2 Electrochemistry (Semester 2)

TERM 2 CHEMISTRY CHAPTER 2 : ELECTROCHEMISTRY TEACHER ESTHER NGIENG
2.1 REDOX REACTIONS
1. Reduction and Oxidation
Oxidation Reduction
A process where electrons are lost A process where electrons are received
Increase in the oxidation state Decrease in the oxidation state
2. An oxidising agent undergo reduction while a reducing agent undergoes

oxidation.
3. Oxidation states of an element in a compound

Species Oxidation state
Free element (Cl2, O2, Br2, I2…) 0
Fluorine -1
Group 1 elements (Li, Na, K, Rb, Cs) +1
Group 2 elements (Be, Mg, Ca, Sr, Ba) +2
Group 13 elements +3
Hydrogen +1 (combine with non-metals)
-1 (combine with metals)
Oxygen -2
-1 (peroxide)
4. Writing half-equations
Step 1: Calculate the oxidation states for both reactant and product
Step 2: Differences of oxidation state:
(i) Oxidation state ↑, electrons are placed at the right side of
equation (OIL – Oxidation is LOSE electrons)
(ii) Oxidation state ↓, electrons are placed at the left side of
equation (RIG – Reduction is GAIN electrons)
Step 3: Balanced the number of atoms in both side of the equation
Step 4: Balance the other atoms

(i) Balance oxygen by adding water
(ii) Balance hydrogen by adding H+
Step 5: Based on the difference of oxidation state and number of atoms, the
number of electrons lose / gain are filled.
Exercise 1
Reaction Oxidation Reaction Half equation
state change
1
H2 → H+ 0 to +1 OXIDATION H2 → 2H+ + 2e-

Cl2 → Cl- 0 TO -1 REDUCTION Cl2 + 2e- → 2Cl-
O2 → O2- 0 TO -2 REDUCTION O2 + 4e- → 2O2-
Fe2+ → Fe3+ +2 TO +3 OXIDATION Fe2+ → Fe3+ + e-
Exercise 2
Substanc Changes of oxidation Half equation
e state and process
ClO3- →
Cl-
Cr2O72- →
Cr3+
MnO4- →
MnO2
5. A disproportionation reaction is a REDOX reaction where OXIDATION and

REDUCTION occur simultaneously on the SAME substance.
Exercise 3
Chlorine react with sodium hydroxide and disproportionate to become aqueous sodium
chloride and sodium hypochlorite.
REDUCTION
2
Equation: Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
Oxidation state:
OXIDATION
Exercise 4
Silicone monoxide disproportionate to silicon oxide and silicon under high temperature.
Equation:
Oxidation state:
2.2 STANDARD ELECTRODE POTENTIAL, Eᵒ

1. Half-cell and redox equation
 Danielle cell
Suggested answers
3
Salt bridge
Zinc metal
Negative electrode: Zinc metal

Positive electrode: Copper metal
Half-cell: each metal in contact with a solution of its ions
At the negative electrode:

zinc metal
2+
Half-cell equation: Zn(s) → Zn (aq) + 2e-
At the positive electrode:

copper metal
2+
Half-cell equation: Cu (aq) + 2e- → Cu(s)
2+ 2+
Overall reaction equation / redox equation: Cu (aq) + Zn(s) → Cu(s) + Zn
(aq)
2. Cell diagram (cell notation)
4
 When an inert electrode (Pt) is used, the species with the lowest oxidation
no. (the least oxidised form) is written next to the electrode
Pt │Fe2+ (aq) , Fe 3+(aq)
Function of salt bridge

(a) To complete the circuit by allowing the movement of ions
(b) To prevent the solution from mixing
Exercise 5
2Fe3+(aq) + H2(g) → 2Fe2+(aq) + 2H+(aq)

Based on the above reaction, write the cell notation.
Pt(s) │H2(g) │H+(aq) ║Fe3+(aq), Fe2+(aq) │ Pt(s)
Exercise 6
For the cells below, write the anode and cathode reactions and also the net
cell reaction:
(a) Pt(s) │ Ti2+(aq), Ti3+(aq) ││ Ni2+(aq) │ Ni(s)
Half equation (Anode): Ti2+(aq) → Ti3+(aq) + e-
Half equation (Cathode): Ni2+(aq) + 2e- →Ni(s)
Net cell / Overall equation : 2Ti2+(aq) + Ni2+(aq) → 2Ti3+(aq) + Ni(s)
(b) Pt(s) │ I- (aq)│ I2 (g) ││Pb4+(aq), Pb2+(aq) │Pt(s)
Half equation (Anode): 2I- (aq)→ I2 (g) + 2e-
5
Half equation (Cathode): Pb4+(aq) + 2e- → Pb2+(aq)
Net cell / Overall equation : Pb4+(aq) + 2I- (aq) → Pb2+(aq) + I2 (g)
3. Standard Electrode Potential, Eᵒ
3.1 Definition:
electromotive force (e.m.f.) / potential produced when a half-cell of the

element immersed in a 1.0 mol dm-3 solution of its ion is connected to
standard hydrogen electrode (SHE) at 298 K and 1.0 atm.
 Platinum is used as inert electrode for systems with no metallic

electrode of its own.
3.2 Standard Hydrogen Electrode (SHE)
 Labelled diagram: hydrogen gas, H2 (1.0 atm)

