CHAPTER 4

Electrochemistry

1
 SCOPE
 Oxidation and reduction
 Balancingnet ionic equations for
redox reaction in acidic solution
 Electrochemical cells
 Galvanic cells
 Shorthand notation
2
 SCOPE
 Cell EMF
 Standard Reduction Potential
 Spontaneity of Redox Reactions
 EMF and Free Energy Change
 Electrochemical Decomposition

3
 LESSON OUTCOMES
At the end of this lecture, students should
be able to:
• Identify the oxidizing and reducing agents
in a redox reaction
• Write equations for oxidation and reduction
half-reaction and use them to balance the
net equation.
• Describe galvanic cells
4
 LESSON OUTCOMES
At the end of this lecture, students should
be able to:
• Draw cell diagram
• Write shorthand notation
• Calculate cell potential
• Calculate ΔG from cell potential

5
 4.1 Oxidation and reduction
LEO - Loss Electron Oxidation
GER - Gain Electron Reduction

Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

This reaction:Zinc increases from 0 in Zn(s) to +2 in
Zn2+(aq).
Hydrogen reduces from +1 to 0.
- This reaction is called oxidation-reduction reactions or
redox reactions.
The transfer of electron during redox reactions can produce
energy in the form of electricity.
Electrochemistry : Relationship between electricity and
chemical reactions.
 4.1 Oxidation and reduction
To determine a given chemical reaction is an
oxidation-reduction reaction.
- Keep track of the oxidation numbers.

Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

0 +1 +2 0

In redox reaction: one substance is oxidized and

another must be reduced.
 4.1 Oxidation and reduction
Oxidation numbers

-Also called oxidation state

-Is the charge that an atom in a molecule would

possess if the shared electron pairs in each
covalent bond were assigned to the more
electronegative element in the bond

-The oxidation number is assigned according to a

set of rules
8
 4.1 Oxidation and reduction
Rules:
-The oxidation number of any free element is 0
- The oxidation number for any simple, monoatomic
ion is equal to the charge
-The sum of all oxidation numbers of the atoms in a
neutral molecule must equal zero. The sum of all the
oxidation numbers in a polyatomic ion must equal
the charge on the ion
-In its compounds, fluorine is –1
-In most of its compounds, hydrogen is +1
- In most of its compounds, oxygen is –2
9
 4.1 Oxidation and reduction
Note that the oxidation number does not
actually equal a charge on an atom
Fractional values of oxidation numbers are
allowed
Oxidation is an increase in oxidation
number
Reduction is a decrease in oxidation
number
10
 4.1 Oxidation and reduction
The substance makes another substance to
be oxidized is called the oxidizing agent or
oxidant.

The substance causing another substance to

be reduced is called a reducing agent or
reductant.
 4.1 Oxidation and reduction
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

0 +1 +2 0
Zn(s) are oxidised (LEO) = cause another substance
to be reduced: H+ is reduced (GER).
Therefore, Zn(s) is a reducing agent and H+(aq) is
an oxidizing agent.

[Oxidising agent is itself reduced]

[Reducing agent is itself oxidized]
 Example
The nickel-cadmium battery- the redox reaction is
as follows:
Cd(s) + NiO2(s) + 2H2O(l)  Cd(OH)2(s) + Ni(OH)2(s)

Identify: Substances that are oxidized and

reduced.
Which are oxidizing and reducing agents?
Solution
1. Assign oxidation numbers.
Cd(s) + NiO2(s) + 2H2O(l)  Cd(OH)2(s) + Ni(OH)2(s)

0 +4 -2 +1 -2 +2 -2 +1 +2 -2 +1

2. Elements that are changing oxidizing number.

Cd: from 0  +2 (LEO)
Ni: from +4  +2 (GER)
3. Cd is oxidized - a reducing agent.
Ni is reduced - an oxidizing agent.
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Many redox reactions take place in aqueous solution
The oxidation and reduction processes are divided
into equations called half-reactions
Both the charge and the number of each type of atom
must be balanced
Charge is balanced by adding electrons to the side of
the equation that is more positive or less negative
The half-reactions are balanced separately, then
combined into the fully balanced net ionic equation
15
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Consider:
Reaction between permanganate ion, MnO4- and
oxalate ion C2O42-.

