Electrochemistry
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Understanding Electrochemistry
ELECTROCHEMISTRY
refers to chemical reactions during which
CHEMICAL ENERGY is converted to ELECTRICAL ENERGY
or
ELECTRICAL ENERGY to CHEMICAL ENERGY.
Electrochemical processors involves oxidation-reduction reactions called redox reactions,
where electrons are transferred between substances.
A Redox reaction can be represented by two half reactions:
An oxidation half reaction and
A reduction half reaction
An easy way to remember which reaction does what, is to use OIL RIG, which
stands for:
Oxidation Is Loss of electrons Reduction Is Gaining of electrons
Real life example of redox reaction is
rusting. Oxygen steals electrons from iron
to form iron oxide, which is commonly
known as rust
Oxidation Reduction
Is the loss of electrons by a substance Is the gain of electrons by a substance
such as an atom, molecule or ion. such as an atom, molecule or ion.
When these substances are oxidised When these substances is reduced
(loses electrons), it is called a (gains electrons), it is called an
REDUCING AGENT OXIDISING AGENT.
The oxidation number of a compound The oxidation number of a compound
that is oxidised increases (becomes that is reduced, decreases (becomes
less negative, or becomes more more negative, or becomes less
positive positive
Electrochemical Cells
Understanding Galvanic (Voltaic) Cells
Converts CHEMICAL ENERGY into ELECTRICAL ENERGY
Template for answering Galvanic Cells
Cell Notation
A shortened cell notation can be used to represent the galvanic cell:
The cell terminals (electrode) are written on the far left and right hand sides of the
cell notation. The anode is always on the left hand side and the cathode on the
right.
Salt bridge
For active electrodes:
Reducing agent Oxidisied species Oxidising agent Reduced species
OR
anode Electrolyte in contact with Electrolyte in contact with cathode
anode cathode
Example:
Zn
Cu
Zn2+ Zn2+ Cu2+ Cu2+
Zn2+ Cu2+
Zn (s) Zn2+ (aq) Cu2+ (aq) Cu (s)
Half-Cell Reaction Potential
As mentioned, a galvanic cell consists of two metals that are connected by a
salt bridge between the individual half-cells which generates electricity using
the reactions that take place that take place at these two metals, each of which
has a different reaction potential.
Every metal has a different half reaction and different dissolving rates.
When two metals with different reaction potential are used in a galvanic cell, a potential
difference is set up between the two electrodes and the result is a flow of current
through the wire that connects the electrodes.
Negative e- on -
The tendency (potential) of an
the electrode
electrode/electrolyte to be oxidised or -
reduced determines which reaction takes -
place at which half-cell +
- +
Positive ions
+
+
In the half cell where OXIDATION occurs, the electrode has a negative charge and the
electrolyte has a positive charge
In the half cell where REDUCTION occurs, the electrode has a positive charge and the
electrolyte has a negative charge
A potential difference forms between the negative electrode and the positive
solution. This is called the electrode potential (half-cell potential)
Reactivity Series
A list of substances which are arranged in order of their ability to act as reducing agents
or as oxidising agents.
The Table of Standard Reduction Potentials lists the standard electrode
potentials (E0 values) for various compounds. There are two tables, they
are similar, but the entries are arranged in opposite directions.
We will be focussing on Table 4B
The tables of Standard Reduction Potentials can be used to:
o identify oxidising and reducing agents
o write balanced redox reaction equations
o predict whether a redox reaction takes place spontaneously or not
o calculate the emf of a voltaic cell by using one of the following formulae (formulas):
Eθcell = Eθcathode - Eθanode
OR
Eθcell = Eθoxidising agent - Eθreducing agent
Table of standard reduction potentials
Table 4B
Half-reactions Eθ (V)
Li+ + e- ⇌ Li - 3,05
K+ + e- ⇌ K - 2,93
Cs+ + e- ⇌ Cs - 2,92
Ba2+ + 2e- ⇌ Ba - 2,90
Sr2+ + 2e- ⇌ Sr - 2,89
Ca2+ + 2e- ⇌ Ca - 2,87
Sn2+ + 2e- ⇌ Sn - 0,14
Pb2+ + 2e- ⇌ Pb - 0,13
Fe3+ + 3e- ⇌ Fe - 0,06
2H+ + 2e- ⇌ H2(g) 0,00
S + 2H+ + 2e- ⇌ H2S(g) + 0,14
Sn4+ + 2e- ⇌ Sn2+ + 0,15
Cu2+ + e- ⇌ Cu+ + 0,16
SO42- + 4H+ + 2e- ⇌ SO2(g)+H2O + 0,17
H2O2 + 2H+ +2 e- ⇌ 2H2O +1,77
Co3+ + e- ⇌ Co2+ + 1,81
F2(g) + 2e- ⇌ 2F- + 2,87
Either of the Standard Reduction Potential Tables given in the exam
sheets may be used
Understanding Table of Standard
Reduction Potentials
When using Table 4B,
the strongest reducing agent is at the top
(therefore the half cell with the most negative reduction potential is at the top)
&
the strongest oxidising agent is at the bottom
(therefore, the half-cell with the most positive reduction potential is at the bottom).
