Chapter 19 Electrochemistry

19.1 Introduction 19.6 Electrolysis

19.2 Electrode potential • Molten electrolytes
• Standard hydrogen electrode (SHE) • Aqueous electrolytes
• Standard electrode potential, Eϴ
is the emf of a ½ cell • Factors in identifying which ion are to be discharge
when it is connected to stand hydrogen electrode at 1
1. The relative electrode potential of the ions
mol dm-3 ion concentration, 298 K and 1 atm.
o Anion selectivity SO42-, NO3-, Cl-, OH-, Br-, I-
• Electrode potential and redox reaction.
2. The concentration of the ions (higher anion conc will
a) The more positive Eϴ, the easier to be reduced, the
be discharge) (higher conc of cation has no effect)
stronger the oxidising power and vice versa
19.7 Quantitative electrolysis
b) The sign of the Eϴ changes when the reaction is in the
reverse • Faraday’s Law of electrolysis = n ∝ Q
c) The value of Eϴ is not influence by the coefficient of a Q=I×t
balance chemical equation
• Faraday’s Law and Avogadro constant
• Calculate the cell potential, Eϴcell
L = charge on 1 mole of electron (F) C mol-1
19.3 Measuring standard electrode potentials
charge on 1 electron (1.60X10-19 C)
1. Metal/metal ion half-cell connected to SHE
L = number of electrons
2. Non-metal/non-metal ion half-cell connected to SHE
moles of electrons (mol)
3. Ion/ion half-cell connected to SHE
19.8 Cells and batteries
19.4 Using Eϴ value
• Primary cells
1. To predict if a rxn will occur
• Secondary cells
2. To predict the direction of electron flow
1. Car lead acid batteries
3. To predict cell voltages, Eϴcell
2. Nickel-metal hydrides (NiMH)
4. To predict the feasibility (don’t always work)
3. Lithium ions
5. To determine oxidising & reducing agent
4. Hydrogen-oxygen fuel cells
6. How E varies with ion concentration
19.5 Ecellϴ and Gϴ
19.1 Redox reactions revisited
 In Chap 7, you have learned to construct equations for redox
reaction from relevant half-equations.

 Reduction and oxidation was based on the concept of

changes in oxidation numbers or the transferring of
electrons.

 Recall how to balance half-equation, construct redox

equation, and to identify oxidising and reducing agent.
19.2 Electrode potential
 Since redox involving electron transfer, the flow of electrons
is always from the reducing agent to the oxidising agent.

 When there is a constant flow of electrons, it generates

electricity.

 Electrolyte: ionic liquid or solution that allow electricity to

flow due to the presence of electron flow.

 Electrode potential is often use to predict whether redox

reaction is feasible.
 When a strip of copper metal is immersed in a Cu2+ solution,
a half-cell is created.

 An equilibrium is established between the metal and the

solution, Cu2+ (aq) + 2e- ⇌ Cu(s)

 At equilibrium, there is a potential difference between the

metal and the aqueous solution of its ions - electrode
potential.
 According to the reactivity series, the more reactive the
metal, the more the metal itself oxidises.

 For example: Zn is more reactive than Cu.

 When Zn metal is placed in a solution containing Zn2+ ions,

some Zn atoms on the surface of the metal are converted to
Zn2+, leaving an excess of electrons on the surface of the Zn
metal. This results in the [O] of Zn.
  Copper is less reactive compared to Zinc.

 The Cu metal is +ve charge because of the electron

deficiency of the Cu2+. This results in the reduction of Cu.

 The electrical potential (voltage) of a half cell could not be

measured. However, the electrical potential of the metal
could be measure using the difference in potential difference
between another metal/metal ion system, such as comparing
Cu half cell with Zn half cell.
What are the
observations when Cu
undergoes reduction?

• Blue Cu2+ solution

fades.
• Red-brown Cu
deposits are form.
The Standard Hydrogen Electrode (SHE)
 A reference electrode used to determine the electrical
potential of interest. 2H+ (aq) + 2e- ⇌ H2(g)

 It is EϴH+(aq)/H2(g) = 0.00 V under standard conditions.

 ϴ means standard conditions, for any half-cell electrode

system
1. 298 K for any standard electrode
2. 1 atmosphere pressure (101kPa) of hydrogen gas H2(g) for
hydrogen electrode,
3. 1 mol dm-3 concentration of H+(aq) (hydrogen ions for
hydrogen electrode)
 The SHE consists of a platinised platinum electrode in a
solution of 1.00 mol dm-3 H+ ions (e.g. aqueous HC/).

