Electrochemistry

dbanda
MULUNGUSHI UNIVERSITY
Email : dannybanda@mu.ac.zm

1
 Definition
 Studyof chemical processes that cause electrons
to move.

 Thismovement of electrons is called electricity,

generated from the movement of electrons from
one element to another in a reaction known as
oxidation-reduction (redox) reaction.

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 Concepts
Electrochemistry has two aspects:
1. It deals with production of electric current as
a result of
chemical reaction.
These reactions are spontaneous.
• Electricity is produced from redox reaction in
which electrons are transferred via an
external conducting source from the oxidation
half cell to the reduction half cell
• The redox reaction takes place in two
different compartments called cells.
• These cells are called Galvanic or Voltaic cells 3
2. It deals with the chemical changes produced
by electric current. Such reactions are non-
spontaneous reactions.
• The electricity current forces a normally
reluctant reaction to take place.
• Electrical energy from an external source
causes non spontaneous chemical reaction to
occur. The cells are called electrolytic cells
and the process is electrolysis
The two aspects of electrochemistry are a
reverse of each other.
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 Definitions
 Cell:a compartment into which a chemical
reaction which is spontaneous or not takes
place

 Electrodes:are surfaces upon which oxidation

or reduction half-reactions occur. They may or
may not participate in the reaction. Inert
electrodes are those that do not enter into
reaction

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 Cathode: is the electrode at which reduction
occurs as electrons are gained by some species
 Terminal is positively charged

 Anode: is the electrode at which oxidation
occurs as electrons are lost by some species
 Terminal is negatively charged

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 Galvanic/Voltaic cells
 Named after Luigi Galvani or Alessandro Volta
respectively.

 This is an electrochemical cell that derives

electrical energy from spontaneous redox
reactions taking place within the cell.

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 Constructing a Galvanic cell

 To produce useful electrical energy.

 Two half-reactions involved in the net reaction

are made to occur in separate containers or
compartments called half-cells.
 in this way, electrons flow through external
wires to complete the circuit.
 the flow of electrons is then used to power
devices.

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 Cell reactions

 The overall reaction that takes place in the

galvanic cell is called the cell reaction.

 This is obtained by combining individual

electrode half-reactions, ensuring the number of
electrons gained in one half-reaction equals the
number lost in the other.

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 Diagrammatic representation of a
galvanic cell
• use spontaneous chemical reactions to generate
electrical energy in the form of an electrical current
 ΔG < 0

e-

Anode Cathode
e.g. Zinc electrode Salt Bridge e.g. Copper electrode

- +

Electrolyte, e.g. Electrolyte, e.g.

ZnSO4 CuSO4

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 Made up of two half cells

 Oxidation (loss of electrons) occurs at the negative anode

 Reduction (gain of electrons) occurs at the positive cathode

 Salt bridge acts to complete the circuit by joining the two half
cells together

Most batteries are made from Voltaic cells!

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 Salt bridge
 A tube that contains an electrolyte that connects
the two half-cells of a galvanic cell.
 allows cells to remain electrically neutral within
the internal circuit, preventing the cell from rapidly
running its reaction to equilibrium.
 Salt bridge allows the movement of ions required
to keep the solutions electrically neutral.
 Salt bridge is filled with a solution of a salt
composed of ions not involved in the cell reaction,
often KNO3 or KCl is used

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For the example above, the reactions occuring are:
Anode: Zn(s)  Zn2+(aq) + 2e- Cathode: Cu2+(aq) + 2e-  Cu(s)

The shorthand notation for this cell is:

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

 Cell notation
• Shorthand way of describing the make up of
a galvanic cell, by convention, in standard
cell notation
 Cell notation
 Anode on left, cathode on right
 Electrons flow from left to right
 Oxidation on left, reduction on right
 Single vertical = electrode/electrolyte boundary
 Double vertical = salt bridge

Anode: Cathode:
Zn →Zn2+ Cu2+ + 2e
+ 2e →Cu
 Cell potentials
 The fact that electrons flow from one electrode to
the other indicates that there is a voltage
difference between the two electrodes.
 This voltage difference is called the Electromotive
Force(emf) and is denoted by E.
 E is measured by using a voltameter.
 It is measured in volts and is also referred to as
Cell Voltage or Cell potential

The cell potential, E, is a measure of how well a cell

reaction can push and pull electrons through a circuit
 Cell Potential
Cell potential is measured in volts (V).

J
1V=1
C

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Potential is expressed as an electrical unit
called the Volt (V)
 Volt is a measure of the amount of energy,
in joules, that can be delivered per coulomb
(SI unit for charge)
 Cell potential , Ecell is the maximum
potential that a given cell can generate
which depends on
– Composition of the electrodes
– Concentrations of the ions in the half-cells
– Temperature
 The electrical energy generated by the spontaneous reaction is
proportional to the cell potential.