Platinum
Hydrochloric acid, HCl or H+ 1.0 mol dm-3, 25ᵒC
 The SHE consists of hydrogen gas (1.0 atm) bubbling around an inert
platinum electrode in a 1.0 mol dm-3 solution of hydrogen ions, H+ at
25ᵒC.
 It is assigned a value 0.00 V.
3.3 Determination of Standard Electrode Potentials

 When connected to the SHE
6
(i) If the half-cell is the POSITIVE terminal (CATHODE) = +Eᵒ

Reduction occurs at the cathode.
For example, Cu2+(aq) + 2e- → Cu(s) Eᵒ =+0.34 V
(ii) If the half-cell is the NEGATIVE terminal (ANODE) = -Eᵒ

Oxidation occurs at the cathode.
For example, Zn2+(aq) + 2e- → Zn(s) Eᵒ =-0.76 V
(iii)
(A) Systems of Metals in Aqueous Solution of Their Ions (Mn+/M)
Half reaction:
Anode
Cathode
Overall equation
Cell diagram
Eᵒ Zn2+/Zn H2/H+ = 0.00 V Eᵒ cell /e.m.f. = +0.76 V
7
(B) Systems of Gases and Their Aqueous Ions
Half reaction:
Anode
Cathode
Overall
equation
Cell diagram
Eᵒ F2/F- H2/H+ = 0.00 V Eᵒ cell /e.m.f. = +2.87 V
8
(C) Systems of Aqueous Ions Only
Half
reaction:
Anode
Cathode
Overall
equation
Cell
diagram
Eᵒ H2/H+ = 0.00 V Eᵒ cell /e.m.f. = +0.77 V
Fe3+/Fe2+
9
Exercise 7
With the aid of a diagram, describe how the standard electrode potential of the Mg 2+(aq)/Mg(s)
half-cell is determined. [6 marks]
M1 Standard electrode potential of the Mg2+(aq)/Mg(s) is
electromotive force (e.m.f.) / potential produced when a half-cell of the magnesium

metal immersed in a 1.0 mol dm-3 Mg2+ solution is connected to standard hydrogen
electrode (SHE) at 298 K and 1.0 atm.
M2 Half-cell equation Anode : Mg2+(aq) → Mg(s) + 2e-
Half-cell equation Cathode: 2H+(aq) + 2e- → H2(g)
M3 The standard electrode potential for SHE is assigned as 0.00 V.

M4 The voltmeter reading of Eᵒ Mg2+(aq)/Mg(s) is + 2.38 V.
M5 “– 2.38 V” indicates magnesium, Mg is negative electrode.
M6 Labelled diagram
magnesium plate
Mg 2+ (1.0 mol dm-3)

25ᵒC
10
3.4 Calculate the standard cell potential using Eᵒ and writing redox equation
 The Eᵒ value will not change when a half-equation is multiplied by a factor.

½ O2 + 2H+ + 2e- → H2O Eᵒ = +1.23 V
O2 + 4H+ + 4e- → 2H2O Eᵒ = +1.23 V
Exercise 8
Complete the table below and calculate the standard cell potential (e.m.f.) for the
electrochemical cell consisting of
(a) Zn2+/Zn and Ag+/Ag half-cells

Half-equation:
Anode Zn(s) → Zn2+ (aq) + 2e-
C
athode Ag+(aq) + e- → Ag(s)
Overall
equation Zn(s) + 2Ag+(aq) → Zn2+ (aq) + 2Ag(s)
Cell diagram
Zn(s) │ Zn2+ (aq) ║ Ag+(aq) │Ag(s)
Eᵒ cell /e.m.f. Eᵒ = Zn2+/Zn = -0.76 V Eᵒ = Ag+/Ag = +0.80 V
Eᵒ cell = Eᵒ cathode - Eᵒ anode
= +0.80 – (-0.76) V
= +1.56 V
(b) Zn2+/Zn and Cr3+/ Cr2+ half-cells
Half-equation:
Anode Zn(s) → Zn2+ (aq) + 2e-
C
athode Cr3+(aq) + e- → Cr 2+(aq)
Overall Zn(s) + 2Cr3+(aq) → Zn2+ (aq) + 2Cr 2+(aq)

equation
Cell diagram Zn(s) │ Zn2+ (aq) ║ Cr3+(aq), Cr 2+(aq) │Pt(s)
Eᵒ cell /e.m.f. Eᵒ = Zn2+/Zn = -0.76 V Eᵒ = Cr3+/Cr 2+ = -0.41 V

