Grade 12 Science Essentials SCIENCE CLINIC 2022 ©

Electrochemistry-Redox
REDOX REACTION TABLE OF STANDARD REDUCTION POTENTIALS (REDOX TABLE)
A redox reaction is a reaction in which there is a transfer of electrons The oxidation and reduction half reactions can also be found using the Table of Standard Reduction Potentials. (We will use Table 4B).
between elements/compounds.
The reactions shown on the table are all written as reduction half reactions, with the reversible reaction arrow (⇌) shown. This
Oxidation is the loss of electrons (oxidation number increases) means that each reaction is reversible. When a reaction is written from the table the arrow must only be one way (i.e. →).
Reduction is the gain of electrons (oxidation number decreases)
The reduction half reaction is written from the table from left to right and the oxidation half reaction is written from right to left.

  

   
The oxidising agent is the substance which accepts electrons.
(It is the substance which is reduced and causes oxidation.)
  
  
  
 
    

  
The reducing agent is the substance that donates electrons.
(It is the substance which is oxidised and causes reduction.)
  
 
 
   
The anode is the electrode where oxidation takes place.
The cathode is the electrode where reduction takes place. 




 
OIL: Oxidation is loss 
   
RIG: Reduction is gain    

   
LEO: Loss of electrons is oxidation Once the half-reactions are identified it is possible to write a balanced reaction, without the spectator ions. A spectator ion is an ion in
GER: Gain of electrons is reduction a redox reaction that does not take part in electron transfer. Remember that the number of electrons lost or gained by each substance
must be the same.
REDCAT: Reduction at cathode
ANOX: Oxidation at anode If the line drawn between the two reactants has a positive gradient, the reaction is spontaneous.
If the line between the reactants are negative, the reaction is non-spontaneous.

STEPS TO WRITING BALANCED REDOX EXAMPLE: EXAMPLE:

REACTIONS USING REDOX TABLE +
Zinc metal reacts with an acid, H (aq) to produce hydrogen gas. Using Magnesium ribbon is burnt in a gas jar containing chlorine
1. IDENTIFY THE REACTANTS the oxidation and reduction half reactions write a balanced equation for gas. Using half reactions write a balanced chemical equation
2. UNDERLINE REACTANTS ON THE REDOX TABLE this reaction. for this reaction.
STEP 1: IDENTIFY THE REACTANTS
3. DRAW ARROWS IN DIRECTION OF REACTION
Ox half-reaction: Mg → Mg2+ + 2e−
Zn(s) and H+(aq)
4. WRITE THE OXIDATION AND REDUCTION HALF-REACTIONS Red half-reaction: Cl2 + 2e− → 2Cl−
5. BALANCE ELECTRONS IF NECESSARY STEP 2: UNDERLINE REACTANTS ON THE REDOX TABLE
Overall reaction: Mg + Cl2 → Mg2+ + 2Cl−
6. WRITE OVERALL REACTION (LEAVE OUT SPECTATORS) STEP 3: DRAW ARROWS IN DIRECTION OF REACTION
EXAMPLE:
STEP 4: WRITE THE OXIDATION AND REDUCTION HALF-
REACTIONS Using half reactions, complete and balance the following reac-
tion: Pb + Ag+
Ox half-reaction: Zn → Zn2+ + 2e−
+
Ox half reaction: Pb → Pb2+ + 2e−
Red half-reaction: 2H + 2e− → H2 Red half reaction: Ag+ + e− → Ag
STEP 5: BALANCE ELECTRONS IF NECESSARY
STEP 6: WRITE OVERALL REACTION (LEAVE OUT SPECTATORS) Ox half reaction: Pb → Pb2+ + 2e−
+ 2+ (x2 red half reaction): 2Ag+ + 2e− → 2Ag
Overall: Zn + 2H → Zn + H2
Overall reaction: Pb + 2Ag+ → Pb2+ + Ag

