UNIT 4.

CELL
POTENTIALS &
THEIR
APPLICATIONS
ELECTROCHEMICAL
CELLS
 Describe and explain the redox process in terms of electron transfer
Describe and/or change in oxidation number.

Explain Explain the terms: standard electrode potential, standard cell potential
OBJECTIVES

Describe Describe the standard hydrogen electrode

Outline methods used to measure standard potentials of: metals and

Outline non-metals, ions of the same elements in different oxidation states.

Explain and predict: the direction of electron flow in simple cells, the
Explain feasibility of a redox reaction.

Outline Outline the differences between Electrolytic and Voltaic cells

Outline Outline the functions of a salt bridge

 ELECTROCHEMISTRY

• Electrochemistry is the study of electron movement in an oxidation or

reduction reaction at a polarized electrode surface.
• Each analyte is oxidized or reduced at a specific potential and the
current measured is proportional to concentration.
• The study of changes between chemical and electrical energy in
electrochemical cells is called electrochemistry.
• The chemical reactions in electrochemical cells are redox reactions.
• REDOX reactions are made up of an oxidation (lose of electrons) and
reduction (gain of electrons).
 WHAT IS AN ELECTROCHEMICAL CELL?

• An electrochemical cell is a device that can generate electrical energy from the
chemical reactions occurring in it,
• or use the electrical energy supplied to it to facilitate chemical reactions in it.

• Consists of two electrodes (anode and cathode)

in contact with an electrolyte
• Oxidation occurs at the anode and reduction
occurs at the cathode
• Generally the left-hand electrode is taken as
the anode and right-hand electrode is taken as
the cathode.
 ELECTROCHEMICAL CELL
• Electrochemical cell is a contained system which uses electrical and
chemical energy.
 TYPES OF ELECTROCHEMICAL CELL

GALVANIC CELLS/ VOLTAIC CELL ELECTROLYTIC CELLS

• Chemical energy is transformed into

• Electrical energy is transformed into
electrical energy in these electrochemical
chemical energy in these cells.
cells.
• An input of energy is required for the
• The redox reactions that take place in
redox reactions to proceed in these cells,
these cells are spontaneous in nature.
i.e. the reactions are non-spontaneous.
• In these electrochemical cells, the anode is
• These cells feature a positively charged
negatively charged and the cathode is
anode and a negatively charged cathode.
positively charged.
• The electrons originate from the species • Electrons originate from an external source
that undergoes oxidation. (such as a battery).
Standard
Hydrogen
Electrode (SHE)
• The 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
Image source:

• The SHE is normally written as the left- http://www.mikeblaber.org/oldwine/chm1046/notes/Electro/CellEMF/CellE

MF.htm

hand electrode
Standard
Hydrogen
Electrode (SHE)

The standard hydrogen electrode consist of:

• hydrogen gas at 101 kPa. (1 atm) in equilibrium with
• an aqueous solution of hydrogen ions at a concentration of 1.00 mol.dm-3.
• a platinum electrode coated with platinum black in contact with both the hydrogen
gas and hydrogen gas and hydrogen ions. (Platinum black is finely divided which
allows close contact between the hydrogen gas and the hydrogen ions).
The half equation for this reaction is:
Measuring Standard
Electrode Potentials

In order to measure the electrode potential relating to the half equation:

• First place a rod of pure magnesium into a 1M solution of Mg2+ ions.

• This is the Mg/Mg2+ half cell.
• then connect this to a standard hydrogen electrode.
• Finally, measure standard electrode potential, Eө, by comparing the voltage of the
half cell with the standard hydrogen electrode
 Measuring Standard
Electrode Potentials

• The two half cells are connected by a salt bridge.

• The salt bridge is a strip of filter paper or other inert porous materials soaked
in saturated potassium nitrate solution.
• The voltmeter should be a high resistance voltmeter.
• Concentration of ions, pH of solution, temperature and pressure of gases all
affect standard electrode potential. So we have to use standard conditions
when comparing electrode potential. These conditions are:
• temperature 25oC (298K)
• concentration of ions 1M
• pressure of any gases involved 101 kPa.
 Measuring Standard
Electrode Potentials

• The standard electrode potential, Eө, of half cell is the voltage measured under
standard conditions with the standard hydrogen electrode as the other half cell.

• For the Mg/Mg2+ half cell connected to the standard hydrogen electrode, the voltage
developed is -2.36V.

• If we replace the Mg/Mg2+ half cell by a Cu/Cu2+ half cell, the voltage is +0.34V.

