3 0 Electrochemistry

TOPIC 3: ELECTROCHEMISTRY
CHAPTER 3.0: ELECTROCHEMISTRY
MAPPING COGNITIVE
TOPIC SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Define electrode potential √
b) Draw a Voltaic / Galvanic cell √
c) Describe the operation of a voltaic cell √
d) State the function of salt bridge √
e) Express half-cell equations and the overall cell reaction equation √
f) Illustrate a galvanic cell using a cell notation √
g) Define:
3.1 Galvanic Cell i. Standard reduction / electrode potential √
ii. Standard cell potential, E°cell
h) Draw and explain standard hydrogen electrode (SHE) √
i) Construct Standard Reduction / Electrode Potential series by
√
using SHE
j) Use the standard reduction / electrode potential values to:
i. Compare the relative strength of oxidizing or reducing agent
√
ii. Calculate standard cell potential, E°cell
iii. Predict the spontaneity of a redox reaction
a) Write Nernst equation for a given galvanic cell √
b) Explain the factors that affect cell potential √
3.2 Nernst c) Use Nernst equation to determine:
Electrochemistry Equation i. Cell potential (emf)
√ √
ii. Concentration or partial pressure of a species
iii. Equilibrium constant (K) when Ecell=0
d) Predict the spontaneity of a cell reaction √
a) Draw an electrolytic cell √
b) Describe the operation of an electrolytic cell √
c) Explain the influence of the following factors on the selective
discharge of a species at the electrode:
i. SRP of the species √
ii. Concentration of the species
iii. Nature of electrodes (active or inert electrode)
d) Predict the electrolysis of the following electrolytes using inert
3.3 Electrolytic electrodes:
Cell i. Molten salt
√
ii. Water
iii. Concentrated and dilute NaCl
iv. Aqueous Na2SO4
e) Predict the products of electrolysis using appropriate examples √
f) State Faraday’s Law of electrolysis √
g) Apply Faraday’s Law in calculation √
h) Set up electrolytic cell and determine the Faraday’s constant √
CHAPTER 3 − ELECTROCHEMISTRY page 1

ELECTROCHEMISTRY
3.1 GALVANIC CELL 3.3 ELECTROLYTIC CELL
3.2 NERNST EQUATION
INTRODUCTION
Definition The study of relationship between electricity and

ELECTROCHEMISTRY chemical reaction
Involves: REDOX REACTION
REDOX REACTION
(Reactions involving reduction and oxidation)
Reduction Oxidation
Gain of electron Loss of electron
Oxidation number decrease Oxidation number increase
Reaction at cathode (RED CAT) Reaction at anode (AN OX)
Example: Example:
Cu2+ (aq) + 2e → Cu (s) Zn (s) → Zn2+ (aq) + 2e

TYPES OF CELLS
ELECTROCHEMICAL CELL
GALVANIC/VOLTAIC CELL ELECTROLYTIC CELL
GALVANIC CELL ELECTROLYTIC CELL
Similarities:
- Oxidation occurs at anode, reduction occurs at cathode.
- Anions move to anode, cations move to cathode.
- Electrons flow: anode → cathode in the external circuit.
Converts chemical energy to Converts electrical energy to

electrical energy. chemical energy.
THIS CELL GENERATES ELECTRICITY THIS CELL USES ELECTRICITY
Spontaneous redox reaction Non-spontaneous redox reaction

(releases energy) (requires energy)
Cathode = positive terminal Cathode = negative terminal

Anode = negative terminal Anode = positive terminal
voltmeter
volt

MAPPING COGNITIVE DOMAINS

SUBTOPIC LEARNING OUTCOMES
C1 C2 C3 C4
a) Define electrode potential √
b) Draw a Voltaic / Galvanic cell √
c) Describe the operation of a voltaic cell √
d) State the function of salt bridge √
e) Express half-cell equations and the overall cell reaction equation √
f) Illustrate a galvanic cell using a cell notation √
3.1 Galvanic g) Define:
Cell i. Standard reduction / electrode potential √
ii. Standard cell potential, E°cell
h) Draw and explain standard hydrogen electrode (SHE) √
i) Construct Standard Reduction / Electrode Potential series by using SHE √
j) Use the standard reduction / electrode potential values to:
i. Compare the relative strength of oxidizing or reducing agent
√
ii. Calculate standard cell potential, E°cell
iii. Predict the spontaneity of a redox reaction
BASIC FEATURES OF ELECTROCHEMICAL CELLS
Both types of cell have common design features:
Two electrodes (anode and cathode)