MnO4-(aq) + C2O42-(aq)  Mn2+(aq) + CO2(g)

1. 2 half eq/reactions: one half eq to represent

oxidation, one half eq to represent reduction
MnO4-(aq)  Mn2+(aq) Eq. 1
C2O42-(aq)  CO2(g) Eq. 2
4.2 Balancing net ionic equations
for redox reactions in acidic solution

2. Balance each half-reaction:

a) balance the elements other than H and O
b) balance the O atoms by adding H2O
c) balance the H atoms by adding the H+
d) balance the charge by adding e-
4.2 Balancing net ionic equations
for redox reactions in acidic solution
Eq. 1: Reduction, MnO4-(aq) Mn2+(aq)
Oxygen: MnO4-(aq)  Mn2+(aq) + 4H2O(l)
Hydrogen: 8H+(aq) + MnO4-(aq)  Mn2+(aq) + 4H2O(l)
Charge:Total charge of reactants:
8(+1) + (-1) = +7
Total charge of products:
(2+) + 4(0) = +2
Therefore;
5e- + 8H+(aq) + MnO4- (aq)  Mn2+ (aq) + 4H2O(l)
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Eq. 2: Oxidation
C2O42-(aq)  2CO2(g) O balance

Charge:Total charge of reactants = -2

Total charge of products = 0
Therefore;
C2O4 2- (aq)  2CO2 (g) + 2e-
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
3. Overall Rxn: Multiply each half-reaction and add.
® No. of e- lost = No. of e- gained

10e- + 16H+(aq) + 2MnO4-  2Mn2+(aq) + 8H2O(l)

5C2O42-(aq)  10CO2(g) + 10e-

Thus, balance net ionic/redox equation:

16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq)  2Mn2+(aq) + 8H2O(l) + 10CO2(g)
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Example
Complete and balance:
Cr2O72-(aq) + Cl-(aq)  Cr3+(aq) + Cl2(g)

Solution
1st: 2 half eq/reactions
Cr2O72-(aq)  Cr3+(aq)
Cl-(aq)  Cl2(g)
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Solution (cont.)
2nd: balance each half reaction
Cr2O7 2-(aq)  2Cr3+(aq)

Oxygen:Cr2O7 2-(aq)  2Cr3+(aq) + 7H2O(l)

Hydrogen: 14H+(aq) + Cr2O7 2-(aq)  2Cr 3+ + H2O(l)
Charge: (+14) + (-2) = +12 (reactant)
(+6) + (0) = +6 (product)
 6e- + 14H+(aq) + Cr2O7 2-(aq)  2Cr 3+(aq) + 7H2O(l)
 4.2 Balancing net ionic equations
for redox reactions in acidic solution
Solution (cont.)
2nd: balance each half reaction
Cl-(aq)  Cl2(g)

2Cl- aq)  Cl2 (g)

Charge: 2 (reactant)
0 (product)
 2Cl- (aq)  Cl2 (g) + 2e-

multiply  3  6Cl-(aq)  3Cl2 (g) + 6e-

 4.2 Balancing net ionic equations
for redox reactions in acidic solution

Solution (cont.)

3rd:Add two half eq/reactions

14H+(aq) + Cr2O7 2-(aq) + 6Cl-(aq)  2Cr 3+(aq) + 7H2O(l) + 3Cl2 (g)
4.3 Electrochemical Cell
Consists of two electrodes, in contact with an electrolyte
Two types:
 Voltaic cell (Galvanic cell).
 Electrolytic cell.
A voltaic(galvanic cell) - an electrochemical cell that
produces electricity as a result of the spontaneous
reaction occurring inside it.
e.g. battery system
An electrolytic cell - an electrochemical cell in which a
non-spontaneous reaction is driven by an external source
of current.
e.g. Chloro - alkali process
4.4 Voltaic Cell/Galvanic Cell
The energy released in a spontaneous redox.
 electrical work.
 through a voltaic (or galvanic) cell.
A strip of zinc is placed in a solution of copper (II) sulfate.
Electrons are transferred form Zn to the Cu2+ ion.
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
The zinc metal and The two solid
Cu2+ (aq) not in metals -
direct contact. connected by
the external
circuit ie.
electrode.

Electrode at which Electrode at which

oxidation occurs reduction occurs
 anode.  cathode.
 4.4 Voltaic Cell/Galvanic Cell
As the voltaic cell operates:
Oxidation of Zn: Zn(s)  Zn2+(aq) + 2e-
Concentration of Zn2+ increases, increase in +ve charge.
Zinc metal is oxidized at the anode - e-s flow through the
external circuit to the cathode.
Reduction of Cu2+: Cu2+(aq) + 2e-  Cu(s)
Decrease in Cu2+ as it is reduced to Cu, Cu electrode gain
mass, increase in -ve charge (more SO42-)

® Salt bridge is required to neutralize this.

