Chapter 1 Redox Equilibrium

1.1 Oxidation and Reduction

Redox reaction: Chemical reaction where oxidation & reduction occur simultaneously.

Oxidation reaction Reduction reaction

Takes place when a reactant gains O2-, Takes place when a reactant lose O2-,
lose H+ & e- , oxidation number increases. gains H+ & e- , oxidation number decreases
Oxidising agent Reducing agent
Substance that causes reduction Substance that causes oxidation
E.g: Acidified potassium manganate(VII) E.g: Chloride ion, Bromide ion, Iodide ion,
Acidified potassium dichromate(VI) solution Sulphate ion, Sulphur dioxide gas
Chlorine water, Bromine water, Iron(III) ion Hydrogen sulphide gas
Positive terminal Negative terminal
The electrode where electrons are accepted The electrode where electrons are released

X: Negative terminal, Y: Positive terminal

-Iron(II) lose electron to become Iron(III)
9 -Pale green turns Yellow
-Purple decolourises, manganate(VII) ions used up
-Galvanometer: Determine electrodes that act as the
c positive terminal & negative terminal.
-Sulphuric acid: -Used to separate the reducing agent from oxidizing agent.
-To complete the circuit by allowing the transfer of ions to occur.
Determine the oxidation number of BrO3-. O is -2.
x + 3(-2) = -1
x = +5
Types of redox reactions
1. Conversion of Iron(II) to Iron (III)

+2 to +3 +3 to +2
-Add reducing agent -Add oxidizing agent
-Bromine water: brown decolourised. Solution -Zinc powder: Partially soluble. Solution turns
turns pale green to yellow brown to pale green.
-NaOH solution: Brown precipitate formed. -NaOH solution: Green precipitate formed.
Insoluble in excess alkali Insoluble in excess alkali.

Reagent Ions Observation

NaOH / Ammonia solution Fe2+ Green precipitate, insoluble in excess alkali
Fe3+ Brown precipitate, insoluble in excess alkali
Potassium hexacyanoferrate(II) solution Fe2+ Light blue precipitation
Public holiday no more Monday blue Fe3+ Dark blue precipitation
Potassium hexacyanoferrate(III) solution Fe2+ Dark blue precipitation
Fe3+ Greenish brown solution
Potassium/ammonium thiocyanate solution Fe2+ Pale red colouration
Personal trainer gets injured somtimes Fe3+ Blood red colouration

2. Displacement of Metal from its Salt Solution

-Add metal into salt solution of another metal
-More electropositive metal will displace less electropositive metal.
-More electropositive = reducing agent
-Less electropositive = oxidising agent
-E.g. In a test tube containing copper strip and silver nitrate solution,
copper more electropositive, acts as reducing agent, lose e- form ions.
Silver ions accept e- , acts as oxidizing agent.
Copper displaces silver from its salt solution.
3. Displacement of Halogen from its Halide Solution
 -Strength of halogens as oxidizing agents decreases down the group, as reducing agent
increases.
-Strength of halide ions as reducing agents increases.
-More electronegative halogen = oxidizing agent (Fluorine)
-Less electronegative halogen = reducing agent (Iodine)
-1,1,1-trichloroethane can identify presence of halogen
Cl Br Iodine
Color of halogen in aqueous solution Yellow Brown Brown
ions: Colourless
Color of halogen in 111-trichloroethane Colourless Brown Purple

-Colour of KBr turns from colourless to brown

-Bromide ion lose electrons to form bromine molecule
-Bromide ions are oxidized to bromine molecule
-Oxidation number of iodine increases from -1 to 0
-Potassium bromide is reducing agent
-Colour of Cl2 turns from greenish yellow to colourless
-Chlorine molecule accepts electron to form Cl ion
-Chlorine molecule is reduced

1.2 Standard Electrode Potential

Electrode potential E0 : The potential difference produced when an equilibrium is established
between metal M and the aqueous solution containing metal Mn+ ions in a
half-cell.
Standard electrode potential: The standard reduction potential. All half-cell equations are written
as
reduction.
E0 value: A measure of the tendency of a substance to accept or donate electrons.
-Electrode potential cannot be measured directly.
-The value is determined based on the difference of electrode potential between two half-cells.
-The electrode potential can be measured by pairing up the electrode to the standard reference
electrode system.