are dipped into an electrolyte.
Electrode Object that conduct electricity between cell and surroundings.
Electrolyte Mixture of ions (usually in aqueous solution) that are involved in

reaction or that carry charge.
Anode Electrode at which oxidation occurs.
Cathode Electrode at which reduction occurs.

Example of voltaic/galvanic cell – Daniell Cell
Salt Bridge Made of a filter paper soaked in an inert electrolyte such as

saturated KNO3 or KCl.
@
An inverted U tube containing a gel permeated with solution
of an inert electrolyte such as KCl, Na2SO4, or NH4NO3.
Function 1. To separate the two electrolytes.

Salt Bridge 2. To maintain the electrical neutrality
3. Complete the circuit by allowing the ions to move
between the two electrolytes.

Operation of Voltaic/Galvanic Cell
Anode (Oxidation) Cathode (Reduction)

*MORE POSITIVE SRP VALUE
Zn (s) → Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- → Cu (s)
Zn atom dissolves and releases the Cu2+ ion in CuSO4 solution accepts the
electrons to form Zn2+ ion. electrons to form Cu atom.
(Copper deposited)
Observation: reddish brown solid deposited
Zn is negative electrode since it is a Cu is positive electrode

source of electrons
Reaction Involved:
Anode : Zn (s) → Zn2+ (aq) + 2e-

Cathode : Cu2+ (aq) + 2e- → Cu (s)
Overall cell reaction :

What happened if there is no salt bridge?

Voltmeter
Anode (Oxidation) Cathode (Reduction)

*MORE POSITIVE SRP VALUE
Zn (s) → Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- → Cu (s)
Zn2+ ions enter the solution. Cu 2+ ions leave the solution.
Causing an overall excess of positive Causing an overall excess of negative

charge. charge.
• The reaction will stop if the net increase in positive or negative charge in
respective half-cell is not neutralized.
• This excess charge build-up can be reduced by using a salt bridge.
Cl- ions from salt bridge K+ ions from salt bridge

move into Zn half cell move into Cu half cell

Exercise
Write half equation and overall equation for the following cell reactions.
ANODE (Ni) :
CATHODE (Ag) :
ANODE (Co) :
CATHODE (Cu) :
ANODE (Mg) :
CATHODE (Sn) :
ANODE (Ba) :
CATHODE (Na) :

CELL NOTATION
Cell Notation Representing a combination of reduction half-cell

notation and oxidation half-cell notation.
Example Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)
Also can be represented as:
Zn (s) | Zn2+ (aq,1.0M) || Cu2+ (aq,1.0M) | Cu (s)
Cell Notation
(INVOLVING GAS)
Anode :
Cathode :
Overall :
Cell Notation :

CELL NOTATION
TRY THIS….
Write cell notation for this voltaic cell:
Anode :
Cathode :
Overall :
Cell Notation :
TRY THIS….
For the cell below, write the reaction at anode and cathode and also the overall
cell reaction.
Zn (s) | Zn2+(aq,1M) || Cr3+ (aq,1M) | Cr (s)
Anode :
Cathode :
Overall :

STANDARD ELECTRODE POTENTIAL
Standard Electrode The cell potential between the standard hydrogen

Potential electrode (SHE) and a half cell system measured under
standard condition (1M, 25°C, 1atm)
Standard Reduction • is a measure of ability of a half-cell to attract

Potential (E°red) electrons towards it (reduction)
• measured under standard condition
(1M, 25°C, 1atm)
TAKE NOTE!!!
The sign of E0
changes when
the reaction is
reversed
Changing the
stoichiometric
coefficients of a
half-cell reaction
does not
change the
value of E0