How to read Table 4B Table of standard reduction potentials
Half-reaction Eθ (V)
Li+ + e- ⇌ Li - 3.05 V
Reducing Agent Strength of Reducing
Strength of Oxidising
Oxidation half-reaction
Agent Increases
Agent Increases
Oxidising Agent
Reduction half-reaction
F2 + 2e- ⇌ 2F- + 2.87 V
The oxidation half-reaction must always be written from right
to left
The reduction half-reaction must always be written from left to
right
Electrolysis
Electrolysis is the chemical process where electrical energy
is converted into chemical energy
This is a process that would not usually occur, therefore we use a battery to split up the
compound into its constituents. This done by pulling or pushing of electrons form the
battery
Let us take Table salt as an example and look at its oxidation numbers
Chlorine loses electrons
Oxidation occurs
+ 1 -1 0 0
2 NaCl (l) 2 Na (l) + Cl2(g)
Sodium gains electrons
Reduction occurs
Understanding Electrolytic Cells
The instrument used in order to conduct electrolysis is an Electrolytic cell.
The positive electrode(anode) is connected to the + terminal of the battery.
• This attracts the negative ions (anions) to move to the anode where they are
oxidised
The negative electrode(cathode) is connected to the - terminal of the battery.
• This attracts the positive ions (cations) to move to the cathode where they are
reduced
• The electrons move via the external circuit to the cathode
Electrodes are made from unreactive substances are placed in the SAME ionic solution.
The electrons flow in the external circuit from the negative pole of the battery to the
cathode (-)
WORKED Exam Question Paper 2, Nov 2022, Q.8
WORKED Exam Question Paper 2, Nov 2022, Q.9
WORKED Exam Question Paper 2, Oct/Nov 2019, Q.8
A standard electrochemical cell is set up using two standard half-cells, as shown in t
the diagram below.
.
8.1 State the energy conversion that takes place in this cell. (1)
The energy conversion is Chemical to electrical
8.2 What is the function of component Q? (1)
This is the Salt bridge and there are various functions for this:
Provides path for movement of ions.
Completes the circuit.
Ensures electrical neutrality in the cell.
Restore charge balance
X is a metal. A voltmeter connected across the cell initially registers 1,49 V.
8.3 Use a calculation to identify metal X. (5)
Provides path for movement of ions.
Completes the circuit.
Ensures electrical neutrality in the cell
/Restore charge balance
WORKED Exam Question Paper 2, Oct/Nov 2019, Q.8
8.4 Write down the NAME or FORMULA of the reducing agent. (1)
The reducing agent wich is also X can wither be given by the
periodic symbol Pb or the chemical name Lead
5. The reading on the voltmeter becomes ZERO after this cell operates for several hours.
1. Give a reason for this reading by referring to the rates of oxidation and
reduction half-reactions taking place in the cell. (1)
Reaction reached equilibrium./(In each half cell) the rate of oxidation is equal to
rate of reduction./Rate of the forward reaction is equal to the rate of the reverse
reaction.
A silver nitrate solution, AgNO3(aq), is NOW added to the chlorine half-cell and
a precipitate forms.
8.5.2 How will the reading on the voltmeter be affected?
(Choose from INCREASES, DECREASES or REMAINS the same) (1)
The Voltmetre reading would INCREASES due to the addition of silver
nitrate solution, AgNO3(aq) added to the chlorine half-cell
8.5.3 Use Le Chatelier's principle to explain the answer to QUESTION 8.5.2. (2)
Due to the increase silver nitrate solution,
AgNO3(aq), which was added to the chlorine half-
cell, the [Cℓ-] should DECREASE in order to
restore balance.
Therefore the Forward reaction is favoured.
Past Exam Question Paper 2, May/June 2019, Q.8
The electrochemical cell below functions under standard conditions.
1. Give a reason why platinum is used as the electrode in half-cell A. (1)
2. Write down the:
1. Energy conversion that takes place in this cell (1)
2. Half-reaction that takes place at the cathode (2)
3. Cell notation for this cell (3)
3. Calculate the initial emf of this cell. (4)
4. Silver chloride is an insoluble salt.
What will be the effect on the cell potential when a small amount of silver nitrate
solution, AgNO3(aq), is added to half-cell A? Choose from INCREASES,
DECREASES or REMAINS THE SAME. (2)
Past Exam Question Paper 2, Oct/Nov 2018, Q.8
8.1 Corrosion is a redox reaction that takes place in the presence of oxygen and
water. Rusting is the corrosion of iron leading to the formation of iron(III)
ions.
.8.1.1 Define oxidation in terms of electron transfer. (2)
A cleaned copper rod and a cleaned iron nail are placed in a beaker
containing water at 25°C, as shown below.
.
After a while it was observed that the iron nail was coated with rust. The
copper rod showed no visible signs of corrosion.
.
8.1.2 Write down the half-reaction for the iron nail. (2)
3. Does iron act as REDUCING AGENT or OXIDISING AGENT in the beaker? (1)
4. Explain the above observation by referring to the Table of Standard
Reduction Potentials
To prevent
. rusting of an underground iron pipe, the pipe is connected to a
metal (Q) that corrodes easily.
8.1.5 You are given two metals, Zn and Cu, to use as metal Q.
Which metal would more suitable? Give a reason. (2)
8.2 A galvanic cell is constructed using a Fe | Fe3+ half-cell and a Cu | Cu2+
.
half-cell.
8.2.1. Write down the overall (net) cell reaction that takes place when the
cell is functioning. (3)
8.2.2. Calculate the cell potential of this cell under standard conditions. (4)