 Alternative, Platinum black (increase contact surface area of H2

gas and H+ ions) covering Platinum electrode (inert).
Electrode potential and redox rxn
1. Electrode potential, E measures the tendency for a reduction
(voltage) process to occur at an electrode. The electrode
potential of the metal depends on several factors.
a) The nature of the electrode
b) Concentration of ions in the electrolyte
c) Temperature
d) Pressure

2. Standard electrode potential, Eϴ is the emf (voltage) of a half-cell

when it is connected to a standard hydrogen electrode under:
a) Ion concentrations at 1.00 mol dm-3
b) 298 K
c) Gas pressure of 1atm (101kPa)

3. Standard cell potential, E θ cell is the emf (voltage) when two half-
cells are connected under 1 mol dm-3 ion concentration, 298 K and
1atm.
4. Important things in predicting the condition of a redox reaction:
a) The more positive Eϴ, the easier to be reduced, the stronger
the oxidising power, and vice versa.
b) The sign of the Eϴ changes when the reaction is in the reverse.

c) The VALUE of Eϴ is NOT influence by the

COEFFICIENT of a balance chemical equation.

Example: Redox of MnO4- with Fe2+

MnO4- (aq) + 8H+ (aq) + 5 e- ⇌ Mn2+ (aq) + 4 H2O (l) Eϴ = +1.52V
Fe3+ (aq) + e- ⇌ Fe2+ (aq) X5 X5 Eϴ = + 0.77 V

Multiply by 5 to Does NOT multiply by 5

balance with the as the VALUE of Eϴ is
MnO4- half equation
NOT influence by the
COEFFICIENT
Most positive Eϴ value

Least positive Eϴ value

Electrochemical cell
 By combining 2 half cells, an electrochemical cell is built.

 There are 2 basic types of electrochemical cells

I. Galvanic cell / Voltaic cell – where spontaneous chemical
reaction occurring inside produces electricity.
II. Electrolytic cell – where external source of electrical energy
causes an otherwise non-spontaneous chemical change.
 Galvanic Cell / Voltaic cell
Electrons flow from 1
electrode to the other
indicate there is a
Voltage difference =
Electromotive force
(emf)

emf: The electrical

potential generated by
electrochemical cell.

 Salt Bridge - It is a tube filled with an inert electrolyte solution such

as KNO3, KCl, Na2SO4, NH4NO3. Usually, a saturated solution is
used. Experiment vid.

 The purpose of the salt bridge is to keep the solutions electrically

neutral and allowing the free flow of ions from one cell to another
while physically separating the 2 half cells. Without the salt bridge,
+ve & -ve charges will build up around the electrodes causing the
reaction to stop.
1. How to know which element undergo oxidation (anode) and
reduction (cathode) in Zn(s)|Zn2+(aq) || Cu2+(aq)|Cu(s) ?
Cu2+ + 2e- ⇌ Cu(s) Eϴ = +0.34V (reduction/cathode)
Zn2+ + 2e- ⇌ Zn(s) Eϴ = -0.76V (oxidation/anode)

2. How to know that Zn-Cu cell takes places spontaneously?

EϴCell = Eϴ(Cathode) - Eϴ(Anode)
= Eϴ(Reduction) - Eϴ(Oxidation)
= Eϴ(more +ve value) - Eϴ(less +ve value)
= +0.34 - (-0.76) = +1.10V

 Eϴcell is positive, the reaction is spontaneous and it is a voltaic cell. It is

a conversion of chemical energy to electrical energy.
 If the Eϴcell is negative, the reaction is non-spontaneous and it is
referred to as an electrolytic cell.

 Standard cell potential, E θ cell is the emf (voltage) when two half-
cells are connected under 1 mol dm-3 ion concentration, 298 K and
1atm.
19.3 Measuring standard electrode
potentials

 There are 3 main types of half-cell whose Eo can be obtained

when connected to a standard hydrogen electrode.