Example:
Cl2(g) + 2e- → 2Cl-(aq) E0 = +1.36 V
Changing the stoichiometric coefficients of a half-cell reaction does not

change the value of E0
½Cl2(g) + e- → Cl-(aq) E0 = +1.36 V
Cl2(g) + 2e- → 2Cl-(aq) E0 = +1.36 V
The sign of E0 changes when the reaction is reversed
2Cl-(aq) → Cl2(g) + 2e- E0 = −1.36 V

HOW TO DETERMINE ANODE AND CATHODE???
From overall cell reaction
Example:
Cu+(aq) + Fe3+ (aq) → Cu2+(aq) + Fe2+(aq)
Anode :
Cathode :
From STANDARD REDUCTION POTENTIAL (E°red)
Based on SRP value,
Anode Cathode
Element with MORE –VE value from SRP Element with MORE +VE value from SRP
table table
More −ve, favour OXIDATION More +ve, favour REDUCTION

→ stronger as reducing agent. → stronger as oxidising agent.
Example:
Cu2+(aq) + 2e → Cu(s) E0 = + 0.34 V

Standard Reduction Potential
Zn2+(aq) + 2e → Zn(s) E0 = − 0.76 V
Based on SRP value, the more positive value, the higher the tendency for reduction
→ will be the cathode!
Anode :
Cathode :

Example 1:
Table below shows the standard electrode potentials for various metals.
B+/B C2+/C D2+/D E2+/E F2+/F

Metal ion/Metal
E°(V) +0.80 –0.28 +0.34 –0.76 +1.42
Arrange the metals given above in order of increasing strength as reducing agent.
Example 2:
Arrange these 4 substances in ascending order of their oxidizing strength,

Cl2 , Br2, I2 and F2 given that :

Example 3:
A galvanic cell is constructed with two half-cells, Sn/Sn2+ and Zn/Zn2+.

The half-cells are connected by a salt-bridge.
(E° Sn2+/Sn = ‒0.14 V ;E° Zn2+/Zn= ‒0.76 V)
Write the half equation at the anode, cathode and the overall cell equation.

STANDARD CELL POTENTIAL, E°cell
Definition The difference in electrical potential between the anode and

STANDARD CELL cathode at standard condition (1M, 25OC and 1 atm) is
POTENTIAL, called:
E°cell
• Standard cell voltage Measured
• Standard electromotive force (emf) by
• Standard cell potential voltmeter
Formula Eocell = Eocathode − Eoanode
CELL POTENTIAL, Ecell
Definition The difference in electrical potential between the anode and

CELL cathode at non-standard condition is called:
POTENTIAL,
Ecell • Cell voltage
• Electromotive force (emf)
• Cell potential
Formula Using Nernst Equation
Ecell = Eocell – 0.0592 log Q

n

Example 1:
Write the cell notation for the reaction below and calculate the standard cell
potential. (Ans : +1.51V)
Cl2 (g) + 2e- → 2Cl- (aq) E°= +1.36 V

F2 (g) + 2e- → 2F- (aq) E°= +2.87V
Solution:

Example 2:
An electrochemical cell is made by connecting a zinc electrode immersed in

ZnSO4 solution and an aluminium electrode immersed in Al(NO3)3 solution. By
referring to the standard reduction potential table,
(a) write the half-cell reactions at each electrode and the overall cell reaction.
(b) write the cell notation.
(c) calculate the standard cell potential. (Ans : +0.9V)
[EºZn2+/Zn = −0.76 V, EºAl3+/Al = −1.66 V]
Solution:

SPONTANEOUS & NON SPONTANEOUS REACTIONS
A redox reaction is.…

▪ spontaneous when E0cell is positive (GALVANIC/VOLTAIC CELL)
▪ non spontaneous when E0cell is negative (ELECTROLYTIC CELL)
▪ If E0cell = 0, the reaction is at equilibrium
Example:
Predict whether the following reaction will occur spontaneously or not at standard
conditions
(a) Cu2+(aq) + Fe2+(aq) ⎯→ Cu+(aq) + Fe3+(aq) (Ans : E0cell < 0, non spontaneous)
EºCu2+/Cu+ = +0.15 V, EºFe3+/Fe2+ = +0.77 V
(b) 2Al3+(aq) + 3Ca(s) ⎯→ 2Al(s) + 3Ca2+(aq) (Ans : E0cell > 0,spontaneous)
EºAl3+/Al = −1.66 V, EºCa2+/Ca = −2.87 V
(c) 3Fe2+(aq) ⎯→ Fe(s) + 2Fe3+(aq) (Ans : E0cell < 0, non spontaneous)
EºFe2+/Fe = −0.44 V, EºFe3+/Fe2+ = +0.77 V