ᵒ ᵒ ᵒ
E cell = E cathode -E anode
= -0.41 – (-0.76) V
= +0.35 V
11
(c) Cl2/Cl- and I2/I- half-cells
Half-equation:
Anode 2I- (aq) → I2(s) + 2e-
C
athode Cl2 (g) + 2e- → 2Cl- (aq)
Overall
equation 2I- (aq) + Cl2 (g) → I2(s) + 2Cl- (aq)
Cell diagram Pt(s)│2I- (aq) │ I2(s) ║ Cl2 (g) │Cl- (aq) │Pt(s)
Eᵒ cell /e.m.f. Eᵒ = Cl2/Cl- = +1.36 V Eᵒ = I2/I- = +0.54 V

ᵒ ᵒ ᵒ
= +1.36 – (+0.54) V
= +0.82 V
(d) Cr2O72-/Cr3+ and Ti3+/Ti2+ half-cells
Half-equation:
Anode Ti2+ (aq) → Ti3 (aq) +e-
C
athode Cr2O72- (aq) + 14H+(aq) +6e- → 2Cr3+(aq) + 7H2O(l)
Overall
equation Cr2O72- (aq) + 14H+(aq) + 6Ti2+ (aq) → 2Cr3+(aq) + 7H2O(l) + 6Ti3 (aq)
Cell diagram Pt(s) │Ti2+ (aq), Ti3+ (aq) ║ Cr2O72- (aq), H+(aq), Cr3+(aq) │Pt(s)
Eᵒ cell /e.m.f. Eᵒ = Cr2O72-/Cr3+ = +1.33 V Eᵒ = Ti3+/Ti2+ = -0.37 V

ᵒ ᵒ ᵒ
= +1.33 – (-0.37) V
= +1.70 V
12
3.5 Predict the stability of aqueous ion from Eᵒ values
1. Certain elements such as transition elements can exhibit variable oxidation

states in their compounds. Example: Fe 2+ and Fe3+ and Cr2+ and Cr3+
2. But the relative stabilities of the ions in aqueous solution are NOT the same.
Eᵒ values can be used to compare the stability of aqueous ion.
Exercise 9
Cobalt(III) chloride, CoCl3 reacts with water to form cobalt(II) ions, Co 2+(aq).
Effervescence occurs and pink colour solution produced.
By using the values of the standard electrode potentials, Eᵒ values, of the
half-cells to explain the above observation. [5
marks]
M1
Half-equation anode: 2H2O(l) → O2(g) + 4H+(aq) +4e-
Eᵒ = -1.23 V
Half-equation cathode: Co3+(aq) + e- → Co2+(aq)

E ᵒ = +1.82 V
M2 Overall equation:
2H2O(l) + 4Co3+(aq) → O2(g) + 4H+(aq) + 4Co2+(aq)
M3
= +1.82 – (+1.23) V
= +0.59 V
M4 Explanation:
Co3+ reacts with water to form Co2+ (pink colour solution) with the
liberation of oxygen gas. (effervescence)
M5
Co2+ ion is more stable than Co3+ ion in aqueous solution.
13
3.6 Predict the power of oxidising and reducing agents from Eᵒ values
1. Written in reduction processes and arranged in increasing order of Eᵒ values.

2. The more positive the Eᵒ values of the oxidising agents / property (favours
reduction), the stronger its oxidising agent.
3. The more negative the Eᵒ values of the reducing agents / property (favours
oxidation), the stronger its reducing agent.
Exercise 10
Between Zn2+ and Cu2+ ion has the most powerful oxidising property? Explain your answer.
[3 marks]
Solution:
M1 Cu2+ ion has the most powerful oxidising property
Explanation:
M2 Zn2+ (aq) + 2e- Zn(s) Eᵒ = -0.76 V
Cu2+ (aq) + 2e- Cu(s) Eᵒ = +0.34 V
M3
More positive the Eᵒ values of the oxidising property, the stronger
its oxidising agent.
14
3.7 Predict the feasibility of a reaction from Eᵒ cell value
1. A positive value of cell e.m.f. indicates a spontaneous reaction under

standard conditions. Energetic feasible
2. A negative value of cell e.m.f. indicates a non-spontaneous reaction under
standard conditions.
3. However, it does not tell us anything about the rate of reaction. (kinetically
feasible). When the rate of reaction is too low to be noticeable then it is
kinetically not feasible.
4. Identify the reactants take place in a chemical reaction described.
Both position of reactants species must be in opposite. Medium in the salt
such as K+, Na+, SO42- and F- are usually not taking part in the reaction as they
are stable ions.
Exercise 11
Explain your answer why there is nothing happen at the end of reaction.
Anode: H2(g) → 2H+ (aq) +2e- Eᵒ= 0.00 V
Cathode: Cu 2+(aq) + 2e- → Cu(s) Eᵒ= +0.34 V

= +0.34 – 0.00 V
= +0.34 V
Comment :
Since the Eᵒ cell is positive, the reaction can occur spontaneously. (energetically feasible)
In actual fact, nothing seems to happen as the rate of reaction is too low and the reaction is
said to be kinetically not feasible.
Exercise 12
Deduce the spontaneity of these reaction using relevant standard reduction value.
(a) Chlorine gas is bubbled into titanium(III) ion
Half-equation and standard reduction potential