® If not, no further redox can take place.
4.4 Voltaic Cell/Galvanic Cell
As the voltaic cell operates:

Can use porous barrier instead of salt bridge

Oxidation and reduction proceed:

- ions from the salt bridge migrate to neutralize charge.

Anions migrate toward the anode.

Cations migrate toward the cathode.

A summary of voltaic cell
Electrons flow spontaneously from anode to cathode.
Anions move toward the anode and cations toward
the cathode

Electron flow
Anode Cathode
- +

Porous barrier
Anions or salt bridge
Cations
 Example
The following oxidation-reduction is spontaneous:
Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2 + 7H2O(l)

A solution containing K2Cr2O7 and H2SO4 is poured into one

beaker and a solution of KI is poured into another. A salt
bridge is used to join the beakers. A metallic conductor that
will not react with either solution is suspended in each
solution, and the two conductors are connected with wire
through a voltmeter. Indicate the reaction occurring at the
anode, the reaction at the cathode, the direction of electron
migration, the direction ion migrations, and the signs of the
electrodes.
Solution
Divide into half-reactions:
® Cathode, Reduction: Cr2O7 2- (aq) 2Cr3+
Balance - half-reaction method.
Cr2O7 2-(aq) + 14H+(aq) + 6e-  2Cr3+(aq) + 7H2O(l)

® Anode, Oxidation: I-(aq)  I2

Balance - half-reaction method.
6I-(aq)  3I2(s) + 6e-
 Solution (cont.)
Anion  toward anode
Cation  toward cathode

e-

- Salt bridge
+
anion cation
anode cathode

6I- (aq)  3I2 (s) + 6e- Cr2O7 2-(aq) + 14H+(aq) + 6e-  2Cr 3+(aq) + 7H2O
 4.5 Shorthand Notation
Shorthand notation for describing the
components of an electrochemical cell
e-
Zn Cu
anode Salt bridge cathode

ZnSO4(aq) CuSO4(aq)

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

oxidation reduction
4.5 Shorthand Notation
Other example of a shorthand notation/cell diagram:
Cr(s) | Cr3+(aq) || Ag+(aq) | Ag(s)
To deduce cell reaction from a given shorthand
notation/cell diagram:
Left hand side (LHS) - oxidation (anode)
Right hand side (RHS) - reduction (cathode)
e.g. LHS Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) RHS
oxidation reduction
Zn  Zn2+ + 2e- Cu2+ + 2e-  Cu
e.g. Pt(s) | H2(g) | H+(aq) || Cu2+(aq) | Cu(s)
(inert or inactive electrode, e.g carbon graphite)
4.6 Cell EMF
Why e- flow spontaneously through the external
circuit?
Due to a difference in potential energy.
The potential energy of e- is higher in the
anode.
Potential energy at anode  than cathode.
e- flow spontaneously from anode to cathode.
4.6 Cell EMF
The potential difference between two electrodes is
measured in units of volt.
J
1 V1
C
1 volt: the potential difference required to impart 1J
of energy to a charge of 1 Coulomb (C).
The potential difference is called electromotive
(causing e- motion) force or emf.
The emf of a cell , Ecell : cell potential.

Ecell is measured in volts - refer as the cell voltage.

 4.6 Cell EMF
Any cell reaction, proceed spontaneously: the Ecell will be
positive.
The emf (Ecell) depends on:
- specific reactions occur at cathode-anode.
- the concentrations of reactants and products.
- Temperature.

Under standard conditon: 1 M concentration for reactants

and products @ 25°C.
- The emf is called the standard emf or the standard cell
potential.
- Denoted as E°cell.
4.7 Standard Reduction Potential
Reduction at cathode
Determine E°cell
Reduction at anode
 The cell potential
- E°cell = E°red (cathode) - E°red (anode)
- E°red : standard reduction potentials.
- Every voltaic cell involves two half-cells.
® not possible to directly measure the E°red of a
half-reaction.
4.7 Standard Reduction Potential
The reference half-reaction is the reduction
of H+ (aq) to H2(g) under standard
conditions.

E°red = 0 V

This is called a standard hydrogen electrode

(SHE).
Hydrogen electrode (gas electrode)
H2(g)
Pt wire

PtH2(g)H+(aq) H+(aq)

Pt gauze coated
with Pt black
(To catalyse the reaction)
4.7 Standard Reduction Potential
Oxidation of Zn and reduction of H+
Zn (s) + 2H+ (aq)  Zn2+ (aq) + H2 (g)
 The Zn2+/Zn electrode is the anode and SHE is the
cathode.
 The cell voltage is 0.76 V.
- using the E°red of H+ = 0, the standard reduction
potential E°red for Zn2+/Zn half-reaction.