E0 H+ = -0.00V , E0 Zn = -0.76V
-Zn more electronegative, greater tendency to be
oxidized. Zn becomes negative terminal. Electrons
move from Zn electrode to Pt electrode.
-Function of salt bridge: To allow ions flow from one
solution to another to complete the circuit.
 E0 positive value E0 negative value
E.g. Silver E.g. Magnesium
-E0 value of Ag more positive & -E0 value Mg more negative & electropositive
electronegative -Mg on the right side is stronger reducing
-Ag+ on the left side is stronger oxidizing agent
agent -Easier to lose electrons and undergo
-Easier to gain electrons and undergo oxidation
reduction -Size of electrode decreases
-Size of electrode increases -Intensity of colour and concentration of ions
-Intensity of colour and concentration of ions increases
decreases
-Conversely, Ag on the right side is weaker
-Conversely, Ag on the right side is weaker oxidizing agent. Difficult gain electrons.
reducing agent. Difficult lose electrons

To determine whether reaction can occur between an atom and an ion in a compound.
-To become ions, atom must be more negative to undergo oxidation.
-To become atoms, ion must be more positive to undergo reduction.
1.3 Voltaic cell
Simple chemical cell
-2 different metal plates dipped into an electrolyte & connected with connecting wires.
-Also known as voltaic cell / galvanic cell
-Chemical cell is the set-up that apply redox reaction to convert chemical energy to electrical energy
-Redox reaction occurs in the cell causes flow of electrons and produce electric current.
-Voltmeter detects potential difference to indicates presence of electric current.
More electropositive metal: Negative terminal (release electrons)
More electronegative metal: Positive terminal (accept electrons)
 To determine the voltage of voltaic cell
1. Magnesium is more electropositive than copper
2. Magnesium donates two electrons to become Mg2+
ion.
3. Mg2+ released into NaCl solution.
4. Electrons flow through connecting wire towards Cu.
5. Electrons can be accepted by positive ions in
electrolyte, like Mg2+, H+, Na+.
6. H+ is more electronegative than Mg2+ & Na+.
7. H+ is selectively discharged at Cu plate by accepting
electrons to form hydrogen gas.
-If electrodes are made of Copper metal, theres no potential difference. No electrons flow between
same metal.
-Electrons flow in the opposite direction of electric current.
1.4 Electrolytic cell
Electrolytes: substances that can conduct electricity in either the molten state or aqueous solution
undergo chemical changes.
Non-electrolytes: substances that cannot conduct electricity at all states.
 Conductor Electrolyte
Substances that conduct electricity in Substances that conduct electricity in molten
solid/molten state state / aqueous solution
Do not undergo chemical changes Undergo chemical changes
Substances that conduct electricity without Substances that conduct electricity and
undergoing decomposition undergo decomposition into their constituent
elements
Conduct electricity due to presence of free Conduct electricity due to presence of free
moving electrons moving ions
Electrical conductivity decreases as Electrical conductivity decreases as
temperature increases temperature increases
E.g. metals and graphite E.g. ionic compounds, acids, alkali

Electrolysis: Process whereby compounds in the molten state or an aqueous solution decompose
into their constituent elements by passing electricity through them.
-Anions move to anode, cations move to cathode.
During electrolysis, why does the bulb light up when lead(II) bromide has melted?
-Because when lead(II) bromide melts, lead(II) ions and bromide ions can move freely.

Term Definition
Electrode A conductor in the form of a wire, rod or plate which carries electric current in and
out of the electrolyte during electrolysis.
Active An electrode which takes part in chemical reactions during electrolysis.
electrode E.g. metal electrodes such as copper, silver and mercury.

Inert An electrode which does not take part in chemical reactions during electrolysis.
electrode E.g carbon (graphite) and platinum electrodes.

Anode An electrode which is connected to the positive terminal of the source of electricity
in an electrolytic cell.
-Undergo oxidation, releases electrons

Cathode An electrode which is connected to the negative terminal of the source of

electricity in an electrolytic cell.
-Undergo reduction, gains electrons

.
 Factors of ion to Electrode Ion chosen to be discharged
be discharged
E0 value Anode Anions with a more negative E° value in the standard electrode
potential series will be easier to be discharged and oxidised.

Cathode Cations with a more positive E° value in the standard electrode

potential series will be easier to be discharged and reduced.
Concentration Anode (i)This factor is only considered for the selection of ions at the
of solution anode if the aqueous solution contains halide ions.
(ii) Halide ions with a higher concentration in the electrolytes will
be discharged at the anode, even though the E° value of the
halide ions are more positive.

Cathode Cations with a more positive E° value in the standard electrode

potential series will be easier to be discharged and reduced.
Type of Anode (i)This factor is only considered for active electrodes
electrode (ii)No anions are discharged.
(iii)Metal atoms at the anode release electrons to form metal
ions.

Cathode Cations with a more positive E° value in the standard electrode

potential series will be easier to be discharged and reduced.