M1
M2 Overall equation
15
M3
M4 Since the Eᵒ cell is negative, the reaction can occur non-spontaneous

______________________________.
(b) Potassium iodide and acidified potassium manganate(VII) solution

M1
M2 Overall equation
M3
M4 Since the Eᵒ cell is positive, the reaction can occur spontaneous
______________________________.
(c) Aqueous iron(II) sulphate and acidified potassium dichromate(VI) solution

M1
M2 Overall equation
M3

______________________________.
16
(d) Acidified hydrogen peroxide and manganese(IV) oxide

M1
M2 Overall equation
M3

______________________________.
17
3.8 Factor affecting standard electrode potential, E
a) Concentration - depending of the species at each side of equilibrium,

changing concentration will caused Eᵒ value to increase / decrease
– increasing the concentration of both cell
Standard electrode potential Position of equilibrium Eᵒ cell value
Fe2+(aq) + 2e- → Fe(s) Equilibrium shift to Eᵒ cell > -0.44 V
Eᵒ = -0.44 V right (less negative)
Br2(l) + 2e- → 2Br-(aq) Equilibrium shift to left Eᵒ cell < +1.07 V
Eᵒ = +1.07 V (less positive)
b) Pressure –
 if the standard electrode potential is involving gas, changing P
will also influence the position of equilibrium
 ↑ P will shift the equilibrium to the direction with less total mole
increasing the pressure of the standard electrode potential
Standard electrode potential Position of equilibrium E cell value
F2(g) + 2e- → 2F-(aq) Equilibrium shift to E cell > +2.87 V
Eᵒ = +2.87 V right (more positive)
2HOCl(aq) + 2H+(aq) + 2e- → Equilibrium shift to left E cell < +1.64 V
Cl2(g) + 2H2O(l) (less positive)
Eᵒ = +1.64 V
c) Temperature – all electrochemical cell is exothermic process

 ↑ T will cause equilibrium to shift to backward reaction, hence to
the left, decreasing the E value.
Temperature Position of equilibrium E cell value
Increase, ↑ Equilibrium shift to left ↓ E value
Decrease, ↓ Equilibrium shift to right ↑ E value
2.3 NERNST EQUATION (NON-STANDARD CELL POTENTIALS), E
18
Nernst equation shows the relationship between the electrode potential and
the concentration of ions.
1. To calculate E of a half-cell involving using Nernst equation

 The concentration of solid is NOT included in the Nernst equation.
Exercise 13
Calculate the electrode potentials for the following half-cells at 298K.

(a) Ag+ (1.5 mol dm-3)│Ag(s)
(b) Co3+ (0.50 mol dm-3)│Co2+ (0.20 mol dm-3)
19
(c) MnO4- (1.2 mol dm-3); H+(0.80 mol dm-3)│Mn2+ (0.60 mol dm-3)
2. To calculate Ecell of an electrochemical cell using Nernst equation
 Similar as in chemical equilibria, pure SOLID and pure LIQUID will NOT
be involved in the calculation as their concentration is too great/constant.
Exercise 13
Based on the cell diagram given, write the overall equation, calculate the Eᵒcell and Ecell the
of the reaction.
(a) Cr(s) │Cr3+(0.010 mol dm-3)║Ni2+(0.20 mol dm-3)│Ni(s)
Standard
electrode
potential for
half-cell
20
Overall
equation
Eᵒcell Eᵒcell = -0.25 – (-0.74) V
= +0.49 V
Nernst
equation,
Ecell
(b) Mg(s) │Mg2+(0.500 mol dm-3)║Fe3+(1.80 mol dm-3), Fe2+(0.750 mol dm-3)│Pt(s)
Standard
electrode
potential for
half-cell
Overall
equation
Eᵒcell Eᵒcell = +0.77 – (-2.38) V
Nernst = + 3.15 V
equation,
Ecell
(c) Pt(s)│Sn2+(0.300 mol dm-3), Sn4+(0.500 mol dm-3)║Mn3+(1.20 mol dm-3),

Mn2+(0.250 mol dm-3)│Pt(s)
Standard
electrode
potential for
half-cell
Overall
equation
Eᵒcell Eᵒcell = +1.49 – (- 0.15) V
= + 1.64 V
21
Nernst
equation,
Ecell
1.64 V
+1.67 V
(d) Al(s) │Al3+(0.500 mol dm-3)║Pb4+(0.60 mol dm-3), Pb2+(0.35 mol dm-3)│Pt(s)
Standard
electrode
potential for
half-cell
Overall
equation
Eᵒcell Eᵒcell = +1.69 – (-1.66) V
= 3.35 V
Nernst
equation,
Ecell
3. Concentration cell
A concentration cell from two half-cells composed of the same material
but different ion concentration.
22
According to Le Chatelier principle’s, an increase in concentration of ions will shift the

