ELECTROCHEMISTRY

OVERVIEW
1. OXIDATION AND REDUCTION

2. OXIDATION NUMBERS

3. RULES FOR ASSIGNING O.N.

4. ASSIGNING OXIDATION NUMBERS

5. COMMON OXIDISING AND

REDUCING AGENTS

6. WRITING REDOX EQUATIONS

OXIDATION AND REDUCTION
OXIDATION AND REDUCTION

Therefore, we can define oxidation and reduction by using

electron transfer as a basis

Oxidation

• An increase in oxidation number

• A loss or apparent loss of electrons
OXIDATION AND REDUCTION

Therefore, we can define oxidation and reduction by using

electron transfer as a basis

Reduction

• An decrease in oxidation number

• A gain or apparent gain of electrons
REMEMBERING OXIDATION
AND REDUCTION
OILRIG

Oxidation Is Loss (of electrons)

Reduction Is Gain (of electrons)

LEO the lion goes GER

Lose Electrons = Oxidation

Gain Electrons = Reduction

OXIDATION AND REDUCTION
Oxidation and reduction occur simultaneously in
chemical reactions
OXIDATION AND REDUCTION
Oxidising Agent: Oxidises other substances but is
reduced in the process

Reducing Agent: Reduces other substances but is

oxidised in the process
OXIDATION AND REDUCTION
Oxidising Agent: Oxidises other substances but is
reduced in the process

Reducing Agent: Reduces other substances but is

oxidised in the process
OXIDATION NUMBERS
This is a method of describing the combining power of
elements

The value is numerical

OXIDATION NUMBERS
The use of these oxidation numbers is extended to covalent
compounds

Some are assigned positive ON while others are assigned

negative ON by using certain rules
 RULES FOR ASSIGNING
ONS
1. The oxidation number of atom of elements in the
uncombined states, such as Na, Ca, Al, are all zero.
Similarly the oxidation numbers of iodine in I2, oxygen in
O2 and sulphur in S8 are zero
 RULES FOR ASSIGNING
ONS

2. In ionic compounds the oxidation number is equal to the

charge on the ion. The oxidation number of an element is
not always the same. Iron has an oxidation number of +2
in Fe2+ and an oxidation number +3 in Fe3+.
 RULES FOR ASSIGNING
ONS
3. The sum of the oxidation numbers of all the atoms or ions
in a compound is zero
 RULES FOR ASSIGNING
ONS
3. The sum of the oxidation numbers of all the atoms or ions
in a compound is zero
 RULES FOR ASSIGNING
ONS
4. The sum of the oxidation numbers of all the atoms in an
ion is equal to the charge on the ion.
 RULES FOR ASSIGNING
ONS
5. Some elements nearly always employ the same oxidation
number in their compounds. They are used as reference
points when assigning oxidation numbers to tother elements.
APPLICATION: ASSIGNING
OXIDATION STATES
1. Assign an oxidation state of S in SO2 and N in NH4+.
APPLICATION: ASSIGNING
OXIDATION STATES
2. In the following equation identify the oxidising and reducing
agents

(a) 2Fe(s) + 3Cl2(g) → 2FeCl3(s)

COMMON OXIDISING AND
REDUCING AGENTS
ELECTROCHEMISTRY 2
 OVERVIEW
1. ELECTROCHEMICAL CELLS

2. ELECTROLYTIC CELLS

3. GALVANIC CELLS

4. COMPONENTS OF GALVANIC CELLS

5. DRAWING ELECTROCHEMICAL CELLS

6. DRAWING CELL DIAGRAMS

7. STANDARD HYDROGEN ELECTRODE

8. CALCULATING THE EMF

9. EMF, OXIDISING/REDUCING POWER AND

ELECTRODE ASSIGNMENT

10. FEASIBILITY OF REACTIONS

11. NERNST EQUATION

 ELECTROCHEMICAL
CELLS
• Electrochemical cells either use chemical reactions
to generate electricity, or, conversely, use electricity
to provide energy for useful chemical reactions.

• The two main types of electrochemical cells are:

• Electrolytic cells 

• Galvanic cells (Voltaic cells)

 ELECTROCHEMICAL
CELLS
• Electrolytic cells is an electrochemical cell in which
a non-spontaneous reaction is driven by an external
source of current

• Galvanic cells is an electrochemical cell that

produces electricity as a result of a spontaneous
reaction occurring inside of it

• Both types of cells have many useful applications

 ELECTROLYTIC CELL

• Electrolytic cells consist of two electrodes that are

immersed in a conducting liquid, usually an aqueous
solution or a molten salt.

• An electrical supply is connected to the electrodes and

provides the energy to drive a reaction in the
solution (electrolysis).

• E.g. The isolation of sodium (Na) and chlorine (Cl) from

sodium chloride (NaCl).
 GALVANIC CELL

• The operation of a galvanic (or voltaic) cell is opposite to that

of an electrolytic cell i.e anode/cathode have opposite signs
to the ones they would have had in an electrolytic cell.