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 Grade 12 Science Essentials SCIENCE CLINIC 2022 ©
Electrochemistry- Galvanic/Voltaic cell
A galvanic cell reaction is always a spontaneous, EMF OF THE CELL ZINC-COPPER CELL
exothermic reaction during which chemical energy   
The emf of the cell is calculated using one of the following equations: 
is converted to electrical energy. A electric cell/
battery is an example of a galvanic cell. 
Eθcell = Eθcathode − Eθanode
STRUCTURE Eθcell = Eθreduction − Eθoxidation A positive εθ value indicates   
Two half-cells (usually in separate containers): a spontaneous reaction 

Anode – where oxidation takes place – negative Eθcell = Eθoxidising agent − Eθreducing agent  
electrode
 
 
Cathode – where reduction takes place – positive The emf of the half-cells are determined using the standard hydrogen
electrode half-cell




The anode and cathode connected together through

an external circuit, which allows for current to flow
Standard hydrogen half-cell
from the anode to the cathode The hydrogen half-cell is allocated a reference potential of 0,00 V. All  
other half-cells will have a potential which is either higher or lower
   
than this reference. This difference is the reading on the voltmeter The zinc half-cell (–): The copper half-cell (+):
 placed in the circuit.
• Zinc electrode • Consists of a copper electrode
   • Zinc salt solution • Copper salt solution




 

   
(e.g. zinc (II) nitrate) (e.g. copper (II) nitrate)
  
 %
"!
 • Zn is a stronger RA than • Cu2+ is a stronger OA than Zn2+,
Cu, ∴Zn oxidises ∴Cu2+ reduces
• Oxidation reaction occurs: • Reduction reaction occurs:
Zn → Zn2+ + 2e− Cu2+ + 2e− → Cu
• Anode • Cathode
    • Electrode decreases in mass • Electrode increases in mass
 
 


SALT BRIDGE   #
%

 $ Ox: Zn (s) → Zn2+ (aq) + 2e−
The salt bridge connects the two half-cells. It is filled Red: Cu2+ (aq) + 2e− → Cu (s)
with a saturated ionic solution of either KCl, NaCl, H2 is bubbled through the electrolyte over the inert platinum electrode.
KNO3 or Na2SO4. A concentrated solution is used to Reduction potentials are measured under standard conditions: Nett cell: Zn (s) + Cu2+(aq) → Zn2+ (aq) + Cu (s)
reduce the internal resistance. The ends of the tubes temperature 25 °C; 298 K For the zinc-copper cell:
are closed with a porous material such as cotton wool concentration of the solutions 1 mol·dm−3
or glass wool. The anode reaction is: Zn (s) → Zn2+ (aq) + 2e−; Eθ = −0,76 V
pressure 1 atm; 101,3 kPa (only relevant for gases) The cathode reaction is: Cu2+ (aq) + 2e− → Cu (s); Eθ = +0,34 V
Functions of the salt bridge:
Completes the circuit (which allows current to flow) Eθ cell = Eθ cathode − Eθ anode
Maintains the electrical neutrality of the electrolyte The cell-notation for the hydrogen half-cell is:
solutions. Pt | H2 (g) / H+ (aq) (1 mol⋅dm−3) = 0,34 − (−0,76)

EQUILIBRIUM IN A CELL = + 1,1 V (spontaneous)

When the circuit is complete the current will begin to EXAMPLE
flow. The current and potential difference of the cell
CELL NOTATION
Consider the cell notation of the following electrochemical cell: 
 
 
 

is related to the rate of the reaction and extent to
which the reaction in the cell has reached equilibrium. Pt | H2(g)/H2SO4(aq) (0,5 mol⋅dm−3)// CuSO4(aq) (1 mol⋅dm−3)/Cu(s)
As the chemical reaction proceeds, the rate of the The experimentally determined cell potential is 0,34 V at 25 °C.  