equilibrium to the right. (reduction occurs)
Zn2+(aq) + 2e- Zn(s)
Half-equation
Oxidation
(more dilute)
Half-equation
Reduction
(more
concentrated
)
Overall
Cell diagram
Ecell Eᵒcell = 0 as the same electrode and the same type of ion are
involved (no potential difference under standard condition)
- dilute
conc
- 0.1
1.0
Exercise 14
Calculate the e.m.f of the concentration cell for
Fe(s) │Fe3+(1.0 mol dm-3)(aq)║Fe3+(2.5 mol dm-3)(aq)│Fe(s)
Half-equation
Oxidation
(more dilute)
Half-equation
Reduction
23
(more
concentrated)
Overall
Cell diagram Fe(s) │Fe3+(1.0 mol dm-3)(aq)║Fe3+(2.5 mol dm-3)(aq)│Fe(s)
Ecell
- dilute
conc
- 1.0
2.5
4. A change in the concentration of a species in the cell will cause the

following changes.
(a) When the forward reaction occurs, the cell e.m.f. increases
(b) When the reverse reaction occurs, the cell e.m.f. decreases
5. When an electrochemical cell is allowed to reach until equilibrium is

achieved:
(a) Q = Kc
(b) Ecell = 0
Exercise 15
Consider the following reaction which allowed to reach an equilibrium.
2 Fe3+(aq) + Cu(s) → 2Fe2+(aq) + Cu2+(aq)
Standard
electrode
potential for
half-cells
24
Overall
equation
Ecell
Kc Write the expression for Kc
6. Nernst equation and pH of solution in SHE

(a) The chemical cell are set-up by connecting a SHE to a M 2+/M half-cell in a
diagram below
25
(b) Given the M2+/M half-cell is the ANODE, while SHE is the CATHODE.
M2+/M half-cell (ANODE) : M(s) → M2+(aq) + 2e- Eᵒ = +a V
SHE half-cell (CATHODE) : 2H+(aq) + 2e- → H2(g) Eᵒ = 0 V
(c) Cell diagram of the above reaction
26
2.4 FUEL CELLS
Definition: is an electrochemical cell which converts the chemical energy of a

continuous supply of reactants into electrical energy
27
The fuel hydrogen
The oxidising agent oxygen (REDUCTION)
The electrodes used porous nickel
Standard electrode
potential at the H2(g) +2OH-(aq) → 2H2O(l) + 2e- (oxidation)
negative terminal
Eᵒ = +0.83 V
Standard electrode
potential at the O2(g) +2H2O(l) + 4e- → 4OH-(aq) (reduction)
positive terminal
Eᵒ = +0.40 V
Overall equation 2H2(g) + O2(g) → 2H2O(l)
Eᵒ cell = +1.23 V_____
State the advantages and disadvantages of hydrogen fuel cell.

Advantages
1. Fuel cells can be used produce power for an electric motor as well as directly
producing electricity in place of a generator.
In either case they facilitate the replacement of a gasoline or diesel engine.
28
2. The fuel cell produces no greenhouse gases or other air pollutants. The product of
the chemical reaction is only water and a small amount of heat. The production of
hydrogen may involve some pollutants, but these are far less than what is
produced in combustion.
3. Because the fuel is a material that is readily available, it poses few issues of energy
and national security, unlike the importation of petroleum.
Disadvantages
1. A major obstacle to widespread use of fuel cells is in the storage and distribution
of hydrogen fuel. Hydrogen gas is difficult to contain, and most methods add
considerable weight to a vehicle. Transporting and dispensing the gas will also
require new methods.
Because if its volatility, the safety of hydrogen gas will always be a concern, and
this may hinder public acceptance.
2. The operation of cells in very cold weather is a problem, since water is always
present in and around the cell.
3. Presently the cost of fuel cells is not competitive.
2.5 ELECTROLYSIS
Definition: The process in which electrical energy is used to cause a non-

spontaneous chemical reaction to occur.
Electrolytic cell
29
 Electrolyte
Labelled diagram Substance that have mobile
electron and can conduct
electricity when in aqueous
solution or in molten state
 Electrode
Solids which are immersed into
the electrolyte to direct the
current and undergoes
electrolysis
 Electrolytic cell
Cell consisting of 2 electrodes
immersed in an electrolyte for
carrying out electrolysis
3.5.1 Comparison electrolytic cell and electrochemical cell
Electrolytic cell Compare and Electrochemical cell

contrast
1 Electrical energy to chemical Energy Chemical energy to electrical
energy change energy
30
2 Redox reaction occurs. Types of Redox reaction occurs.