STANDARD HYDROGEN ELECTRODE (SHE)

➢ SHE is used as standard reference half-cell and its Ered is define as 0.00 V
➢ SHE is encased in a glass tube consists of:
• Hydrogen gas bubbled at 1 atm into 1.0 M HCl(aq) at 25 C
• A platinum electrode partially immersed in the HCl(aq)
➢ The function of platinum electrode:

• Provides a surface on which the reaction can take place
• Serves as electrical conductor to the external circuit
Observation at SHE:
1. No gas bubbles produced – SHE is an ANODE (OX)
H2 (g) → 2H+ (aq) + 2e-
2. Colourless gas bubbles produced – SHE is a CATHODE (RED)
2H+ (aq) + 2e- → H2 (g)


Determination of the Ered of Copper electrode
Observations:
1. Voltmeter reading = 0.34 V

2. The blue colour of Cu2+ solution
fades.
3. Mass of Cu electrode increases.
Conclusion:
Cu2+ undergoes reduction
Pt (s) | H2 (g,1atm) | H+ (aq,1M) || Cu2+ (aq,1M) | Cu (s)
Anode :
Cathode :
Cell reaction :
Calculate E°Cu2+/Cu
(Ans : +0.34V)


Determination of the Ered of Zinc electrode
Observations:
1. Voltmeter reading = 0.76 V

2. Mass of Zn electrode decrease.
Conclusion:
Zn undergoes oxidation
Zn (s) | Zn2+ (aq,1M) || H+ (aq,1M) | H2 (g,1atm) | Pt (s)
Anode :
Cathode :
Cell reaction :
Calculate E°Zn2+/Zn :
(Ans : -0.76V)

Exercise 1:
Pt | H2 (g) | H+(aq) || Br2(g) | Br- (aq) | Pt E0cell = +1.07 V
a. Draw a diagram to show the apparatus and chemicals used for the cell above.
b. Determine the standard reduction potential for Br2 (Ans : +1.07V)
Exercise 2:
A cell is set up between a Cl2 electrode and a SHE electrode.
Pt(s) | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt(s) E0cell = + 1.36 V
a. Draw a diagram to show the arrangement of apparatus and chemicals used.
b. Determine the standard reduction potential for Cl2 and discuss the chemical
reactions occurring in the electrochemical cell. (Ans : +1.36V)


C1 C2 C3 C4
a) Write Nernst equation for a given galvanic cell √
b) Explain the factors that affect cell potential √
3.2 Nernst c) Use Nernst equation to determine:
Equation i. Cell potential (emf)
√ √
ii. Concentration or partial pressure of a species
iii. Equilibrium constant (K) when Ecell=0
d) Predict the spontaneity of a cell reaction √
The Ecell for a reaction under non-standard condition can be determined by

using The Nernst equation
ORIGINAL Ecell = Eocell – RT ln Q

NERNST nF
EQUATION
R = 8.314 JK-1mol-1
T = temperature in K
F = Faraday constant = 96500 C
n = number of moles electron transferred
Derivation At 298 K and R = 8.314 J K-1 mol-1 with 1F = 96500C ,
Ecell = Eocell – 2.303 RT log Q

nF
Ecell = Eocell – 2.303 (8.314)(298) log Q

n (96500)
NERNST
EQUATION
Reaction Take Note:

quotient, Q Reaction quotient will take aqueous and gaseous state!
aA (s) + bB (aq) → cC (aq) + dD(g)
Q = [C]c PDd
[B]b

Requirements 1. Determine anode and cathode → to determine Eo cell

to use Nernst 2. Balance redox equation → to determine Q and n
Equation
Example 1: Example 2:
Write down expressions for Q: Write down expressions for Q:
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) O2(g) + 4H+(aq) + 4Br-(aq) 2H2O(l) + 2Br(l)