A. Metal/metal ion half-cell - SHE

B. Non-metal/non-metal ion half-cell - SHE
C. Ion/ion half-cell - SHE
 A) Metal/metal ion half-cell - SHE

Oxidation (Anode) Cathode (Reduction)

Reaction Fe(s) ⇌ Fe2+ (aq) + 2 e¯ 2 H+ (aq) + 2e¯ ⇌ H2(g)
Electrode Iron platinum
Solution Fe2+ (aq) (1 M) H+ (aq) (1 M)
1 M FeSO4 solution 1 M HCl or 0.5 M H2SO4
Gas pressure Hydrogen at 1atm
Potential - 0.44V 0.00 V
 Metal/metal ion - Metal/metal ion

Example 1 Example 2
Reaction Cu2+ (aq) + 2e¯ ⇌ Cu(s) Zn2+ (aq) + 2 e¯ ⇌ Zn(s)
Electrode copper Zinc
Solution Cu2+ (aq) (1 M) Zn2+ (aq) (1 M)
1 M CuSO4 solution 1 M ZnSO4 / Zn(NO3)2 solution

Potential + 0.34 V - 0.76 V

 B) Non-metal/non-metal ion half-cell -
SHE

Example 1 Example 2
Reaction 2 H+ (aq) + 2e¯ ⇌ H2(g) Cl2 (g) + 2e¯ ⇌ 2 Cl¯ (aq)
Electrode platinum platinum
Solution H+ (aq) (1 M) Cl¯(aq) (1M)
1 M HCl or 0.5 M H2SO4 1 M sodium chloride
Gas Pressure hydrogen at 1 atm chlorine at 1 atm

Potential 0.00V +1.36V

 C) Ion/ion half-cell - SHE

Example 1 Example 2
Reaction Fe3+ + e¯ ⇌ Fe2+ MnO4¯ + 8 H+ + 5e¯ ⇌ Mn2+ + 4 H2O

Electrode platinum platinum

Solution Fe3+ (1 M) AND Fe2+ (1 M) MnO4¯ (1 M),AND Mn2+ (1 M) AND
H+
Potential + 0.77 V + 1.52 V
19.4 Using Eϴ values
1) To predict if a rxn will occur
2) To predict the direction of electron flow (e- flows from the
more –ve Eϴ value to the more +ve Eϴ value)
3) To predict cell voltages
4) To predict the feasibility (don’t always work)
5) To determine oxidising & reducing agent
6) How Eo varies with ion concentration
Nernst Equation
1) To predict if a rxn will occur
 Example:
 Find out whether silver metal will be oxidised by aqueous nickel.
Ag+ (aq) + e– ⇌ Ag(s) Eϴ = +0.80V
Ni2+ (aq) + 2e– ⇌ Ni(s) Eϴ = –0.25V

 Ag+ (aq) + e– ⇌ Ag(s) Eϴ = +0.80V

 More +ve value, means reduction takes place, forward rxn is
feasible and backward rxn is not feasible.

 Ni2+ (aq) + 2e– ⇌ Ni(s) Eϴ = –0.25V

 Less +ve value compared to Ag, means oxidation takes place,
backward rxn is feasible and forward rxn is not feasible.

 silver metal will NOT be oxidised by aqueous nickel

3) To predict cell voltages
 Eϴcell = Eϴreduction - Eϴoxidation
 Example:
 Find out whether silver metal will be oxidised by aqueous nickel.
Ag+ (aq) + e– ⇌ Ag(s) Eϴ = +0.80V
Ni2+ (aq) + 2e– ⇌ Ni(s) Eϴ = –0.25V

◦ Method 1:
Reduction: 2Ag+ (aq) + 2e– → 2Ag(s) Eϴ = +0.80V
Oxidation: Ni(s) → Ni2+ (aq) + 2e– Eϴ = +0.25V
2Ag+(aq) + Ni(s) → 2Ag(s) + Ni2+ (aq) Eϴ = + 1.05V

◦ Method 2: *Note: Eo values substituted are ‘as given’ from the Data
Booklet.
Eϴcell = Eϴreduction - Eϴoxidation
= +0.80 - (-0.25V) = +1.05V
silver metal will NOT be oxidised by aqueous nickel
4) To predict the feasibility (don’t always work)
 A redox reaction is energetically feasible under standard conditions if the
standard cell potential (Eϴcell value) of the reaction is positive; vice-versa.

 Feasibility, or spontaneity, means whether or not a proposed rxn is

able to happen (possible in terms of energetic (thermodynamics)). It does
not mean that a reaction will happen.

 A +ve Eϴcell value does not give information about the rate of reaction.

 Example of +ve Eϴcell value but no reaction.