 

 




  

 


  
forward reaction will decrease, so the rate of transfer
of electrons will also decrease which results in the If a value of 0,00 V is given to the hydrogen half-cell, it means that






 



   


Eθcell value decreasing. the value of the copper half-cell must be 0,34 V.
The cell potential will continue to decrease gradually When the half-reactions do not include conductors (metals), unreactive electrodes
Eθ cell = Eθ cathode − Eθ anode
until equilibrium is reached at which point the cell are used, e.g. carbon or platinum.
potential will be zero and the battery is “flat”. 0,34 = Eθ (Cu) − 0,00 Pt(s)/H2(g)(1 atm)/H+(aq)(1 mol·dm–3)//Br2(g)(1 atm)/Br–(aq)(1 mol·dm–3)/Pt(s)
Le Chatelier’s principle can be applied to increase the
θ
EMF, with conditions that favour the forward reaction. E (Cu) = + 0,34 V Ca(s)/Ca2+(aq)(1 mol·dm–3 )//Fe3+(aq)(1 mol·dm–3), Fe2+(aq)(1 mol·dm–3)/C(s)

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 Grade 12 Science Essentials SCIENCE CLINIC 2022 ©
Electrochemistry- Electrolytic cells
An electrolytic cell reaction is always a non-spontaneous, ELECTROREFINING OF COPPER EXTRACTION OF ALUMINIUM (HALL-HEROLT PROCESS)
endothermic reaction which requires a battery. The electrical
energy is converted to chemical energy. Electrolytic cells When copper is purified, the process is similar to electroplating. Aluminium is found in the mineral known as bauxite which contains primarily
require a DC power source. Impure (blister) copper is used as the anode and the cathode is aluminium oxide (Al2O3) in an impure form.
pure copper.
STRUCTURE Bauxite is not found in South Africa so is imported from Australia for refining.
At the anode the copper is Step 1: Converting impure Al2O3 to pure Al2O3
Two electrodes (in the same container): oxidised to produce Cu2+  
 
Anode – where oxidation takes place – positive electrode Bauxite treated with NaOH – impure Al2O3 becomes Al(OH)3
ions in the electrolyte. The    
Cathode – where reduction takes place – negative electrode mass of the impure copper
 Al(OH)3 is heated (T > 1000 °C)
The anode and cathode are connected to an external circuit, anode decreases. 
which is connected to a DC power source. Al(OH)3 becomes pure Al2O3 – alumina
At the cathode the Cu2+ 
ions in the electrolyte is Step 2: Melting Al2O3

reduced to form a pure Alumina is dissolved in cryolite (sodium aluminium hexafluoride – Na3AlF6).
copper layer on the
cathode. The mass of the 













 Melting point reduced from over 2000 °C to 1000 °C.
cathode anode cathode increases.

Reduces energy requirements, costs and less environmental impact.

Step 3:
The less reactive elements and compounds found in the impure
 
copper anode are precipitated to the bottom of the reaction ves- Molten Alumina (Al2O3) – cryolite mixture placed in reaction vessel

sel. The more reactive metals (stronger reducing agents) are also
Anodes (+) are carbon rods in mixture
oxidised. The ions of these metals remain in the solution. Cu2+ is a

    
Cathode (-) is the carbon lining of the tank
stronger oxidising agent, thus it is preferentially reduced at the

cathode. Cu2+ stays constant. At cathode Al3+ ions are reduced to Al metal
ELECTROPLATING Oxidation (anode): Cu (s) → Cu2+ (aq) + 2e− 
 


Electroplating is the process of depositing a layer of one metal Reduction (cathode): Cu2+ (aq) + 2e− → Cu (s)
onto another metal.  


Nett cell: Cu2+ (aq) + Cu (s) → Cu2+ (aq) + Cu (s)
EXAMPLE: Silver plating of a metal spoon impure pure 

  
 

 
 
ELECTROLYSIS OF COPPER (II) CHLORIDE
The anode is silver, it will be oxi-
dised to Ag+ ions. The mass of the  
  
silver electrode decreases.

  



The cathode is the object (spoon)
 


to be plated. The Ag+ ions from the 

electrolyte will be reduced to form

silver metal, which plates the 

spoon. The mass of the cathode 

Oxidation (Anode): 2O2− (aq) → O2(g) + 4e− ×3
(spoon) increases. 


