cathode, copper ions are reduced, but the zinc ions and iron ions remain in solution because they
are more difficult to be reduced than copper.
Gradually, the impure copper anode dissolves and the copper cathode grows.
G. Pollution Problems Associated with the Electroplating Industry

In electroplating industries, several pollutants are produced and discharged to the environment.
These pollutants include:

(a) The acidic and alkaline solutions which cause the deterioration of the drainage system, corrosion
of pipes and ships. They may kill the aquatic lives as well.
(b) The heavy metal ions (Cu2+, Ni2+, Cr3+ and so on) may be absorbed and accumulated in the
bodies of the marine organisms and finally passed to the top of the biological food chain (e.g.
human beings) and causes the chronic and acute diseases.
(c) For better plating effect, some highly toxic ions such as cyanides may be used in electroplating.
To cope with the pollutions
a. Acidic or alkaline effluents are usually neutralized before discharge.
b. Less harmful substances can be used to replace the toxic chemicals currently used in the
electroplating process, e.g. Cr(III) instead of Cr(VI) compounds.
c. Metals ions can be recycled, e.g. by precipitation of metal hydroxides, electrodeposition or

ion-exchange methods.
d. Evaporation of effluent to reduce the volume of waste solution.
e. Pass the effluent through waste treatment facilities.
f. Develop proper disposal scheme and develop water control zones.
Classwork
In set-up X, A and B are two different metals. Hydrogen is collected above electrode D after some time.
a. What is the direction of electron flow in the external circuit? Explain your answer.
b. What would be the change in the dilute sulphuric acid in set-up Y after some time? Explain your
answer.
c. What is the function of set-up X in this experiment?
d. Which of the metals, A or B, forms ions more readily? Explain your answer.
G. Factors affecting the rate of electrolysis
a. Increase the current or increase the voltage
b. decrease the total resistance by
(i) adjust the variable resistor (if any) to a lower resistance
(ii) move the electrodes closer
(iii) use electrodes of larger surface
(iv) push the electrodes deeper into the electrolyte
(v) use more concentrated electrolyte
H. Environmental Impact of the electroplating industry

A. Water pollution problems associated with industrial effluents 排放物
(i) the effluents are often hot, coloured, poisonous and corrosive
(ii) the effluents contain acids, alkalis, metal salts, toxic chemicals (e.g. potassium cyanide KCN),
organic solvents etc
(iii) the effluents can

- speed up corrosion of pipes and ships
- kill aquatic life, mainly due to heavy metal ions, toxic chemicals and organic solvents
- cause health hazard to humans. People may be poisoned by eating contaminated seafood.
B. Control of chemical waste disposal in Hong Kong

In 1993, the Hong Kong Government enacted the Waste Disposal (Chemical Waste) Regulation.
(i) Chemical waste producers such as electroplating factories are now required to register with the
Environmental Protection Department EPD 環保署.
(ii) Some of these waste producers install equipment to treat the chemical waste themselves.
(iii) Those that do not are required to store the chemical wastes in special containers, which are then
collected and sent at regular intervals to the Chemical Waste Treatment Centre CWTC 化學廢物處
理中心 for proper treatment and disposal.
Classwork
Suggest methods to reduce pollution from electroplating factories.
Solution
1. Recycling
Electrolytes should be recycled rather than disposed after used.
2. Treatment of effluents
(i) Neutralize acidic effluents with sodium carbonate.
(ii) Neutralize alkaline effluents with sulphuric acid.
(iii) Remove heavy metal ions by precipitation them as hydroxides or carbonates by adding
NaOH(aq) or Na2CO3(aq).
(iv) Reduce chromate ion CrO42- to chromium ion Cr3+ first by adding sodium sulphite; then
precipitate chromium(III) ions out as chromium(III) hydroxide by adding sodium hydroxide
solution.
(v) remove heavy metals ions by electrolysis
I. Importance of Redox Reactions in Modern Ways of Living
Scientists make use of redox reactions in different areas to improve our standard of living.
1. Making of vinegar 醋
Vinegar is produced by fermentation of ethanol in a liquid. During the process, ethanol is oxidized to
ethanoic acid, which is the key ingredient in vinegar.
CH3CH2OH + 2[O] → CH3COOH + H2O
Vinegar is widely used in seasoning food and in preserving food.
2. Food additives – antioxidants