 H2 (g) + Cu2+ (aq) → 2 H+ (aq) + Cu (s) Eϴcell = + 0.34 V

 There is no reaction because the activation energy of the reaction is too

high (kinetically slow).
5) To determine [O] & [H] agent
 The [O] strength
going down Grp 7
elements decreases.

 Therefore the
reactivity going down
Grp 7 elements
decreases.

 MnO4- / H+ is a
stronger [O] agent
compared to Cr2O72-
/ H+.
6) How E varies with ion concentration

 When using Eo, all solutions have a concentration of 1.00 mol

dm-3.

 When the concentration of the ion changes, standard

conditions are not met and therefore the Eo has to response
to the change in concentration.
 Cr2O72- + 14 H+ + 6 e- ⇌ 2 Cr3+ + 7 H2O Eϴ = +1.33V [H]
 Fe3+ + e- ⇌ Fe2+ Eϴ = +0.77V [O]

INC [Cr2O72-] → Eqm shift RHS → Favours [H],→ Eϴ = > +1.33V

INC [Fe3+] Eqm shift RHS → Favours [H] , → Eϴ = > +0.77V
Dec [Cr2O72-] → Eqm shift LHS → Favours [O], → Eϴ = < +1.33V
Dec [Fe3+] → Eqm shift LHS → Favours [O], → Eϴ = < +0.77V

 In the S.E.P series, the increase in [reactants] will make the electrode
potential more positive.
 In the S.E.P series, the increase in [products] will make the electrode
potential more negative.
 Any change that shifts the equilibrium to the right will increase the electrode
potential.
 Any change that shifts the equilibrium to the left will decrease the electrode
potential.
 Cr2O72- + 14 H+ + 6 e- ⇌ 2 Cr3+ + 7 H2O Eϴ = +1.33V [H]
 Fe3+ + e- ⇌ Fe2+ Eϴ = +0.77V [O]

INC [Cr2O72-] → Eqm shift RHS → Favours [H],→ Eϴ = > +1.33V

INC [Fe3+] Eqm shift RHS → Favours [H] , → Eϴ = > +0.77V
Dec [Cr2O72-] → Eqm shift LHS → Favours [O], → Eϴ = < +1.33V
Dec [Fe3+] → Eqm shift LHS → Favours [O], → Eϴ = < +0.77V

1. What is the electrode potential of this reaction?

+0.56V

2. Which 2 ion concentrations should be increase in order for the

electrode potential of the reaction to be more positive (more
feasible)?
Increase [Cr2O72-] and [Fe2+]
 When the concentrations are changed from 1.00 mol dm-3,
or when the temperature is not at 25○C, the standard
conditions are not met.

 Under non-standard conditions, how to predict Eo?

 By using the Nernst equation, the Eo can be calculated under

non-standard conditions.

z
 z

 Where
 E is the electrode potential under non-std conditions
 Eo is the standard electrode potential
 R is the gas constant, 8.314 J K-1mol-1
 T is kelvin temp
 Z is the no of e- transferred in the rxn
 F is the Faraday constant, 96500 C mol-1
 In x = 2.303 log10x

z
 

E = + 0.31 V. Check with Le Chatelier’s principle, when the reactant conc

decreases, equilibrium position will shift to the LHS, thus decreases the E value
from +0.34 to +0.31.
 Example 2:
 What is the electrode potential of a Fe3+/Fe2+ system when
the concentration of the Fe3+ ions is 1.0 mol dm-3, and the
Fe2+ ions is 0.20 mol dm-3?

Fe3+ + e- ⇌ Fe2+ Eϴ = + 0.77 V

 Example 3:
 What is the electrode potential of a Cl2/Cl- system when the
solution of chloride ions contain 0.10 mol dm-3?

Cl2 + 2e- ⇌ 2Cl- Eϴ = + 1.36 V

 Example 4:
 Use the Nernst equation to calculate the E for the Fe3+(aq)
Fe2+(aq) half cell when Fe3+(aq) = 0.001 mol dm-3 and
Fe2+(aq) = 0.001 mol dm-3.
 Exercise
1. Calculate the value of the electrode potential at 298 K of a
Ni(s)/Ni2+(aq) electrode that has a concentration of Ni2+(aq)
ions of 1.5 mol dm-3. Eϴ = -0.25 V.