• In a galvanic cell, electrical energy is produced by a chemical

redox reaction, instead of a chemical reaction being produced
by electricity. 

• E.g. Redox reaction for a galvanic cell is the reaction between

aqueous solutions of zinc (Zn) and copper (Cu2+) where zinc is
oxidised (Zn2+) and copper is reduced (Cu)
 COMPONENTS OF A
GALVANIC CELL
• Electrolyte

• Anode

• Cathode

• Salt Bridge
 ELECTROLYTE

• A n e l e c t r o l y t e i s a  c h e m i c a l
compound  that dissociates into ions
and therefore is capable of
transporting electric charge

• An electrolyte is an electric conductor

• Unlike metals the flow of charge is

not a flow of electrons, but is a
movement of ions
 ANODE

• The site of oxidation (loss of electrons); the metal’s

oxidation number increases

• the metal atom, M(s), on the surface loses "n" electrons

to the electrode and enter the solution as the ion, Mn+(aq),
meaning that the metal atoms are oxidised

• When oxidation occurs these electrons are left on the

surface of the electrode (deposited) and these electrons
then migrate to the cathode
 CATHODE

• The site of reduction (gain of electrons)

• The metal’s oxidation number decreases

• Hence, the metal ion, Mn+(aq),  from the solution will

interact with the surface of the electrode, gaining "n"
electrons from it, and convert to metal atoms, M(s) -
this means that the ions are reduced
 SALT BRIDGE

• U-shaped tube filled with a concentrated salt solution

• The solution in this tube provides a way for ions to

travel between the two electrode solutions so that
they can remain electrically neutral in charge

• This enables the continuous flow of electrons as a

build up of ions in either electrode compartment can
cause the reaction to cease
|
QUICK REMINDER!
 CONSTRUCTING AN
ELECTROCHEMICAL CELL
 CONSTRUCTING THE
CORRESPONDING CELL DIAGRAM

A single vertical line represents the phase boundary between

the electrode and the solution.

The double vertical line represents the salt bridge/porous

barrier between the half cells.
 STANDARD HYDROGEN
ELECTRODE
• A  Standard Hydrogen Electrode (SHE)  is an
electrode that scientists use for reference on all half-
cell potential reactions.

• The value of the standard electrode potential is zero,

which forms the basis one needs to calculate cell
potentials using different electrodes or different
concentrations.
 STANDARD HYDROGEN
ELECTRODE
• Platinized platinum immersed in 1M H+
ions

• Hydrogen gas is bubbled over the

platinum electrode

• At the surface there is an equilibrium

set up between hydrogen gas and ions

• The potential which develops is given

assignment 0.00 V

• The standard electrode potential of

other species can be found with a SHE
What are the 2 reactions possible at the Pt surface?
set up along with the species in
question and the emf measured
 STANDARD ELECTRODE
POTENTIAL
• Standard electrode potential  is the measure of
the individual potential of a reversible electrode at standard
state, i.e., metal immersed in one of its ions at an effective
concentration of 1M and gases at a pressure of 1 atm.

• Values for standard electrode potentials are most often

tabulated at 25°C and with reference to a  standard
hydrogen electrode (SHE).

• The standard electrode potential has the symbol,  Eθ

 ELECTROMOTIVE FORCE

• Abbreviated EMF, Eθcell

• It is the maximum potential difference between two electrodes of

a galvanic or voltaic cell.

• This quantity is related to the tendency for an element, a

compound or an ion to acquire (i.e. gain) or release (loss) electrons

Eθcell = Eθcathode - Eθanode

CALCULATING THE EMF OF A
CELL

|
CALCULATING THE EMF OF A
CELL

|
|
RELATIONSHIP BETWEEN STANDARD
ELECTRODE POTENTIALS AND
ELECTRODE ASSIGNMENT

• At the site of oxidation, the • At the site of reduction, the

substance itself is oxidised substance itself is reduced
• Hence, this is the reducing • Hence, this is the oxidising
agent agent

Anode is home to the Cathode is home to the

reducing agent oxidising agent
RELATIONSHIP BETWEEN STANDARD ELECTRODE
POTENTIALS AND ELECTRODE ASSIGNMENT

The more positive the Eθ value the stronger the oxidising agent
To which electrode does the oxidising agent belong?
 WHICH ELECTRODE DO
THESE SPECIES BELONG?
 `

• When considering feasibility/spontaneity of a reaction we consider

the change in Gibbs Free Energy associated with the system

• For a spontaneous reaction, ∆G < 0

• For a non-spontaneous reaction, ∆G > 0

• For a reaction at equilibrium, ∆G = 0

• Gibbs Free energy is related to the EMF of a cell by,

∆G = - nFEθcell
PREDICTING THE FEASIBILITY OF
REACTIONS USING EMF OF A CELL

• Gibbs Free energy is related to the EMF of a cell by,

∆G = - nFEθcell

What do the n and F stand for?

• Therefore, a positive Eθcell value satisfies the criterion for

spontaneity the reaction is therefore feasible/
spontaneous