Oxidation occurs at anode while reactions Oxidation occurs at anode while
reduction occurs at cathode. reduction occurs at cathode.
3 Cathode is the negative Charge of Cathode is the positive electrode
electrode while anode is the electrodes while anode is the negative
positive electrode. electrode.
3.5.2 Factors affecting the types of products formed during electrolysis

(i) The value of electrode reduction potential, Eᵒ/ the position of
the ions in the electrochemical series when inert electrodes
are used in an aqueous solution
Molten state (liquid formed from solid by heating)
Exercise 16
Molten lead(II) bromide, PbBr2(s) Dissociation equation:
Half-equation at cathode: REDUCTION

Half-equation at anode:OXIDATION
Molten magnesium oxide, MgO(s) Dissociation equation:
Half-equation at anode:
Half-equation at cathode:
Aqueous Solution
Exercise 17
Electrolyte Ions Half equation at Product Half equation at Product

present anode (+) anode cathode (-) cathode
31
(a)Copper oxygen Copper

(II)sulphate, gas
CuSO4
a
colourles
s gas
that
relight
glowing
wooden
splinter
(b) Lead(II) Iodine Lead

iodide,PbI2
(c) oxygen hydrogen

Potassium gas gas
hydroxide,
KOH
(ii) The concentration of ions in the electrolyte
 Species with a higher concentration is preferentially discharged. But factor

concentration is NOT applied if the difference of Eᵒ is very big.
32
 If concentrated halide ions like Cl-, Br- and I- are used, halide ions will be
selected for discharged to produce halogens instead of H2O.
 Overvoltage effect
- additional voltage which is required for gases such as H2(g) and O2(g)
which produced at metal electrode as a result from kinetic factors, such
as the large activation energy required for gases to form at the
electrode.
Exercise 18
Electrolysis of sodium chloride (NaCl) 2.0 mol dm-3 aqueous solution
Ions at anode(+):
Ions at cathode(-):
Half equation for substance attracted to anode Half equation for substance attracted to
cathode
Product anode: Chlorine gas Product cathode: Hydrogen gas
(iii) The nature of electrodes used

 Occur for active electrodes such as Cu and mercury electrodes.
Exercise 19
Electrolysis of saturated sodium chloride, NaCl(aq) using mercury as cathode
Na+(aq) is selected for discharged as sodium produced forms sodium amalgam,

Na/Hg even though the Eᵒ value is very negative as compare to H2O.
Exercise 20
Electrolysis of AgNO3(aq) using silver as anode
Silver is oxidised to Ag+ ion instead of water and anode dissolves.
3.5.3 Faraday’s First Law and Faraday’s Second Law
33
(i) Definition Faraday’s First Law

the amount of substance produced at each electrode is directly
proportional to the quantity of charge flowing through the cell.
Exercise 21
(a) An aqueous solution of copper(II) sulphate is electrolysed using a current of 0.50 A for
4 hours. Calculate the mass of copper, Cu deposited at cathode.
(b) An aqueous solution of chromium(III) sulphate was electrolysed for five hours, using a
constant current of 1.5 A. Calculate the mass of chromium deposited and the volume
34
of oxygen gas produced at s.t.p. [Ar Cr:52.0; F=96 500 C mol -1]
Exercise 22
Calculate the time needed to produce the following at s.t.p. if a current of 5.0 A is used in the
35
electrolysis.
(a) 1.395 g iron from 1.0 mol dm-3 solution of iron(II) sulphate
(b) 6.213 g zinc from 2.0 mol dm-3 solution of zinc chloride
[Ar : Fe, 55.8; Zn, 65.4; Cu, 63.5; Ag,108; 1F = 96500 C mol -1; Molar volume = 22.4 dm 3 at
s.t.p.]
(c) 112 cm3 chlorine from 5.0 mol dm-3 solution of potassium chloride
36
(d) 6.72 dm3 oxygen from molten aluminium oxide
[Ar : Fe, 55.8; Zn, 65.4; Cu, 63.5; Ag,108; 1F = 96500 C mol -1; Molar volume = 22.4 dm 3 at
s.t.p.]
(ii) Definition Faraday’s Second Law
37
If the same quantity of electricity is passed through different

electrolytes, the mass of substance liberated at electrode is inversely
proportional to the charge of ions.
38
Exercise 23
When a certain amount of electric charge flows through an aqueous solution of silver nitrate,
3.24 g of silver is deposited on the cathode. Calculate:
(a) The mass of copper and
(b) The mass of Al, that will be deposited by the same quantity of charge
39
Exercise 24
An electric current produced 0.56 g of aluminium from molten aluminium oxide. If the same
current was used to electrolysed molten lead(II) bromide, calculate the mass of lead deposited.
40
2.6 APPLICATION OF ELECTROCHEMISTRY
2.6.1 Corrosion/Rusting of iron

READ TEE
2.6.2 Extraction of aluminium
2.6.3 Anodisation of aluminium
2.6.4 The diaphragm cell / Chlor-alkali cell
2.6.5 Treatment of industrial effluent
2.6.6 Electroplating of coated plastics
2.6.1 Corrosion/Rusting of iron

Definition for Rusting of iron
deterioration (kemerosotan) of iron metal to iron(III) oxide that occur naturally
under continuous exposure to air and water. In such case, iron(III) oxide
caused the iron to become brittle (rapuh) hence deteriorate the iron metal.
41
Rusting process in iron under ACIDIC CONDITION