2. Calculate the electrode potential of a silver/silver ion

electrode, Ag(s)/Ag+(aq), at 0 ○C when the concentration of
Ag+(aq) ions is 0.0002 mol dm-3. Eϴ = +0.80 V.
3. To calculate the e.m.f. value for the reduction of H+ at 1.0
X10-7 mol dm-3 to H2 at 1.0 atm; 2H+ +2e- ⇌ H2.

4. To calculate the electrode potential E for the half-reaction

Sn4+ +2e- ⇌ Sn2+ at 25 °C if [Sn2+] = 0.40 mol dm-3 and
[Sn4+] = 0.10 mol dm-3.
5. Find the electrode potential of the Ca2+ (0.4 M) | Ca half
cell. Eϴ = -2.87V

6. A half rxn equation of a cell is given below:

I2 + 2e- ⇌ 2I-, Eϴ = +0.54 V
If the E value of the half cell reduces to +0.490 V, calculate the
concentrations of iodide ions in the aqueous solution of
the system.

7.Find the value of the electrode potential of the following

cell diagram.
MnO4- (0.8 M) | H+ (0.6 M), Mn2+ (0.5 M) | Pt(s). Eϴ = +1.52 V
 Find the E cell value when the concentration of both half-
system are not at std conditions of 1 M.

1. A voltaic cell is set up at 25○C with the half-cells Al3+ (0.0010

M) | Al and Ni2+ (0.50 M) | Ni. Write an equation for the
reaction that occurs when the cell generates and electric
current and determine the cell potential.
2. To calculate the e.m.f. of the Zn/Cu cell where [Cu2+] =
0.020 mol dm-3 and [Zn2+] = 0.040 mol dm-3. Write an
equation for the reaction that occurs when the cell
generates an electric current and determine the cell
potential.

E = +1.09 V
3. The following diagram shows a voltaic cell that was set up using
non-standard conditions.
a) Based on the diagram, build a balance ionic equation.
b) Calculate the Eϴcell under these conditions.
c) Describe the Eϴcell calculated in a) by using the words increase,
decrease, or no change, when [Fe3+] further decreases from 0.05M.

Ag+ (aq) + e– ⇌ Ag(s) Eo = +0.80V

Fe3+ + e- ⇌ Fe2+ Eo = + 0.77 V
 Overview of
19.4 Using Eϴ values
 3) EϴCell
= Eϴ(more +ve value) - Eϴ(less +ve value)
= 0.80 – (0.34)
= +0.46V 1) Feasibility
EϴCell = +ve value = feasible
under std conditions
2) Electron flow
-from oxidation
4) Feasibility
pole (more -ve E)
does not mean
to reduction pole
a guarantee
(more +ve E)
workable rxn. It
may be
extremely slow
but still feasible.
5)
Stronger oxidant Ag+ + e- ⇌ Ag(s) Eϴ = +0.80V Weaker reductant
Weaker oxidant Cu2+ + 2e- ⇌ Cu(s) Eϴ = +0.34V Stronger reductant

6)
INC [Ag+] from 1.00 mol dm-3 INC [Cu2+] from 1.00 mol dm-3
→ Eqm shift RHS → Eqm shift RHS
→ Eϴ = > +0.80V → Eϴ = > +0.34V
 19.5 Ecellϴ and Gϴ
 In the previous chapter, a –ve sign for Gibbs free energy, Gϴ
indicates a spontaneous reaction. Hence there is a
mathematical relationship between the Ecellϴ and Gϴ

n = number moles of e- transferred

−RT ln Keq = Gϴ = - n Eϴcell F
Eϴcell = Volts = J C-1
F = Faraday constant, 96500 C mol-1
 Take note of units! *Not in syllabus. Gϴ = −RT ln Keq
 CAIE tends to use J mol-1 for Gϴ but the actual unit is only
J !!!

 In a galvanic cell, a spontaneous redox reaction drives the

cell to produce electric potential, the Gϴ must be -ve.
 The opposite, where Gϴ is +ve when electrons flow
spontaneously through the electrochemical cell.
 If the redox is spontaneous, the cell produces voltage and
finally stops because the 2 electrodes are at the same
electrical potential.

 The relationship between and Gϴ, K, and Ecellϴ can be

represented by the following diagram.
 Example 1:
 Calculate the change in Gibbs free energy of an
electrochemical cell for the following redox reaction:

Pb2+ + Ni → Ni2+ + Pb Eϴcell = + 0.12 V

Gϴ = - n EϴCell F where F = 96500 C mol-1

Volts = 1 J C-1
 Example 2:
 Construct a balance equation between the Al3+/Al and
Br2/Br- cell and calculate the Eϴcell. Comment on the
feasibility of the reaction.