The usage of
NERNST
EQUATION
1 To calculate cell potential at non-standard state (Ecell)
Example 1:
Determine the Ecell for the following cell:
Zn(s) | Zn2+ (aq, 0.02M) || Cu2+(aq, 0.40 M) | Cu(s)
[Given E˚ Cu2+|Cu = +0.34 V ; E˚ Zn2+|Zn = −0.76 V] (Ans : +1.14V)
Step 1: Determine E°cell Step 3: Nernst Equation
Step 2: Write half cell and balance

redox equation
Anode :
Cathode :
Overall :

Example 2:
Determine the Ecell for the following cell:
Cu(s) | Cu2+ (aq, 0.03M) || Ag+ (aq, 0.002M) | Ag(s)
[Given E˚ Cu2+|Cu = +0.34 V ; E˚ Ag+|Ag = +0.80 V] (Ans : +0.345V)

redox equation
Anode :
Cathode :
Overall :

The usage of
NERNST
EQUATION
2 To calculate Concentration or Pressure
Example 1:
The Ecell for the following electrochemical cell:
Zn(s) | Zn2+ (aq, 0.1 M) || Ni2+ (aq, x M) | Ni (s)
is 0.34 V at 25oC. Calculate the concentration of nickel ion, x M in the cell.
[ Eo Zn2+|Zn = –0.76 V ; Eo Ni2+|Ni = –0.25 V ] (Ans : 1.806 x 10-7M)

redox equation
Anode :
Cathode :
Overall :

Example 2:
The emf of the following cell is found to be 0.54 V at 25C.
Zn(s) | Zn2+(aq, 1.0 M) || 2H+(aq, ? M) | H2(g, 1.0 atm) | Pt
Calculate the molar concentration of H+ solution.
[ Eo Zn2+|Zn = –0.76 V ; Eo H+|H2 = 0.00 V ] (Ans : 1.92 x 10-4 M)

redox equation
Anode :
Cathode :
Overall :

The usage of
NERNST
EQUATION
3 To calculate K, equilibrium constant when Ecell = 0
Example:
Determine the equilibrium constant (K) for the following reaction.
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) (Ans : 3.47 x 10 15)

redox equation
Anode :
Cathode :
Overall :

Predict spontaneity of a cell reaction
▪ Spontaneous when Ecell is positive

▪ Non-spontaneous when Ecell is negative
▪ If Ecell = 0, the reaction is at equilibrium.
Spontaneity of a reaction
Standard condition Non-standard condition

Calculate Eocell Calculate Ecell (use Nernst Equation)
Eocell is +ve – spontaneous reaction Ecell +ve – spontaneous reaction
Eocell is –ve – non-spontaneous Ecell –ve – non-spontaneous reaction
Exercise:
A galvanic cell consists of a lead anode immersed in a 1.00 M solution of Pb(NO3)

and a platinum cathode that has gaseous hydrogen bubbling over it at a pressure
of 1.00 atm. The hydrogen ion concentration of the solution is 1.30 ×10-5 M.
i. Write the cell notation for this reaction

ii. Calculate the cell potential, Ecell
iii. Predict the spontaneity of the reaction.
[Eo Pb2+/Pb = -0.13V; Eo H+/H2 = 0.00V]

FACTOR AFFECTING CELL POTENTIAL, Ecell
ORIGINAL Ecell = Eocell – RT ln Q

NERNST EQUATION nF
1. Concentration of Expressions of Q
reactant and
product. - Decrease [product] or Pproduct (pressure) will increase
@ the Ecell value.
Partial pressure of
reactant and - Increase [reactant] or Preactant (pressure )will increase
product. the Ecell value.
2. Temperature - Lowering or increasing the temperature will change

the value of Ecell.
3. Type of half cell (increases Eocell will increases Ecell)
- using half cell with more –ve SRP value as anode will
increase Eocell, will increase Ecell
- using half cell with more +ve SRP value as cathode