-Aqueous solution contains anions and cations of compound, hydrogen and hydroxide ions from
partial dissociation of water
-Cations of compound and H+ ions move to cathode
-Anions of compound and OH- ions move to anode

Electrolysis of copper(II) sulphate

-Aqueous solution consists of Cu2+,SO42- , H+,OH-
-Cu2+ & H+ move to cathode.
-Cu2+ are selectively discharged and accepts 2 e- to form
Copper atom
-Cu2+ is more positive E0 value, it is reduced selectively
-SO42- ,OH- move to anode
-OH- are selectively discharged by donating 2e- to form
oxygen and water.
-Water molecule has more positive E0 value, it is discharged
selectively
-Intensity of blue colour of electrolyte decreases as
concentration of Cu2+ decreases when more copper
deposited on cathode
-Electrolyte become more acidic due to H+ & SO42- left.
 Study effects of ion concentration in HCl solution on the
selection
of ions to be discharged at electrode
0.001moldm-3 : Colourless gas relights glowing wooden split
2moldm-3 : Greenish-yellow gas with pungent smell. Gas turns
blue litmus paper red then white.
-Aqueous solution consists of H+,Cl-,OH-
-Cl-,OH- move to anode
-H+ move to cathode. It is discharged to form H2 gas.

Electrolysis of 0.001moldm-3 HCl Electrolysis of 2moldm-3 HCl

OH- are selectively discharged to form O2 & Cl- are selectively discharged to form Cl2 gas
H2O
Because OH- ion is lower in electrochemical Because concentration of Cl- is higher in
series electrolyte
Concentration of electrolyte increases gradually Concentration of electrolyte decreases
as water is decomposed into hydrogen gas and gradually as H+ and Cl- ions are removed from
oxygen gas electrolyte

Operational definition : definition in the context of the experiment by describing

what must be done and what should be observed.

Operational definition of electrolysis in this experiment:

Process that produces gas bubbles at anode when carbon electrodes connected to batteries are
dipped into hydrochloric acid

Study effects of types of electrodes on the selection of ions to be discharged at the

electrode

Electrode Observation
Anode Cathode Electrolyte
Carbon Colourless gas which Brown solid Intensity of blue
relights glowing wooden split deposited on colour of electrolyte
is produced cathode decreases
Copper Copper electrode dissolves. Cathode becomes Intensity of blue
Electrode becomes thinner. thicker colour of electrolyte
remains unchanged

Carbon electrode
-Aqueous solution consists of Cu2+,SO42- , H+,OH-
-Cu2+ & H+ move to cathode.
-Cu2+ is lower than H+ in electrochemical series. Thus, it is selectively discharged to form Cu
metal.
-SO42- ,OH- move to anode
-OH- is lower than SO42- in electrochemical series. Thus, it is selectively discharged to form O2 &
H2O.
-Blue decreases because concentration of Cu2+ decreases when more Cu deposited on cathode.

Copper electrode
-Cu2+ & H+ move to cathode.
-Cu2+ is lower than H+ in electrochemical series. Thus, it is selectively discharged to form Cu
metal.
 -SO42- ,OH- move to anode
-These ions are not discharged. Instead, copper electrode dissolves to form Cu2+
-Blue remains unchanged because rate of Cu2+ discharged to form copper atom at cathode is the
same as rate of copper atom from the anode dissolves to form Cu2+ ion.
Comparison between electrolytic cell and voltaic cell
Similarities:
-Each cell consists of an electrolyte.
-Each cell consists of two electrodes.
-The process of donation of elections occurs at the anode while the process of acceptance of
electrons occurs at the cathode.
-Electrons flow from the anode to the cathode in the external circuit.
Differences:

Voltaic cell Electrolytic cell

Different type of metal Type of Same type of metals

electrodes

Chemical energy - electrical energy Conversion of Electrical energy - chemical energy

energy

Electrons flow from the more Flow of electrons Electrons flow from the positive
electropositive metal (negative electrode to the negative electrode
terminal) to the less electropositive through the external wire.
metal (positive terminal)

The anode (negative terminal) is Charges of The anode (positive terminal) is

negatively charged. electrodes positively charged.
The cathode (positive terminal) is The cathode (negative terminal) is
positively charged. negatively charged.

Oxidation occurs at the anode Oxidation and Oxidation occurs at the anode
(negative terminal) while reduction reduction (positive electrode) while reduction
occurs at the cathode (positive occurs at the cathode (negative
terminal). electrode

Electroplating and Purification of Metals

Electroplating: Process of depositing a layer of metal on another substance using electrolysis
-Electroplating of metals through electrolysis is done by making the object being electroplated as
the cathode, the pure electroplating metal as the anode, and an aqueous solution containing the
ions of the electroplating metal as the electrolyte.
Study electroplating of iron spoon with copper
-During electrolysis using Cu as anode, iron as cathode
-Copper dissolves to form Cu2+ ions.
-At cathode, copper metal deposited on spoon
-Electroplating occurs
-The purification of copper by electrolysis is carried out with a piece of pure, thin copper as the
cathode; impure copper as the anode; and an aqueous salt solution of copper, such as copper(II)
nitrate, 𝐶𝑢(𝑁𝑂3)2 as electrolyte.