Gϴ = - n EϴCell F where F = 96500 C mol-11

Volts = 1 J C-1
 Example 3:
 Use relevant Eϴ values to show that the reaction of MnO2
and potassium, K are feasible under acidic conditions and at
298 K.

MnO2 + 4H+ + 2e- ⇌ Mn2+ + 2H2O Eϴ = + 1.23 V

K+ + e- ⇌ K Eϴ = - 2.92 V

Gϴ = - n EϴCell F where F = 96500 C mol-1

Volts = 1 J C-1
 Example 4:
 Calculate the Gϴ for the following reactions, and hence
predict whether they are feasible.
a) Zn + Mg2+ → Zn2+ + Mg
b) Cl2 + H2O → ½ O2 + 2Cl- + 2H+
 Example 5:
 Construct a balance equation to show Fe and Fe3+ reacts to
form Fe2+. Calculate the Eϴcell and comment on the feasibility
of the reaction.

 Write the equilibrium constant, K for the Eϴcell and give its
unit. Given Gϴ = −RT ln K, calculate the equilibrium
constant K. (R = 8.314 J K-1mol-1)
19.6 Electrolysis
 Electrolysis is the decomposition of the electrolytes to its
constituents elements by using electrical current.

 It is often used to extract metals that are high in the

reactivity series.

 Migration of ions. Which ions to which electrode?

◦ Cations move towards cathode (– terminal) and undergo
reduction (gaining of electrons)
◦ Anion move towards anode (+ terminal) and undergo
oxidation (losing of electrons)
 Two types of electrolytes
a) Electrolysis of molten electrolytes
b) Electrolysis of aqueous electrolytes
Electrolysis of molten electrolytes
 Using pure molten ionic compounds with 2 ions.

 Example ZnCl2:
Cation: Zn2+ → Cation moves towards cathode (reduction)
→ Zn2+ is reduced : Zn2+ + 2e- → Zn
Anion: Cl- → Anion moves towards anode (oxidation)
→ Cl- is oxidised : 2Cl- → Cl2 + 2e-
Electrolysis of aqueous electrolytes
 Aqueous solutions containing more than one cation AND
more than one anion.

 Example: Electrolysis of brine (Concentrated NaCl) that

contain Na+, Cl-, H+, and OH-.

 The following are the factors that are taken into

consideration to identify which ion are to be discharge.
1. The relative electrode potential of the ions
2. The concentration of the ions
3. Types of electrodes used (not in syllabus)
1. The relative electrode potential of the ions
 At cathode: regardless to its concentration, cation with the
most positive of Eθ value will be discharge (highest position in
electrochemical series)

 At anode:
 at lower concentration (≤ 1.00 mol dm–3), anion with the
most negative of Eθ value will be discharge (lowest position in
electrochemical series)
 at higher concentration (> 1.00 mol dm–3), a higher
concentration of that anion will be discharge regardless to its
position in electrochemical series
  At cathode: regardless to its concentration, cation with the
most positive of Eθ value will be discharge (highest position
in electrochemical series)
Cation reactivity series Electrochemical series
 At anode:
 at lower concentration (≤ 1.00 mol dm–3), anion with the
most negative of Eθ value will be discharge (lowest position
in electrochemical series)
 at higher concentration (> 1.00 mol dm–3), a higher
concentration of that anion will be discharge regardless to its
position in electrochemical series

 At the anode, using GRAPHITE electrodes , the ease of

discharge of anions follows the order:

SO42-, NO3-, Cl-, OH-, Br-, I-

Increasing ease of discharge
Increasing ease of oxidation

 *****NO3- and SO42- are never discharge.

2. The concentration of the ions
 If the quantity of a species is high in an electrolyte, the more
tendency it will be discharge because at a higher
concentration, the number of ions per unit volume is higher.

 The concentration of a species will not be significant if the

distance between the 2 species is far apart in the
electrochemical series.
 2018 summer 42 Q3

 2018 summer 41 Q3
 2011 summer 42 Q3

 2007 summer Q1
3.Types of electrodes used (not in syllabus)
 Inert electrodes are not involved in redox reaction;
 Eg : carbon/platinum. They easily discharge H+ ions.