will increase the Eocell, will increase Ecell

Exercise
The potential for the following electrochemical cell at 25oC is 0.34 V.
Pt (s)│H2 (g, 1 atm)│H+ (aq, 1.0 M)║Cu2+ (aq, 1.0 M)│Cu (s)
(a) Explain how the concentration of the solution at the anode and the cathode
would change after the cell had been discharged continuously.
(b) Calculate the standard electrode potential of copper. (Ans : +0.34V)
(c) When sulphuric acid is used in the above cell at 25oC and pressure of
hydrogen is 1.0 atm, the cell potential is 0.53 V. Calculate the pH of
sulphuric acid used. (Ans : 3.21)
Answer:
(a) At the anode :
At the cathode :
(b) Ans: E°Cu2+|Cu = +0.34 V

(c) Ans: pH = 3.21


C1 C2 C3 C4
a) Draw an electrolytic cell √
b) Describe the operation of an electrolytic cell √
c) Explain the influence of the following factors on the selective discharge of a
species at the electrode:
i. SRP of the species √
3.3 Electrolytic ii. Concentration of the species
Cell iii. Nature of electrodes (active or inert electrode)
d) Predict the electrolysis of the following electrolytes using inert electrodes:
i. Molten salt
ii. Water √
iii. Concentrated and dilute NaCl
iv. Aqueous Na2SO4
e) Predict the products of electrolysis using appropriate examples √
ELECTROLYSIS Electrolysis is a chemical process that uses electricity for a

non-spontaneous redox reaction to occur.
Apparatus for carrying out electrolysis: ELECTROLYTIC

CELL
ELECTROLYTIC CELL
• It is made up It is made up of 2 electrodes immersed in an electrolyte.
• A direct current is passed through the electrolyte from an external source.
• Molten salt and aqueous ionic solution are commonly used as electrolytes.

Features of 1. Converts electrical energy to chemical energy.

Electrolytic Cell
2. Anode is +ve terminal (Oxidation)
Cathode is –ve terminal (Reduction)
3. Non-spontaneous redox reaction, requires energy to

drive it.
Electrolysis 1. Electrolysis of molten salts

Process
2. Electrolysis of water
3. Electrolysis of CONCENTRATED and DILUTED NaCl
4. Electrolysis of Aqueous Na2SO4

1. ELECTROLYSIS OF MOLTEN SALTS
Experimental arrangement: To predict the products at both anode and

cathode:
1. Identify what species exist in the

electrolyte.
2. Identify which species will move to anode

and which species will move to cathode.
3. Determine the half equations at both anode

and cathode.
• It requires high
temperature.
Species present in electrolyte:
Anode (+) Cathode (−)
Species
moves to
Half-cell
equation
Observation
Overall Anode :
equation
Cathode :
Overall :

2. ELECTROLYSIS OF WATER
Experimental arrangement: To predict the products at both anode and

cathode:
1. Identify what species exist in the

electrolyte.
2. Identify which species will move to anode

and which species will move to cathode.
3. Determine the half equations at both anode

and cathode.
Species
moves to
Half-cell
equation
Observation
Overall Anode :
equation
Cathode :
Overall :

3. ELECTROLYSIS OF AN AQUEOUS SALT
PROBLEMS!!
Aqueous salt solution contains water, anion, and cation.
Water is an electro-active substance that may be oxidized or reduced in the

process depending on the condition of the electrolysis.
(Cathode) 2H2O (l) + 2e- → H2 (g) + 2OH- (aq) E0 = −0.83 V

Reduction of
water molecules
(Anode) 2H2O (l) → O2 (g) + 4H+ (aq) + 4e- E0 = −1.23 V

Oxidation of
water molecules
ELECTROLYSIS OF NaCl (**GENERAL)
Species moves to
Take Note!!! The product of electrolysis of More +ve value E°SRP

aqueous NaCl at anode → reduction
depends on the
concentration of the
electrolyte.