 The standard cell potential (the cell potential measured when all
the species are in their standard states) is given by:

E°cell = E°cathode - E°anode

Vertical │denotes different phase
 Fe(s)│Fe2+(aq)║Fe3+(aq),Fe2+(aq)│Pt(s)

 Cu(s)│Cu2+(aq)║Cl2(g)│Cl-(aq)│C(s)
 Sample Question


 Standard Cell Potentials

The cell potential at standard conditions

can be found through this equation:

 = Ered
Ecell  (cathode)  Ered
 (anode)

Because cell potential is based on

the potential energy per unit of
charge, it is an intensive property.
Electrochemistry
 Cell Potentials
• For the oxidation in this cell,
 = 0.76 V
Ered

• For the reduction,


Ered = +0.34 V
Calculate cell potential

Electrochemistry
 Cell Potentials

 = Ered
Ecell  (cathode)  Ered
 (anode)
= +0.34 V  (0.76 V)
= +1.10 V

Electrochemistry

© 2012 Pearson Education, Inc.

 Reduction potential
 The natural tendency to acquire electrons and proceed as a
reduction.
 Measured under standard conditions, it is called Standard
reduction potential
 standard reduction potential for the half reaction

Cu2+(aq) + 2e- → Cu(s)

is
EoCu2+ or EoCu2+/Cu
 When two half cells are connected to make a galvanic cell,
the one with the larger Eo cell acquires electrons from the
half cell with the lower Eo cell, which then undergoes
oxidation.

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 Eo cell taken as a positive number,
represents the difference between the Eo
cell of one half cell and the Eo cell of the
other.

Eocell = [ standard reduction potential of

substance reduced] - [standard reduction
potential of substance oxidized]

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 Standard Reduction Potentials
Reduction
potentials for many
electrodes have
been measured
and tabulated.
Electrochemistry
 Standard Reduction Potentials
 The total cell potential is the sum of the potentials
for the two half reactions at each electrode
 Ecell = Ecath + Ean
 From the cell voltage we cannot determine the
values of either – we must know one to get the
other
 Enter the standard hydrogen electrode (SHE)
 All potentials are referenced to the SHE (=0 V)
 SHE
 The SHE consists of a Pt electrode in contact with
H2(g) at 1 atm in a solution of 1 M H+(aq).
 The voltage of this half-cell is defined to be 0 V
 An experimental cell containing the SHE half-cell
with other half-cell gives voltages which are the
standard potentials for those half-cells
Ecell = 0 + Ehalf-cell
 Zinc half-cell with SHE
 Cell measures 0.76 V
 Standard potential for Zn(s) = Zn2+(aq) + 2e = 0.76
V
 Oxidizing and Reducing Agents
• The strongest oxidizers
have the most positive
reduction potentials.
• The strongest reducers
have the most negative
reduction potentials.

Electrochemistry

© 2012 Pearson Education, Inc.

 Oxidizing and Reducing Agents
• The greater
the difference
between the
two, the greater
the voltage of
the cell.

Electrochemistry
 The Nernst Equation

 For the reaction; aA +bB → cC + Dd
Where a , b , c and d are number of moles of
species


 The Nernst equation
 Working in nonstandard conditions


E  E  0.0592 log Q
n
 Example

Calculation of pH of a solution in
Electrochemistry

 Question

 Free Energy, G
G for a redox reaction can be found by
using the equation

G = nFE

where n is the number of moles of

electrons transferred, and F is a
constant, the Faraday:
1 F = 96,485 C/mol = 96,485 J/V-mol
Electrochemistry

© 2012 Pearson Education, Inc.

Free Energy

Electrochemistry
Question

G = nFE

Electrochemistry
 Electrolytic cells
In these cells non spontaneous chemical reactions are
forced to occur by the input of electrical energy. The
process is electrolysis.
“Lysis” means splitting apart
Thus, in electrolysis reluctant reactions are made to
split by electricity
An electrolytic cell consists of a container for the
reaction material with electrodes immersed in the
reaction material and connected to a source of direct
current (DC)
Both inert and active electrodes can be used
The principles of electrolysis are the same as those
Electrochemistry
that apply to electrochemical process carried out in
galvanic cells
Electrolytic cells
Electrolytic cells, like galvanic cells, are composed of two half-
cells--one is a reduction half-cell, the other is an oxidation half-cell.
The direction of electron flow in electrolytic cells, however, may be
reversed from the direction of spontaneous electron flow in galvanic
cells, but the definition of both cathode and anode remain the same,
where reduction takes place at the cathode and oxidation occurs at the
anode.
Because the directions of both half-reactions have been reversed, the
sign, but not the magnitude, of the cell potential has been reversed.
Power
Supply