At anode At cathode
Overall
E ᵒ cell = Eᵒ cathode -Eᵒ anode
At anode At cathode
Overall
Forming rust:
Rusting process in iron under AlKALINE CONDITION

At anode At cathode
Overall

At anode At cathode
Overall

Forming rust:
42
Prevention of corrosion (rusting of iron)
(i) Electroplating
Iron object to be plated as cathode and electroplating metal as anode while the
electrolyte is an aqueous solution of electroplating metal ions
(ii) Sacrificial anode

Metals which is more electropositive than iron such as magnesium is used as
sacrificial anode. Magnesium is oxidised instead of iron. Iron acts as cathode is
protected from rusting.
(iii)
Galvanisation
43
The process where the surface of iron is coated with a layer of zinc.
Iron will NOT rust as zinc is present. Zinc will be oxidised instead of iron as zinc is
more electropositive than iron.
2.6.2 Extraction of aluminium from bauxite, Al2O3.2H2O
44
(a) Electrolyte : Aluminium oxide in molten cryolite at 900ᵒC

Cathode :Carbon Al 3+ + 3e- → Al
Anode : Carbon 2O2-→ O2(g) + 4e-
Al2O3 is an ionic compound with a high melting point of about 2070 ᵒC.
Cryolite is used to lower temperature to 900ᵒC.
(b) The oxygen gas will react with the hot carbon electrode to form carbon dioxide and
carbon moxoxide.
The anode will be corroded slowly and must be replaced from time to time.
(c) Extraction of aluminium using electrolysis requires large amount of energy and is an
expensive process as a high current is used to maintain the temperature.
(d) Aluminium is recycled.

Extraction of 1 mole of aluminium requires 297 kJ whereas recycling from used
aluminium only requires 26.1 kJ. This process saves about 91%.
2.6.3 Anodisation of aluminium
45
Platinum or Carbon
aluminium object
(a) Meaning of anodisation

An electrolytic process whereby a metal anode is oxidised to form a
protective layer of the metal oxide
(b) Purpose
To increase the thickness of the oxide layer.
To increase corrosion resistance
(c) Anode(+) : Aluminium metal

Oxygen gas reacts with aluminium anode to form aluminium oxide as
coating.
2H2O → O2(g) + 4H+ + 4e-
4Al + 3O2(g) → 2Al2O3
Cathode(-) : Inert electrode such as carbon or platinum
Electrolyte : dilute sulphuric acid
2.6.4 The diaphragm cell /Chlor-alkali cell(Chlor=chlorine, alkali=alkali metal,

Na)
46
NaCl(aq) + NaOH(aq)
Asbestos diaphragm
(a) Anode(+) : Titanium or graphite

Half equation : 2Cl-(aq) → Cl2(g) +2e-
Cathode(-) : steel/ nickel

Half equation : 2H2O(l) +2e- → 2OH-(aq) + H2(g)
Overall equation
2H2O(l) + 2NaCl(aq) → Cl2(g) + 2NaOH(aq) + H2(g)
Electrolyte : Brine ( saturated NaCl)
(b) The brine in the anode compartment is kept at a slightly higher pressure than the brine
in the cathode compartment.
 The OH- ions are prevented from moving through the asbestos diaphragm into the
anode compartment, and
47
 Na+ ions can migrate to the cathode compartment more readily
(c) The asbestos diaphragm allows the flow of ions through it but prevents chlorine from
reacting with hydrogen and sodium hydroxide solution.
(d) Disadvantage of diaphragm cell is sodium hydroxide solution produced is NOT pure
as it is contaminated with some unelectrolysed sodium chloride
2.6.5 Treatment of industrial effluent

Industrial waste water which sometimes contain heavy metal ion (Ni2+, Cr3+,
Cd2+)
Bad effect to human health
Metals ion can contaminate drinking water and cause heavy metal
poisoning.
Accumulate in human body to form carcinogen and triggered cancerous
cell in human body
These ions are reduced to metals at cathode by electrolysis under
controlled conditions where the heavy metals are deposited at cathode,
are filtered off from electrolyte and are collected for reused.
Half equations: Mn+ + ne- → M
Common method to remove heavy metal : applying electrolytic membrane
discharging the metal ions to form metal and absorbed by membrane layer.
2.6.6 Electroplating of coated plastics
48
Meaning: the coating of one metal on the surface of another using electrolysis
Purpose:
To improve the appearance of the plastic objects
To increase the resistance to corrosion
Initially, the plastic object is coated with a thin layer of graphite so that it can conduct
electricity
Anode : Pure metal (silver, gold, nickel or chromium)
Cathode: plastic object to be plated
Electrolyte : An aqueous solution of electroplating metal ions

Example : Half equation occur for electroplating process of silver
Anode : Ag(s) → Ag+(aq) + e-
Cathode : Ag+(aq) + e- → Ag(s)
49

2 Electrochemistry (Semester 2)

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2 Electrochemistry (Semester 2)

Uploaded by

Copyright:

Available Formats

TERM 2 CHEMISTRY CHAPTER 2 : ELECTROCHEMISTRY TEACHER ESTHER NGIENG

2.1 REDOX REACTIONS

1. Reduction and Oxidation

2. An oxidising agent undergo reduction while a reducing agent undergoes

3. Oxidation states of an element in a compound

Step 4: Balance the other atoms

H2 → H+ 0 to +1 OXIDATION H2 → 2H+ + 2e-

5. A disproportionation reaction is a REDOX reaction where OXIDATION and

Equation: Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)

2.2 STANDARD ELECTRODE POTENTIAL, Eᵒ

Negative electrode: Zinc metal

At the negative electrode:

At the positive electrode:

2. Cell diagram (cell notation)

Function of salt bridge

2Fe3+(aq) + H2(g) → 2Fe2+(aq) + 2H+(aq)

Pt(s) │H2(g) │H+(aq) ║Fe3+(aq), Fe2+(aq) │ Pt(s)

Half equation (Anode): Ti2+(aq) → Ti3+(aq) + e-

Half equation (Cathode): Ni2+(aq) + 2e- →Ni(s)

Net cell / Overall equation : 2Ti2+(aq) + Ni2+(aq) → 2Ti3+(aq) + Ni(s)

(b) Pt(s) │ I- (aq)│ I2 (g) ││Pb4+(aq), Pb2+(aq) │Pt(s)

Half equation (Anode): 2I- (aq)→ I2 (g) + 2e-

Half equation (Cathode): Pb4+(aq) + 2e- → Pb2+(aq)

Net cell / Overall equation : Pb4+(aq) + 2I- (aq) → Pb2+(aq) + I2 (g)

3. Standard Electrode Potential, Eᵒ

electromotive force (e.m.f.) / potential produced when a half-cell of the

 Platinum is used as inert electrode for systems with no metallic

3.2 Standard Hydrogen Electrode (SHE)

 Labelled diagram: hydrogen gas, H2 (1.0 atm)

Hydrochloric acid, HCl or H+ 1.0 mol dm-3, 25ᵒC

3.3 Determination of Standard Electrode Potentials

(i) If the half-cell is the POSITIVE terminal (CATHODE) = +Eᵒ

(ii) If the half-cell is the NEGATIVE terminal (ANODE) = -Eᵒ

(A) Systems of Metals in Aqueous Solution of Their Ions (Mn+/M)

Eᵒ Zn2+/Zn H2/H+ = 0.00 V Eᵒ cell /e.m.f. = +0.76 V

(B) Systems of Gases and Their Aqueous Ions

Eᵒ F2/F- H2/H+ = 0.00 V Eᵒ cell /e.m.f. = +2.87 V

(C) Systems of Aqueous Ions Only

M1 Standard electrode potential of the Mg2+(aq)/Mg(s) is

electromotive force (e.m.f.) / potential produced when a half-cell of the magnesium

M2 Half-cell equation Anode : Mg2+(aq) → Mg(s) + 2e-

Half-cell equation Cathode: 2H+(aq) + 2e- → H2(g)

M3 The standard electrode potential for SHE is assigned as 0.00 V.

Mg 2+ (1.0 mol dm-3)

 The Eᵒ value will not change when a half-equation is multiplied by a factor.

(a) Zn2+/Zn and Ag+/Ag half-cells

Eᵒ cell /e.m.f. Eᵒ = Zn2+/Zn = -0.76 V Eᵒ = Ag+/Ag = +0.80 V

Eᵒ cell = Eᵒ cathode - Eᵒ anode

(b) Zn2+/Zn and Cr3+/ Cr2+ half-cells

Overall Zn(s) + 2Cr3+(aq) → Zn2+ (aq) + 2Cr 2+(aq)

Eᵒ cell /e.m.f. Eᵒ = Zn2+/Zn = -0.76 V Eᵒ = Cr3+/Cr 2+ = -0.41 V

(c) Cl2/Cl- and I2/I- half-cells

Eᵒ cell /e.m.f. Eᵒ = Cl2/Cl- = +1.36 V Eᵒ = I2/I- = +0.54 V

(d) Cr2O72-/Cr3+ and Ti3+/Ti2+ half-cells

Eᵒ cell /e.m.f. Eᵒ = Cr2O72-/Cr3+ = +1.33 V Eᵒ = Ti3+/Ti2+ = -0.37 V

3.5 Predict the stability of aqueous ion from Eᵒ values

1. Certain elements such as transition elements can exhibit variable oxidation

Half-equation cathode: Co3+(aq) + e- → Co2+(aq)

2H2O(l) + 4Co3+(aq) → O2(g) + 4H+(aq) + 4Co2+(aq)

1. Written in reduction processes and arranged in increasing order of Eᵒ values.

M1 Cu2+ ion has the most powerful oxidising property

Cu2+ (aq) + 2e- Cu(s) Eᵒ = +0.34 V

3.7 Predict the feasibility of a reaction from Eᵒ cell value

1. A positive value of cell e.m.f. indicates a spontaneous reaction under