Reduction (Cathode): Al3+ (aq) + 3e− → Al (l) ×4

 Nett cell: 2Al2O3 (aq) → 4Al (l) + 3O2 (g)
The anode and electrolyte always
contains the plating metal. Oxidation (anode): 2Cl− (aq) → Cl2 (g) + 2e−
Reduction (cathode): Cu2+ (aq) + 2e− → Cu (s) Due to the high temperature of the reaction, the oxygen produced reacts
Oxidation (anode): Ag (s) → Ag+ (aq) + e−
Reduction (cathode): +
Ag (s) + e− → Ag (s) Nett cell: 2Cl− (aq) + Cu2+ (aq) → Cl2 (g) + Cu (s) with the carbon electrodes to produce carbon dioxide gas. The carbon
electrodes (anodes) therefore need to be replaced regularly.
Nett cell: Ag+ (aq) + Ag (s) → Ag+ (aq) + Ag (s)
Aluminium extraction uses a large amount of electrical energy, therefore the
+ Chlorine gas is produced at the anode, while copper metal is pro-
∴ [Ag ] stays constant cost of aluminium extraction is very high.
duced at the cathode.

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 Grade 12 Science Essentials SCIENCE CLINIC 2022 ©
Electrochemistry- Electrolytic cells
ELECTROLYSIS OF SOLUTIONS MEMBRANE CELL
In the electrolysis of NaCl, the Na+ ions are not reduced as might be An ion-exchange membrane is used to separate the sodium and chloride ions of the sodium chloride. The selectively permeable ion-
expected. To identify which ions are oxidised/reduced apply the exchange membrane is a fluoro-polymer which allows only Na+ ions to pass through it. The cell consists of two half cells separated by the
following rules (based on relative strength of OA/RA): membrane. The electrolytic cell has the lowest environmental impact. It is also the most cost effective to run, as the internal resistance is
far lower than that of the diaphragm and mercury cells.
OXIDATION (ANODE):
Either the anion or H2O will be oxidised. 

 



− − − − 
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If a HALOGEN ION (Cl , Br , I , not F ) is present, the HALOGEN ION
is oxidised.
The cathode is filled with pure water 



If no halogen ion is present, or the concentration is very low, water is
oxidised according to: At cathode - Reduction: 
"#
 
"#

2H2O (l) → O2 (g) + 4H+ (aq) + 4e− 2H2O (l) + 2e− → H2 (g) + 2OH− #
$
"#
$
"#

REDUCTION (CATHODE):

  
$

Either the cation or H2O will be reduced.
The anode is filled with the brine solution !




If a GROUP I OR GROUP II METAL CATION is present, WATER will be 
"#
&
"#

At anode - Oxidation: &
"# $

reduced according to:
2Cl− (aq) → Cl2 (g) + 2e−
2H2O (l) + 2e− → H2 (g) + 2OH− (aq) %
"#
%
"#

Water is reduced because it is a stronger oxidising agent than other
group I and II elements. If any other cation is present, the cation will
Nett cell: 2Cl− (aq) + 2H2O (l) → Cl2 (g) + H2 (g) + 2OH− (aq)
ELECTROLYSIS OF NaCl (CHLOR-ALKALI INDUSTRY) Overall reaction: 2NaCl (aq) + 2H2O (l) → Cl2 (g) + 2NaOH (aq) + H2 (g)
Brine (concentrated NaCl solution) is placed in an electrolytic cell to
produce chlorine gas, hydrogen gas and sodium hydroxide solution.
Overall reaction: 2NaCl(aq) + 2H2O(l) → Cl2(g) + 2NaOH(aq) + H2(g)
At the anode, Cl− ions are oxidised to form Cl2 (g). Cl2 gas bubbles
form on the electrode.
At the cathode, water is reduced to form H2 (g) and OH− (aq). H2 (g)
ctrode.
bubbles form on the electrode.






Oxidation (anode): 2Cl− (aq) → Cl2 (g) + 2e−
Reduction (cathode): 2H2O (l) + 2e− → H2 (g) + 2OH− (aq)
Nett cell: 2Cl− (aq) + 2H2O (l) → Cl2 (g) + H2 (g) + OH− (aq)
Overall reaction:
2NaCl (aq) + 2H2O (l) → Cl2 (g) + 2NaOH (aq) + H2 (g)
The electrolysis is conducted in specialised electrolytic cells to control
the reaction process and allow reactions to occur under controlled con-
ditions.

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