PREDICTING THE PRODUCTS OF ELECTROLYSIS
Factors influencing 1. Standard Reduction Potential, E°

the products:
2. Concentration of ions.
3. Types of electrodes used:

• Inert : carbon, platinum
• Active : copper, silver
• Effect concentration on selective discharge
➢ Applies only to the discharge of anions (−ve ion)

ELECTROLYSIS OF A VERY DILUTE NaCl SOLUTION
Species
moves to
Species
selected to
discharge
Half-cell
equation
Observation
Overall Anode :
equation
Cathode :
Overall :

ELECTROLYSIS OF A CONCENTRATED NaCl @ AQUEOUS NaCl SOLUTION
Species
moves to
Species
selected to
discharge
Reason
Half-cell
equation
Observation
Overall Anode :
equation
Cathode :
Overall :

ELECTROLYSIS OF AN AQUEOUS Na2SO4 SOLUTION
Species
moves to
Species
selected to
discharge
Reason
Half-cell
equation
Observation
Overall Anode :
equation
Cathode :
Overall :
*Please refer to page 45

PREDICTING THE PRODUCTS OF ELECTROLYSIS
• Types of Electrodes
➢ Applies only to the discharge of anions (−ve ion)
Active Electrodes Inactive/Inert Electrodes
• Examples : Cu metal, Zn metal, • Examples : carbon, platinum (Pt)

Ag metal
• DO take part in electrolysis • DON’T take part in electrolysis
• Ions present at anode are • Ions present at anode are important

unimportant

** ADDITIONAL NOTES
Electrolysis of an Aqueous Salt
PROBLEMS!!
Aqueous salt solution contains water, anion, and cation.
Water is an electro-active substance that may be oxidized or reduced in the

process depending on the condition of the electrolysis.
Predicting the Product of Electrolysis of aqueous salt

(USING INERT ELECTRODE)
FIRST STEP Identify the movement of ions present at cathode and anode.
SECOND At the cathode (-) (Choose the MORE POSITIVE SRP value)
STEP
Cation of Less Reactive Metal vs Water
• Cation of Less Reactive metal likes (Cu2+, Ag+, Zn2+ Au3+) will
be reduced because they have higher SRP value than water.
Cation of Reactive Metal vs Water
• Cation of Reactive metal likes (Li+, Na+, K+) will NEVER be

reduced because they have lower SRP value than water.
THIRD STEP At the anode (+) (Choose the MORE NEGATIVE SRP value)
Concentration of ions
• Choose ion with lower SRP value unless electrolyte contains

concentrated [halide ions], such as Cl-, Br-, l- except F-.
• Oxoanions like (SO2-4, NO-3, PO3-4) ions cannot be oxidized.

Species
moves to
Species
selected to
discharge
Reason
Half-cell
equation
Observation


C1 C2 C3 C4
f) State Faraday’s Law of electrolysis √
3.3 Electrolytic
Cell g) Apply Faraday’s Law in calculation √
h) Set up electrolytic cell and determine the Faraday’s constant √
FARADAY’S LAW
Describes the relationship between the amount of electricity passed through an

electrolytic cell and the amount of substances produced at electrode.
Definition States that the quantity of substance formed at an

Faraday’s First electrode is directly proportional to the quantity of
Law electric charge supplied.
of Electrolysis
Q = electric charge in coulombs (C)

m = mass of substance discharged
To calculate The amount of charge (Q) that flows through electrolyte is

electric charge in given by:
coulombs (C)
Q = It
where Q = quantity of charge (C)

I = electric current (A)
t = time (s)
Faraday constant is the charge on 1 mole of electron

(F)
1 mole of electrons = 1 F = 96500 C

Example 1:
An aqueous solution of CuSO4 is electrolysed using a current of 0.150A for 5

hours. Calculate the mass of copper deposited at the cathode. [Mr (Cu) = 63.5]
Solution: [Ans: 0.889 g]

Example 2:
Electrolysis of molten calcium bromide, using carbon electrodes carried out CaBr2.
If an electric current of 5.0 A was passed through the molten salt for one hour,
calculate the quantity of electric, in Faraday and the mass of calcium produced.
Solution: [Ans: 0.187 F]

Example 3:
In an electrolysis, a current of 2.50 A flowed through an aqueous solution copper

(II) sulphate, CuSO4 for 3 hours. Calculate the volume of O2 collected if the
electrolysis was carried out at STP.
Solution: [Ans: 1.57 L]