Study purification of copper

-During electrolysis using impure copper as anode, pure
copper as cathode
-Impure copper plate is ionized and impurities fall to the
bottom of beaker.
-Cu2+ discharged at pure copper plate. A layer of copper is
deposited on pure copper plate
-Purification occurs.

1.5 Extraction of Metal from Its Ore

-Non reactive metals such as gold and silver do not need to be extracted because they exist as
metal elements.
-Reactive metals like iron and aluminium require a particular way to be extracted from their
respective ores.
-The methods for extracting reactive metals are based on the position of the metal in the reactivity
series of metal.

Via electrolysis
-Reactive metals like aluminium, Al can be extracted from its ore using electrolysis.
-In the extraction of aluminium, Al, aluminium ore or bauxite is firstly purified to obtain aluminium
oxide, which is then melted down to enable the process of molten electrolysis to be conducted.
-The melting process uses an extremely high energy since the melting point of aluminium oxide is
2000 °C.
-To overcome this problem, cryolite, is melted together to lower its melting point.

-Molten aluminium sinks to the bottom of the layer because its density is higher, and then is drained
out through a designated channel.
-During the process of electrolysis for molten aluminium oxide carbon dioxide is formed
-The purification process of bauxite creates a residue in a form of red sludge that is toxic.
Via reduction process of carbon
- Iron metal, which is less reactive than carbon can be extracted by carbon reduction process.
- Process is carried out in blast furnace by heating up iron ore with coke and limestone.

Via more reactive metal

-When metals are heated together, the more reactive metal can extract the less reactive metal from
its metal oxide.
-This reaction releases large amounts of heat that produce metal in molten state.
-E.g. in a thermite reaction, aluminium powder, Al is heated together with iron(III) oxide powder
-The more reactive aluminium, Al reduces iron(III) oxide to produce molten iron, Fe.
-Some other metals like chromium, Cr and titanium, Ti can be extracted from their respective metal
oxides using reduction by more reactive metals.
1.6 Rusting
Rusting: Corrosion of metal.
Corrosion of metal: redox reaction in which a metal is oxidized naturally to its ions, resulting in
partial or complete destruction of the metal.
Rusting of iron
1. Iron serves as anode which undergo oxidation. It loses electrons to form iron(II) ions.
2. Electrons flow to the water where there is dissolved oxygen.
3. Oxygen gains electrons and is reduced to form hydroxide ions.
4. Iron(II) ions combine with hydroxide ions to form Iron(II) hydroxide.
5. It is further oxidized by oxygen to form hydrated iron(III) oxide which is known as rust.
-Presence of acids and salts accelerate rusting.
Effect of Other metals on rusting
-Phenolphthalein indicator is used to test presence of OH- ions which indicate whether the metal is
rusted.
-Potassium hexacyanoferrate(III) solution is an indicator that is used to observe the intensity of dark
blue colouration
-Jelly is used to enable us see blue & pink colourations clearly without mixing together.

Test Pair of Intensity of dark Pink Inference regarding

tube metals blue colouration colouration rusting
I Fe Low Present Iron rusts a little
II Fe+Mg None Present Iron does not rust
III Fe+Zn None Present Iron does not rust
IV Fe+Sn High Present Iron rusts quickly
V Fe+Cu Very high Present Iron rusts very quickly

Test tube II
-Mg more electropositive than Fe. It loses electrons more readily than iron.
-Mg is oxidized. It acts as anode.
-Electrons flow to Fe which acts as cathode.
-At cathode, the electrons are gained by oxygen
-Oxygen undergo reduction producing OH ions that give pink colouration with phenolphthalein.
-Fe doesn’t corrode. Blue colouration is absent.
Test tube V
-Fe more electropositive than Cu. It loses electrons more readily than Cu.
-Fe is oxidized. It acts as anode.
-Fe and Cu have large difference in electropositivity, rusting occurs very quickly, producing large
amount of iron(II) ions, explaining the high intensity of blue colouration in test tube.
-Electrons flow to Cu which acts as cathode.
-At cathode, the electrons are gained by oxygen
-Oxygen undergo reduction producing OH ions that give pink colouration with phenolphthalein
Rusting prevention
. 1. Protective coating 2. Alloying
-Oil, grease (engines) , Paints, plastics -E.g. stainless steel: Chronium, nickel, carbon
-Galvanising (zinc plating) , tin plating (can)
3. Sacrificial protection
-Attached to a more electropositive metal
-Being more electropositive, metal will become sacrificial and acts as anode to be oxidized