• The sign of the cell voltage depends on whether the half cell donates or receives
electrons with respect to the standard hydrogen electrode.
 STANDARD CELL POTENTIAL, Eөcell
• We can calculate the voltage of an electrochemical cell made up of two half cells
whose Eө values relative to the standard hydrogen electrode are known.
• The voltage measured is the difference between the Eө values of the two half cells.
This is called the STANDARD CELL POTENTIAL, Eөcell

The standard cell potential is

the voltage develop under
standard conditions when
two standard half cells are
joined.
Standard
Reduction
Potentials
at 25oC
 Galvanic
Cell/
Voltaic Cell
 THE DIRECTION OF ELECTRON FLOW IN CELLS

So when the following two half cells are

connected
Cu2+(aq) + 2e- ↔ Cu(s) Eө= +0.34 V
Zn2+(aq) +2e- ↔ Zn(s) Eө= -0.76 V

When we connect two half cells:

• The half cell with the more positive (less negative) value of Eө is the cathode.
• The half cell with the less positive (more negative) value of Eө is the anode.

• the Cu/Cu2+ half cell is the cathode

• the Zn/Zn2+ half cell is the anode
 THE DIRECTION OF ELECTRON FLOW IN CELLS

the Cu/Cu2+ half cell is the cathode REDUCTION

the Zn/Zn2+ half cell is the anode OXIDATION

• According to Eө values, Zn(s) is better at releasing electrons and Cu2+ ions are better at
accepting electrons
• So the direction of electron flow in the external wires
is from Zn/Zn2+ half cell to the Cu/Cu2+ half cell.
The redox reactions are:
Cu2+(aq) + 2e- → Cu(s) Eө= +0.34 V
Zn(s) → Zn2+(aq) +2e- Eө= +0.76 V
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq) Eөcell= +1.10V
 STANDARD CELL POTENTIAL
The two relevant half equations are:

• To find the value of Eөcell we subtract the less positive (or more negative) Eө value
from the more positive (less negative) Eө value. So in this case:

Eөcell = Eөcathode–Eөanode
Eөcell = EөCu -EөZn
Eөcell = +0.34-(-0.76)
Eөcell = +1.10 V
 SALT BRIDGE
• A solution of either KNO3 or
NH4NO3 in agar solution is
prepared
• It is poured hot into a double bent
U-tube kept in an inverted
condition and allowed to cool
when the agar sets into a gel
• The ends of this tube are put into
the two solutions avoiding mixing
but bridging them to maintain
electrical contact
Functions of Salt Bridge
it connects the solutions of two half - cells and
completes the cell circuit
it prevent transference or diffusion of the
solutions from one half cell to the other
it keeps the solution of two half - cells
electrically neutral
it prevents liquid – liquid junction potential i.e.
the potential difference which arises between
two solutions when they contact with each other
 CELL NOTATION
• A convenient way of representing electrochemical cells is called a cell notation.
• For a cell constructed from two metals/metal ions systems we write the cell diagram as
shown bellow.
• The reduced forms are on the outside of the diagram.

Reduced form Oxidised forms Reduced form

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

Phase change Salt bridge

Oxidation Reduction
 CELL NOTATION

ANODE CATHODE

Zn(s) / Zn2+(aq) // Cu2+(aq) / Cu(s) Eө = +1.1V

Oxidation Reduction

• The sign of Eө in these diagrams represents the

polarity (+ or -) of the right hand electrode in
the diagram.
• In this case the Cu/Cu2+ half cell is + with
respect to the Zn/Zn2+ half cell.
• If we write the cell diagram the other way
round, the Eө is negative.

Cu(s) / Cu2+(aq) // Zn2+(aq) / Zn(s) Eө= - 1.1V

• An electrochemical cell may be prepared by
combining any two half-cells.
• Such cells and half-cells are conveniently
described by an abbreviated notation together ELECTROCHEMICAL
with appropriate conventions so that the CELLS: NOTATIONS
convention will correspond to the chemical AND SIGN
reaction taking place in the cell. CONVENTION
• Moreover, the conventions used for the cells must
be compatible with other thermodynamic
conventions.
The following notations are used by convention for
describing cells and half-cells:
1. The half-cells written in the sequence
electrode│electrolyte represents oxidation
ELECTROCHEMICAL
and if the sequence is electrolyte│electrode, it CELLS: NOTATIONS
means reduction. AND SIGN
CONVENTION
2. A complete cell is written such that the left hand side
represents the oxidation reaction half-cell (anode) and the
right hand side represents the reduction half-reaction half-
cell (cathode) cell as shown below:
Zn (s)│ZnSO4 (aq)│CuSO4 (aq)│Cu (s)
ELECTROCHEMICAL
• The vertical line in the middle means that the two solutions
CELLS: NOTATIONS
are in direct contact. If, however, contact between the two
AND SIGN
solutions is made through a salt bridge two vertical lines are
CONVENTION
placed between the two electrolytes as shown below:

Zn (s)│ZnSO4 (aq)││CuSO4 (aq)│Cu (s)

• These are also written simply as-
Zn (s)│Zn2+ (aq)││Cu2+ (aq)│Cu (s)
Difference Between
Primary Cell and
Secondary Cell