E°cell = E°red (cathode) - E°red (anode)

0.76 V = 0 V - E°red (anode)
 E°red (anode) = -0.76 V
4.7 Standard Reduction Potential
 A standard reduction potential of -0.76 V can be
assigned:
Zn2+(aq, 1 M) + 2e-  Zn(s) = -0.76 V
Note:
Changing the stoichiometric coefficient in a half-
reaction does not effect the value of the standard
reduction potential.
e.g: 2Zn 2+ (aq, 1 M) + 4e-  2Zn (s)
E°red = -0.76 V
Cell Potentials

For a spontaneous process:

Eocell = Eocathode – Eoanode > 0
Example
For the Zn-Cu 2+ voltaic cell, E°cell = 1.10 V and
the Zn electrode is the anode.
E°red of Zn 2+ = -0.76 V
Calculate the E°red for the reduction of Cu2+ to Cu.

Solution
E°cell = E°red (cathode) - E°red (anode)
1.10 V = E°red (cathode) - (-0.76 V)
E°red (cathode) = 1.10 V - 0.76 V = 0.34 V
Example
Calculate the E°cell for this reaction.
Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+ + 3I2 + 7H2O

Solution
half-reaction:
Cathode:
Cr2O72-(aq) + 14H+(aq) + 6e-  2Cr3+ + 7H2O
Anode:
6I-(aq)  3I2(s) + 6e-
 Solution
E°red = Cr2O7 2-  Cr3+ = 1.33 V
E°red = I2  I- = 0.54 V

E°cell = E°red (cathode) - E°red (anode)

= 1.33 V - 0.54 V
= 0.79 V

Note:
The value of I2  I- is not multiplied by 3.
Intensive property: does not depend on the specific
stoichiometric coefficients.
4.7 Standard Reduction Potential (E°red)

E°cell = E°red(cathode) - E°red(anode)

The standard reduction potentials (E°red) provide a
measure of the driving force for a reduction to occur.
More +ve of E°red - the greater the driving force for
reduction.
Spontaneous operation - cathode must have more
+ve E°red than at the anode
4.7 Standard Reduction Potential (E°red)
The cell potential, E°cell is the difference between the
standard reduction potential of the cathode
reaction, E°red (cathode) and anode reaction, E°red
(anode).

Voltaic cell - the cathode reaction will be the higher

on the scale.
4.7 Standard Reduction Potential (E°red)
More positive

Cathode (reduction) The difference between

E°red
the standard reduction
E°red (V)

E°cell potentials  push e-

through an external
E°red circuit.
Anode (oxidation)

More negative
4.7 Standard Reduction Potential (E°red)
The more positive the E value for a half reaction,
the greater the tendency for the reactant of the
half-reaction to be reduced and therefore to
oxidize another species.

F2(g) + 2e-  2F-(aq) E°red = 2.87 V

F2 is more easily reduced species and is the

strongest oxidizing agent.
[easily reduced  strongest oxidizing agent]
 4.7 Standard Reduction Potential (E°red)
Lithium ion, Li+ is the most difficult species to reduce:
the poorest oxidizing agent.

Li+(aq) + e-  Li(s) E°red = -3.05 V

Oxidation: Li(s)  Li+(aq) is easily oxidized, great

tendency to transfer e-  the strongest reducing agent.
E°red = +ve  Strongest oxidizing agent
E°red = -ve  Strongest reducing agent
The list of E°red values provides an ordering of the ability
of substances to act as oxidizing or reducing agent.
The standard reduction potentials E°red is related
to oxidizing or reducing agent
Strongest oxidizing
agent Most +ve

F2(g) + 2e- 2F-(aq)

Increasing strength of

Increasing strength of
oxidizing agent

reducing agent
2H+(aq) + 2e- H2(g)

Li+(aq) + e- Li(s)

Most -ve
Strongest reducing
agent
Example

Determine which one of the three metals Zn, Fe, and Na

is the most active metal, given the following data:

Na+(aq) + e-  Na(s) Ered = -2.71 V

Zn2+(aq) + 2e-  Zn(s) Ered = -0.76 V

Fe2+(aq) + 2e-  Fe(s) Ered = -0.44 V

Solution
An active metal is one that is easily oxidized (that is, a
good reducing agent). Metals with large negative
standard reduction electrode potentials (large positive
standard oxidation potentials) are good reducing
agents. Sodium metal is the most active metal because
its reduction reaction has the largest negative standard
reduction potential (largest positive oxidation
potential). Na(s) is, therefore, the most active metal
(best reducing agent) of those listed.
4.8 Spontaneity of Redox Reactions
Voltaic cell - reaction occurs and produces a positive
emf must be spontaneous.
E°cell = E°red (cathode) - E°red (anode)
 if we make a general equation:
E°
E°==E°
E°red (red. process) - E° red(ox.
red (red. process) - E°red (ox.process)
process)

• General statement about the spontaneity of a reaction

and its associated emf:
- A positive value of E indicates a spontaneous process, and
- A negative value of E indicates a non spontaneous process.
Example
Using the standard reduction potential, determine
whether the reactions are spontaneous under standard
conditions:
Cl2(g) + 2I-(aq)  2Cl-(aq) + I2(s)
Reduction: Cl2(g) + 2e-  2Cl-(aq) E°red = 1.36 V
Oxidation: 2I-(aq)  I2 (s) + 2e- E°red = 0.54 V

Solution
E° = (1.36 V) - (0.54 V) = 0.82 V
E° is positive - this reaction is spontaneous and could be
used to build a voltaic cell.
4.9 EMF and Free-Energy Change
Gibbs free energy G is a measure of the spontaneity of
a process that occurs at constant temperature and
pressure.
EMF of a redox reaction indicates whether the reaction
is spontaneous.
Relationship exists between emf and the free-energy
change.
G
G == -nFE
-nFE
n = the no. of moles of electrons transferred in the reaction.
F = Faraday constant - quantity of electrical charge of 1 mol electron.
1 F = 96,500 C/mole = 96,500 J/V-mole
*n and F are positive quantities
4.9 EMF and Free-Energy Change
G
G==-nFE
-nFE
E positive  leads to a negative G
E positive and G negative indicate that a reaction is
spontaneous.
When both the reactants and products are in their
standard states:

G
Go==-nFE
o o
-nFEo

Note: the n is not the sum of the number of electron

used in oxidation and reduction.
Example
Calculate G°
2Br-(aq) + F2(g)  Br2(l) + 2F-(aq)

Solution
Reduction: F2(g) + 2e-  + 2F-(aq) E°red = 2.87 V
Oxidation: 2Br-(aq)  Br2(l) +2e- E°red = 1.06 V

E = 2.87 - 1.06 = 1.81 V

Stoichiometry of the half-reactions tells us that 2 mol of
electrons are transferred during the reaction. [n = 2]
G° = -nFE°
= -(2 mol e-)(96,500 J/V-mole)(1.81 V)
= -349 kJ
 4.10 lectrochemical decomposition
What is electrolysis?
When electricity is passed
through a molten ionic
Compound or through
a solution of an
Electrolyte, a chemical
reaction called
electrolysis can occur

61
4.10 Electrochemical decomposition
The DC source serves as an ‘electron pump’,
pulling electrons away from one electrode and
pushing them through the external wiring onto
the other electrode

Because of the nature of the chemical change in

an electrolysis cell, the positive electrode
becomes the anode, to which the anions move

The negative electrode is the cathode,to which

the cations move
62
 4.10 Electrochemical decomposition
Comparison of electrolytic and galvanic cells
• The names anode and cathode are assigned
according to the nature of the reaction taking place
at the electrode

• In an electrolytic cell, the cathode is negative and

the anode is positive

• In a galvanic cell, the cathode is positive and the

anode is negative 63
4.10 Electrochemical decomposition
Electrolysis in aqueous solutions
- Need to consider oxidation and reduction of the solute as
well as oxidation and reduction of water

K+(aq) + e-  K(s) E o = - 2.92V

2H2O(l) + 2e-  H2(g) + 2OH- Eo= - 0.83 V
H2O is reduced at the cathode, not K +

S2O82-(aq) + 2e-  2SO42-(aq) Eo= 2.01 V

O2(g) + 4H+ (aq) + 4e-  2H2O(l) Eo = 1.23V
At the anode, O2 is formed.
The half reaction with smaller reduction
potential occurs more easily as an
oxidation.
64
4.10Electrochemical decomposition
Stoichiometry of electrochemical reactions
• The amount of chemical change that occurs during
electrolysis is directly proportional to the amount of electric
charge that is passed through an electrolysis cell

• The SI unit of electric current is ampere

• The amount of product can be calculated using Faraday’s law
• Amount of product = I t / nF
Where I = current (A), t = time (s)
n = mol electrons transferred
F= Faraday’s constant (96500 C mol-1) 65
THE END

66