 When different type of electrodes are used;

 Eg: Mercury/Zinc/Copper, these electrodes easily discharges
other cations and not H+ ions.
 The reactive electrode create a pontential and hence have
overpotential towards certain ions.

 This difference in behavior of the electrode being selective in

the discharge processes of ions is due to the overpotential
these electrodes have towards certain ion that prevents it
from being discharge.
 Eg: Mercury electrode has a high overpotential / overvoltage
towards H+ ions but a low overpotential towards Na+ ions
(for example)

 So by varying the type of electrode, we can select the type of

ions to be discharge selectively.

 Brine electrolysis (salt solution), a mercury cathode used.

 Mercury is intentionally selected because it has an

overpotential for H+ ions. Hence H+ ions are not selected for
discharge at the mercury cathode. In fact, Na+ which does
not have an overpotential towards mercury is selected and
discharged as Na atom. The sodium then forms an amalgam
with mercury. (Na | Hg)
SO42-

SO42-
 • Watch out for anode that is reactive
• Watch out for electrode that has the same

Exercise element as the electrolyte ions

• => In this case the reactive anode will undergo
oxidation instead of the ions (cation)

For the following molten or aqueous salt,

i. draw the electrolytic cell with labels
ii. predict the product with observation at each electrodes and
electrolyte
iii. write the half-equation at the cathode and anode
iv. write the overall ionic equation (if any)

a) Molten barium chloride

b) Molten magnesium oxide
c) Molten aluminium oxide
d) Diluted sodium chloride
e) Diluted copper(II) sulfate
f) Concentrated sodium chloride
g) Concentrated lead(II) nitrate
h) Concentrated copper(II) sulfate
i) Concentrated copper(II) sulfate using copper electrodes
(cathode) and zinc electrodes (anode)
j) Concentrated silver(I) nitrate
k) Concentrated silver(I) nitrate using silver anode and iron cathode
l) Concentrated zinc nitrate using copper electrodes
m) Diluted gold(I) nitrate using gold anode and a silver ring as
cathode
 Example where reactive metal is used as the electrode.
19.7 Quantitative electrolysis
 Quantitative electrolysis deals with the amount of substances
produced/deposited during electrolysis.

 The relationship between the amount of substance produced

during electrolysis and the amount of electrical charge is given
by Faraday’s Law of electrolysis.

 The electrical charge is the charge carried by the electrons

when they flow through the electrical circuit.

 1 mol of e- carries a charge of -96500 C. This is the same

charge as the charge on 1 e-.
(1.603 X 10-19 C) X (6.022 X 1023 mol-1) = 96500 C mol-1
e X L = F
 Faraday’s First Law of Electrolysis
 Faraday’s first law of electrolysis states that the amount of
substance produced during electrolysis is directly proportional
to the amount of electrical charge that flows through the
electrolyte.
 Substance = moles / mass or volume of the gas produce
n∝Q
Q=I×t

Quantity of charge Current time

Unit of electrical charge (in amperes, A) (in seconds, s)
(in coulombs, C) (or C s-1)

Coulomb is defined as the quantity of electrical charge

passing when 1 ampere flows for 1 second.
  The amount of electrical charge carried by 1 mole of
electrons is 96500 coulomb.
 The value is called one Faraday, F.
 1 F = 96500 C mol-1
 Therefore 1 mole of electron = 1 F = 96500 C mol-1

Faraday’s Second Law of Electrolysis

 the number of Faradays required to discharge 1 mole of ion
at electrode is equal to its charge on the ion.
Cu2+(aq) + 2e- ⇌ Cu(s)
1 mol 2 mol 1 mol

n Charge on ion (n no of e-) → n Faraday → Amt of electrical charge per mol

→ mass deposited / vol of gas produced during electrolysis
 Example:
 Calculate the mass of Cu that dissolves when a current of
0.75A is passed through a Zn/Cu cell for 45 mins.