Cathode Anode
e.g. inert Ti e.g. inert Ti

- +

Na+
Cl-

Electrolyte, e.g.
NaCl
Question
 Electrolysis of water

Oxidation Half-Reaction 2H2O(l) O2(g) + 4H+(aq) + 4e-

Reduction Half-Reaction 2H2O(l) + 2e- H2(g) + 2OH-(aq)
Overall (cell) Reaction 2H2O(l) 2H2(g) + 2O2(g)
Similarities and Differences Galvanic and Electrolytic Cell:
Electrolytic cells are very similar to voltaic (galvanic) cells
in the sense that :
• both require a salt bridge,
• both have a cathode and anode side,
• and both have a consistent flow of electrons from the
anode to the cathode.
However, there are also striking differences between the
two cells.

The main differences are outlined below:

Electrochemical cell (Galvanic Cell) Electrolytic cell

A Galvanic cell converts chemical energy An electrolytic cell converts electrical

into electrical energy energy into chemical energy.
Here, the redox reaction is spontaneous The redox reaction is not spontaneous and
and is responsible for the production of electrical energy has to be supplied to
electrical energy. initiate the reaction.

The two half-cells are set up in different Both the electrodes are placed in a same
containers, being connected through the container in the solution of molten
salt bridge or porous partition. electrolyte

Here the anode is negative and cathode is Here, the anode is positive and cathode is
the positive electrode. The reaction at the the negative electrode. The reaction at the
anode is oxidation and that at the cathode anode is oxidation and that at the cathode
is reduction is reduction.

The electrons are supplied by the species The external battery supplies the electrons.
getting oxidized. They move from anode They enter through the cathode and come
to the cathode in the external circuit. out through the anode.
Faraday’s Law of Electrolysis: the quantity (moles) of product formed
by an electric current is stoichiometrically equivalent to the amount
(moles) of electrons supplied

Faradays
Current + Time Charge Moles of electrons
constant

Using Faradays Law!

Molar mass
Mass product Moles product
Question
If 306C of charge is passed through a solution of Cu(NO3)2 during an
electrolysis experiment, what is the number of moles of copper metal
deposited at the cathode?
Cu(NO3)2  Cu2+ + 2NO3- Cu  Cu2+ + 2e-

 2 moles of electrons required to reduce 1 mol Cu2+

charge = 306 C
No of moles e- =
Faradays constant 96500 C/mol

= 0.00317 moles of electrons

From reaction stoichiometry, 2 moles electrons ≡ 1 mole Cu
 0.00158 moles Cu deposited
Question
If 612 C of charge is passed through a solution of Cu(NO3)2(aq),
calculate the number of moles of copper metal deposited.
Answer = 0.00317 mol
Question
How long will it take to deposit 0.00235 mol of metallic gold by
electrolysis of KAuCl4(aq) using a current of 0.214A?

KAuCl4(aq)  Au(s) Au3+ + 3e-  Au

 For every 1 mol Au produced, 3 mol electrons required

 For 0.00235 mol Au need 0.00705 mol electrons
Charge
No of moles electrons =
Faradays constant
Charge = moles electrons × Faradays constant
= 0.00705 mol × 96500 C/mol
= 680 C
Charge = current × time Time = Charge/Current
= 680 C / 0.214 A 1C = 1As
= 680 As / 0.214 A
= 3179 s
= 53 mins
Question
How long will it take to deposit 0.0047 mol of gold by electrolysis of
KAuCl4 using a constant current of 0.214 A?
Answer: 106 minutes

Question
How much Ca will be produced in an electrolytic cell of molten CaCl2 if
a current of 0.452 A is passed through the cell for 1.5 hours?
Answer: 0.5 g Ca
 Applications of
Oxidation-Reduction
Reactions

Electrochemistry

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 The Leclanche Cell (DRY CELL)
-It is an example of a primary voltaic cell
-The cell consists of zinc that acts as one of the
electrodes-THE ANODE while the cathode is the
carbon rod in the centre of the cell.

Electrochemistry
The Lead Storage Battery (ACCUMULATOR)

Electrochemistry
Corrosion and…

Electrochemistry
 …Corrosion Prevention
• Corrosion can be prevented by painting, or by attaching a sacrificial
Anode made of Zinc, magnesium or an aluminum alloy.
• As the name implies, sacrificial anodes do not corrode and may have to
be replaced from time to time.
• The ideal anode material has some passivity so that the rate of corrosion
is low.The metals aluminum, chromium, tin, nickel are essentially
unreactive in air, saturated water

Electrochemistry

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Electrochemistry