a. Many foodstuffs are spoiled as a result of air oxidation.
e.g. wine may turn sour
cooking oil may become rancid
b. To reduce the spoilage and prolong storage period of the foodstuff, reducing agents known as
antioxidants are often added to packaged foodstuffs.
c. Antioxidants can prevent food from quick spoiling by competing for the oxygen present for oxidation.
d. Some examples of antioxidants
(i) vitamin C is a natural antioxidant commonly used as a food additive.
(ii) sulphur dioxide in wines and fruit juices.
(iii) BHA / BHT used to prevent oxidation of cooking oil.
e. Oxygen absorbers
(i) To extend the shelf life of packaged food like cakes, tea leaves, etc, a small bag of antioxidant is
often added.
(ii) Oxygen absorbers are small packets of iron powder. The packets are made of a material that allows
oxygen and moisture to enter but does not allow the iron powder to leak out.
(iii) Moisture in the packaged food causes the iron to rust. As it oxidizes, the iron absorbs oxygen.
3. Hand –warmers
(i) The hand warmers make use of the exothermic reaction of the oxidation of iron to keep our hands
warm in winter.
(ii) The iron powder inside is oxidized by atmospheric oxygen, giving out heat energy continuously for
about eight hours.
4Fe(s) + 3O2(g) → 2Fe2O3(s) ∆H = -ve

4. Breathalyzers 呼氣分析儀
(i) A breathalyzers can measure the blood alcohol content (BAC) of drivers
(ii) Breathalyzer contains a solution of acidified potassium dichromate which can be reduced by ethanol
present in a driver’s breath.
K2Cr2O7 + CH3CH2OH → Cr3+ + CH3COOH
(iii) The colour change of the contents in the breathalyzer can be used as an indicator of the BAC.
5. Bleaching
(i) Chlorine bleach which contains sodium hypochlorite (NaOCl).
(ii) When sodium hypochlorite bleaches, the dye is oxidizied to colourless compound.
OCl- (aq) + dye (coloured) → Cl-(aq) + [dye+O] (colourless)
(iii) Sulphur dioxide (or sodium sulphite) is a bleaching agent that bleaches by reducing the dye.
SO2(aq) + dye (coloured) → SO42-(aq) + [dye – O] (colourless)
J. Fuel cells and their applications

(i) Refer to HKDSE CHEMISRY A Modern View Book 3 p.205-209
(ii) Appendix 2
K. Rechargeable lithium cells and their applications
(i) Refer to HKDSE CHEMISRY A Modern View Book 3 p.209-212

(ii) Appendix 3
Appendix 1
Production of Aluminium from Aluminium Ore
A. Aluminium is the most abundant metal in the Earth’s crust. Pure aluminium can be produced from the
chief ore of aluminium – bauxite 鋁土礦. It is a mixture of hydrated aluminium oxide and
hydrated iron oxide.
B. Metallic aluminium has many properties that make it useful.

e.g. lightweight; strong; non-toxic;
surface oxide layer resist corrosion e.g. corrosion resistant;
can be recycled easily
C. Industrial production of aluminium
Procedures
1. Separation of aluminium oxide from iron oxide
Mixture of aluminium oxide and iron(II, III) oxide are dissolved in concentrated NaOH.
The aluminium ion forms a soluble complex ion with the OH-, while the iron ion does not.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
Insoluble iron(II, III) oxide is filtered from the solution.
2. Acid is added to the solution to precipitate aluminium hydroxide Al(OH)3
3. The precipitate is heated to produce dry aluminium oxide
2Al(OH)3(s) → Al2O3(s) + 3H2O(l)
4. The extraction of aluminium from the oxide is done by electrolysis, but first the aluminium oxide
must be made molten so that electricity can pass through it.
5. Aluminium oxide has a very high melting point (over 2000oC). It would be expensive to melt
aluminium oxide.
So aluminium oxide is dissolved in molten cryolite 冰晶石 – an aluminium compound Na AlF 3 6
with a lower melting point. As the melting point of the mixture of aluminium oxide and cryolite is
lower, less fuel is needed. Thus, the use of cryolite reduced the energy cost of the extracting
process.
graphite anode
oxygen evolved
aluminium oxide
dissolved in
molten cryolite
molten
aluminium out
steel tank
graphite cathode molten aluminium
Appendix 2
Fuels Cells and their Applications
A. Major types of fuel cell