Example 4:
An aqueous solution of copper (II) sulphate, CuSO4 is electrolysed using platinum

electrodes. During the electrolysis, a current of 2.50 A was passed through the
solution for 2.00 hours.
i. Write the reaction equations involved at anode and cathode.

ii. Calculate the amount of oxygen gas collected in a mole.
Solution: [Ans: ii) 0.0466 mole]

3 0 Electrochemistry

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3 0 Electrochemistry

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TOPIC 3: ELECTROCHEMISTRY

CHAPTER 3.0: ELECTROCHEMISTRY

CHAPTER 3 − ELECTROCHEMISTRY page 1

3.1 GALVANIC CELL 3.3 ELECTROLYTIC CELL

3.2 NERNST EQUATION

Definition The study of relationship between electricity and

Involves: REDOX REACTION

Gain of electron Loss of electron

Oxidation number decrease Oxidation number increase

Reaction at cathode (RED CAT) Reaction at anode (AN OX)

Cu2+ (aq) + 2e → Cu (s) Zn (s) → Zn2+ (aq) + 2e

CHAPTER 3 − ELECTROCHEMISTRY page 2

GALVANIC/VOLTAIC CELL ELECTROLYTIC CELL

GALVANIC CELL ELECTROLYTIC CELL

Converts chemical energy to Converts electrical energy to

Spontaneous redox reaction Non-spontaneous redox reaction

Cathode = positive terminal Cathode = negative terminal

CHAPTER 3 − ELECTROCHEMISTRY page 3

MAPPING COGNITIVE DOMAINS

BASIC FEATURES OF ELECTROCHEMICAL CELLS

Both types of cell have common design features:

Two electrodes (anode and cathode)

Electrode Object that conduct electricity between cell and surroundings.

Electrolyte Mixture of ions (usually in aqueous solution) that are involved in

Anode Electrode at which oxidation occurs.

Cathode Electrode at which reduction occurs.

CHAPTER 3 − ELECTROCHEMISTRY page 4

Example of voltaic/galvanic cell – Daniell Cell

Salt Bridge Made of a filter paper soaked in an inert electrolyte such as

Function 1. To separate the two electrolytes.

CHAPTER 3 − ELECTROCHEMISTRY page 5

Operation of Voltaic/Galvanic Cell

Anode (Oxidation) Cathode (Reduction)

Zn (s) → Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- → Cu (s)

Observation: reddish brown solid deposited

Zn is negative electrode since it is a Cu is positive electrode

Anode : Zn (s) → Zn2+ (aq) + 2e-

CHAPTER 3 − ELECTROCHEMISTRY page 6

What happened if there is no salt bridge?

Anode (Oxidation) Cathode (Reduction)

Zn (s) → Zn2+ (aq) + 2e- Cu2+ (aq) + 2e- → Cu (s)

Zn2+ ions enter the solution. Cu 2+ ions leave the solution.

Causing an overall excess of positive Causing an overall excess of negative

• This excess charge build-up can be reduced by using a salt bridge.

Cl- ions from salt bridge K+ ions from salt bridge

CHAPTER 3 − ELECTROCHEMISTRY page 7

CHAPTER 3 − ELECTROCHEMISTRY page 8

Cell Notation Representing a combination of reduction half-cell

Example Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)

Also can be represented as:

Zn (s) | Zn2+ (aq,1.0M) || Cu2+ (aq,1.0M) | Cu (s)

CHAPTER 3 − ELECTROCHEMISTRY page 9

Write cell notation for this voltaic cell:

Zn (s) | Zn2+(aq,1M) || Cr3+ (aq,1M) | Cr (s)

CHAPTER 3 − ELECTROCHEMISTRY page 10

STANDARD ELECTRODE POTENTIAL

Standard Electrode The cell potential between the standard hydrogen

Standard Reduction • is a measure of ability of a half-cell to attract

CHAPTER 3 − ELECTROCHEMISTRY page 11

Cl2(g) + 2e- → 2Cl-(aq) E0 = +1.36 V

Changing the stoichiometric coefficients of a half-cell reaction does not

½Cl2(g) + e- → Cl-(aq) E0 = +1.36 V

Cl2(g) + 2e- → 2Cl-(aq) E0 = +1.36 V