Step 1:Write the half equation

Step 2: Find the number of Faraday (Coulombs) required to deposit 1 mole
of product. 1 mole of electron = 1 F = 96500 C mol-1
Step 3: Calculate the charge transferred during electrolysis Q = I × t
Step 4: Calculate the mass using moles = mass / Ar
 Now try this pg 391.
1. Calculate the mass of aluminium produced when a current of
1000 A is passed through a cell containing Al3+ ions for 1
hour.
Step 1:Write the half equation
Step 2: Find the number of Faraday (Coulombs) required to deposit 1 mole
of product. 1 mole of electron = 1 F = 96500 C mol-1
Step 3: Calculate the charge transferred during electrolysis Q = I × t
Step 4: Calculate the mass using moles = mass / Ar
 Example:
 To deduce the charge on the titanium ion in an aqueous
solution of a titanium salt given that 5.60 g of metallic
titanium was deposited at the cathode in an electrolysis by
passing a current of 5.00 A for 2.5 hours.
Faraday constant & Avogadro constant
 The Avogadro constant L, can be calculated using the
electrolytic method.

 1 mol of e- carries a charge of -96500 C. This is the same

charge as the charge on 1 e-,

(1.603 X 10-19 C) X (6.022 X 1023 mol-1) = 96500 C mol-1

eXL=F

 F, Faraday constant
 e, charge of 1 electron
 L, Avogadro constant
 Example 1:
 Find the charge on 1 mole of electrons in a simple
electrolytic experiment of CuSO4 using Cu electrodes using
a current of 0.20 A for 34 mins.
Initial mass of anode: 56.53g
Final mass of anode: 56.40g

 Mass of Cu removed from anode = 0.13g

 Quantity of charge passed, Q = I X t = 0.2 X 34 X 60 = 408 C
 To deposit 0.13g Cu requires 408 C.
 To deposit 1 mol of Cu. 63.5g requires 63.5/0.13 X 408 = 1.99X105 C
 Since Cu2+ (aq) + 2e- ⇌ Cu(s) involves transferring of 2 electrons, the
charge on1 mole of electrons = (1.99 X 105 C)/2 = 99500 C experimental
Faraday constant

 From the answer above, prove that the Avogadro constant is 6.023
X 1023 mol-1. F=eXL
99500 = 1.60 X 10-19 X L
L = 6.219 X 1023
 Example 2:
The following information were obtained when the lead-acid
batteries charges.
Current passed through the cell = 0.500 A
Time current was passed through the cell = 30.00 min
Initial mass of lead cathode = 51.570 g
Final mass of lead cathode = 52.542 g
Use these data to calculate a value of Avogadro number, L to 3 significant
figures. (e = -1.60 X 10-19 C; F = 9.65 X 104 C mol-1 ;Ar Pb = 207.2)

L = F/e = 6.00 X 1023 ~ 6.02 x 1023

 Example 3:
 Find the value for the Avogadro constant from an electrolysis
of dilute aqueous sodium chloride using a current of 0.25 A
for 32 min 10 s. 56 cm3 (at s.t.p.) of gas was evolved at the
cathode.

L = F/e = 6.026 X 1023 ~ 6.02 x 1023

Past Year 2015 Summer41 Q5
Homework
1. What mass of copper could be deposited from a copper(II)
sulphate solution using a current of 0.50 A over 10
seconds?
1.65 X 10-3 g Cu
2. Calculate the mass of silver that can be produced by the
electrolysis of 1 mol L-1 AgCN(aq)using 800 C of electricity
0.895 g
3. A current of 4.00 A was passed through copper(II) sulfate
solution for 965 seconds. What mass of copper was
discharged at the cathode?
1.27 g
4. Calculate the time required to deposit 56 g of silver from a
silver nitrate solution using a current of 4.5 A.
11119.3s / 11129.6 s
5. 30.0 g of samarium, Sm, was discharged by electrolysis with
a current of 2.40 A flowing 24125 seconds. What is the
formula of samarium ions? [Sm = 150]
Sm3+
6. Calculate the moles of copper metal that can be produced
by the electrolysis of following molten copper sulfate using
500 C of electricity.
a) Cu+
b) Cu2+
5.18 x 10-3 mol for Cu+ = 0.329 g
2.59 X 10-3 mol for Cu2+ = 0.164 g
7. Calculate the mass of silver deposited at the cathode
during electrolysis when a current of 1.80 A flows through
an aqueous solution of silver nitrate for 45.0 min.
5.44 g
8. Calculate the volume of hydrogen produced at r.t.p when a
concentrated aqueous solution of sulfuric acid is
electrolysed for 15.0 min using a current of 1.40 A.
0.157 dm3

9. Calculate the volume of oxygen produced at r.t.p when a

concentrated aqueous solution of sodium sulfate is
electrolysed for 55.0 min using a current of 0.70 A.
0.144 dm3