1. alkaline fuel cell
2. phosphoric acid fuel cell
3. molten carbonate fuel cell
4. solid oxide fuel cell
5. proton exchange membrane fuel cell
They all have the same basic design as discussed in P.49, but with different chemicals used as the
electrolyte.
B. Characteristics and Applications of Common types of fuel cells
Proton
Molten Direct
Alkaline fuel Phosphoric Solid oxide exchange
carbonate methanol
cell acid fuel cell fuel cell membrane
fuel cell fuel cell
fuel cell
Liquid
Potassium Molten Solid ceramic Polymeric Polymeric
Electrolyte
hydroxide
phosphoric
acid
carbonate 陶瓷 membrane membrane
Operating
temperature 60-90 200 650 1000 80 60-130
o
( C)
Electrical
Up to 20 kW >50 kW >1 MW >200 kW Up to 250 kW <10 kW
power
Vehicles,
Commercial
Possible Submarines, Large power Power building, Portable
premises,
applications spacecraft stations stations smaller applications
large vehicles
applications
C. Direct methanol fuel cells DMFC
Instead of using pure hydrogen, this type of fuel cell uses methanol directly as the fuel.
CH3OH(l) + H2O(l) CO2(g) + 6H+(aq) + 6e-
methanol CO2
e-
negative electrode
polymeric membrane as electrolyte

e-
H+
e-
positve electrode
oxygen (air) air
1.5O2(g) + 6H+(aq) + 6e- 3H2O(l)
(i) The liquid methanol (CH3OH) is oxidized in the presence of water at the negative electrode
(containing platinum as catalyst), generating carbon dioxide, hydrogen ions and electrons.
CH3OH(l) + H2O(l) → CO2(g) + 6H+(aq) + 6e-
(ii) The electrons travel through the external circuit.
(iii) The hydrogen ions travel through the electrolyte. They react with oxygen from the air and the
electrons from the external circuit to form water at the positive electrode.
1.5 O2(g) + 6H+(aq) + 6e- → 3H2O(l)
(iv) The overall cell reaction is:
CH3OH(l) + 1.5 O2(g) → CO2(g) + 2H2O(l)
(v) Fuel cells may help to ease the chemical cell disposal problems and they require no charging.
Direct methanol fuel cell appears to be the most promising alternative power source for portable
electronic devices.
D. Using Fuel Cells to Power Cars
There are severe concerns over diminishing fuel reserves and pollution problems caused by
petrol-driven cars. Using efficient energy conversion devices such as fuel cells to power cars is a
possible solution.
Fuel cells that convert the chemical energy released by the oxidation of hydrogen into chemical energy
are ideal for vehicles aiming at zero emissions.
Honda FCX
How to generate hydrogen for fuel cells
(i) Electrolysis of water is the most likely method for large-scale hydrogen production. The energy needed
for electrolysis may be obtained from some renewable sources, such as solar, wind or hydroelectric
power.
(ii) In the short term, the most likely solution to generate hydrogen is by extracting it from hydrocarbon
fuels, such as natural gas, methanol or gasoline, by steam reforming.
e.g. CH4 methane is the major component of natural gas.

Methane is mixed with steam in the presence of a catalyst to produce hydrogen and carbon
monoxide.
CH4(g) + H2O(g) ⇔ CO(g) + 3H2(g)

Appendix 3
The Chemistry of Lithium Ion Secondary Cells
A. Lithium is the lightest metal and it is very reactive. These properties give lithium cells the very high
energy densities.
B. In a typical lithium ion secondary cell,

(i) the negative electrode consists of lithium compounds e.g. LiC6 lying between graphite sheets.
(ii) the positive electrode is made of tranistion metal oxide e.g cobalt oxide CoO2
(iii) the electrolyte is a lithium salt in an organic solvent.
C. (i) During discharge, lithium compounds at the negative electrode (anode) give out electrons to form
lithium ions.
i.e. LiC6 → 6C + Li+ + e-
At the positive electrode (cathode): CoO2 + Li+ + e- → LiCoO2
(ii) The lithium ions then dissociate from the negative electrode (anode), migrate across the
electrolyte and insert into the crystal structure of the positive electrode (cathode).
(iii) Electron flows in the external circuit.
Discharging Charging
V
electrons electrons
electrons electrons
separator separator
anode cathode cathode anode
lithium ion electrolyte electrolyte

lithium ion lithium ion lithium ion
d. During the charging process, the process is reversed. Lithium ions pass back and forth between the
electrodes during discharging and charging.
e. Comparison between lithium ion rechargeable cell with other cells
(i) it weighs about half that of a NiMH cell of the same charge capacity i.e. higher charge density.
(ii) It’s voltage range is more suitable for many portable electronic devices like mobile phones, MP3
players, digital cameras, etc
(iii) It can discharge at much larger currents than NiMH cells continuously for a longer period of time.
It is very important for some applications such as the steady conversion over the mobile phones.
(iv) It does not contain mercury, lead or cadmium as the zinc carbon cells, lead-acid accumulators or
nickel cadmium cells NiCd do.
(v) It contains lithium compounds instead of the reactive lithium metal. This makes lithium ion
rechargeable cells safer for use and for transportation.
(vi) It can be recharged and discharged for 1200 cycles within 3 years.
(vii) It only lose about 5% of the charge per month. NiMH and NiCd cells lose about 1 % of the charge
per day.
(viii) It can be fast charged to 70-80 % of full capacity in one hour.
f. Lithium-ion polymer rechargeable batteries

Lithium-ion polymer rechargeable batteries (Li-poly or LiPo) are batteries which have technologically
evolved from lithium-ion rechargeable batteries. In these batteries, the lithium-salt electrolyte is not
held in an organic solvent, but in a solid polymer such as polyethene oxide.
An important advantage of LiPo is that manufacturers can make the battery to any shape. Another
advantage of LiPo over NiMH or NiCd is that the rate of self-discharge is much lower.

Redox Reactions and Electrolysis

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Redox Reactions and Electrolysis

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Part VII Redox Reactions, Chemical Cells & Electrolysis (Part 2)/P.

Part VII Redox reactions, Chemial Cells and Electrolysis

A. The General Setup For Electrolysis

a. Direct current (d.c.) power supply / cell / battery

d. Variable resistor / rheostat

B. Comparing Electrolytic Cells and Electrochemical Cells

Electrolytic cell Electrochemical cell

a. Conduction of electric current by electrolytes

In electrolytes, electric current is conducted by migration of mobile ions.

Pb2+(l) + 2e- → Pb(l) silvery [Reduction]

*Question: Why does not the below reaction occur?

The overall reaction is thus,

Basic concepts - related to aqueous electrolytes

H2O(l) H+(aq) + OH-(aq)

b. Ionization of acids in water

c. Indicators showing whether a solution is acidic or alkaline

Thus 3M NaCl(aq) solution is more concentrated than 0.1M NaCl(aq) solution.

3M NaCl(aq), 5M NaOH(aq) and 12M H2SO4(aq) are regarded as concentrated solutions; in

2. Electrolytes of Aqueous Sodium Chloride Solution

From water: H+(aq) OH-(aq)

Hence, which of the cations is preferentially discharged, Na+(aq) or H+(aq)?

We have to consider the factors affecting preferential discharge of ions.

Cations lower in the E.C.S. are more readily discharged.

From water: H+(aq) OH-(aq)

H2O(l) H+(aq) + OH-(aq)

2H+(aq) + 2e- → H2(g)

2OH-(aq) → 1/2 O2(g) + H2O(l) + 2e-

Note that, volume of hydrogen : volume of oxygen = 2 : 1

This can be shown by combining the two half equations:

a. Name the product liberated at (i) cathode (ii) anode.

From water: H+(aq) OH-(aq)

2H+(aq) + 2e- → H2(g)

Water ionizes continuously to replace the hydrogen ions H+(aq) discharged.

Overall reaction: Combining the two half-equations, we get

From water: H+(aq) OH-(aq)

2H+(aq) + 2e- → H2(g)

2Cl-(aq) → Cl2(g) + 2e-

Overall reaction: Combining the two half-equations, we get:

From water: H+(aq) OH-(aq)

Na+(aq) + e- + Hg(l) → Na/Hg(l) sodium amalgam

2Na/Hg(l) + 2H2O(l) → 2NaOH(aq) + H2(g) + 2Hg(l)

Overall reaction: Combing the two half-equations, we get,

From water: H+(aq) OH-(aq)

Cu2+(aq) + 2e- → Cu(s)

From water: H+(aq) OH-(aq)

Cu2+(aq) + 2e- → Cu(s)

Cu(s) → Cu2+(aq) + 2e-

Products of electrolysis of some aqueous solution

Electrodes Main product at

a. (i) What are the gases produced at electrodes A and B respectively?

a. Which one of the terminals, X or Y, is the negative terminal of the battery?

1. Extracting of reactive metals

At anode: 2Cl-(aq) → Cl2(g) + 2e-

At cathode: Na+(aq) + e- + Hg(l) → Na/Hg(l) sodium amalgam

2Na/Hg(l) + 2H2O(l) → 2NaOH(aq) + H2(g) + 2Hg(l)

Hydrogen is used to make ammonia and hydrogenated vegetable oils.

The process of electroplating:

c. At anode: Copper loses electrons to form copper(II) ions. (Oxidation)

The cathode is a thin sheet of very pure copper.

G. Pollution Problems Associated with the Electroplating Industry

These pollutants include:

c. Metals ions can be recycled, e.g. by precipitation of metal hydroxides, electrodeposition or

d. Evaporation of effluent to reduce the volume of waste solution.