UNIT 12

ELECTROCHEMISTRY

ELECTROCHEMISTRY
Branch of chemistry dealing with
interconversion between chemical and
electrical energy

All electrochemical reactions are oxidationreduction reactions.

ELECTROCHEMICAL CELLS
Two types of electrochemical cell:
1. Electrochemical cells containing
spontaneous chemical reactions are
called voltaic or galvanic cells.
2. Electrochemical cells containing in

nonspontaneous chemical reactions are

called electrolytic cells.

VOLTAIC/GALVANIC CELL
A physical arrangement such that reducing and

oxidizing agents do not come into direct contact

with each other, and the transferred electrons
are allowed to flow through an external circuit.
Electrodes:
ANODE electrode at which oxidation occurs
CATHODE - electrode at which reduction occurs

Salt bridge allows ions to flow in out of

solutions, necessary to maintain
electroneutrality.

VOLTAIC/GALVANIC CELL
Zn(s)+ Cu+2 Cu(s) + Zn+2

SCHEMATIC REPRESENTATION
of
CELL
For the reaction:
Zn(s)+ Cu+2 Cu(s) + Zn+2
Anode on the left, cathode on the right
Single vertical line represents phase boundary
Double vertical lines represent salt bridge

Zn(s)ZnSO4 (conc)CuSO4(conc)Cu(s)

STRENGTH OF OXIDANTS and

REDUCTANTS
It enables us to predict the direction and the
extent of redox reaction.
Electrode potential quantitative measure of

a substance to be oxidized or to be reduced.

Standard potential, Eo electrode potential is

measured when all substances involved in

the half reaction are present in their
standard-state concentrations

Measuring Standard Electrode Potentials

Potential of a single half-reaction can be

measured if standard reduction potential of

zero is assigned to a reference half-reactions,
and report all other reduction potentials
relative to this reference.
The reference half-reaction:

2H3O+(aq) + 2e 2H2O(l) + H2(g)

Cell Voltage difference between two

potentials

E0cell = E0cathode E0anode

Characteristics of
Standard Electrode Potential (Eo)
The standard electrode potential for a half

reaction refers exclusively to a reduction

reaction.
It is independent of the number of moles of
reactant and product shown in the balanced
half-reaction.
It is temperature dependent.
A positive electrode potential indicates that
the half reaction is spontaneous with respect
to SHE half-reaction. A negative sign indicates
the opposite.

INTERPRETING ELECTRODE
IUPAC
electrode potential sign convention:
POTENTIALS
As the tendency for a half-reaction to

proceed in the direction of a reduction

increases, the electrode potential of the
half-cell also increases.

CALCULATING CELL VOLTAGE

Cell Voltage difference between two

potentials

E0cell = E0cathode E0anode

EXERCISE
Calculate the cell voltage of the following cell:
Zn(s)ZnCl2(1 M)Cl2(g) (1 atm), KCl (1 M)Pt

EXERCISE
1. Will permanganate ions, MnO4-, oxidize iron

(II) ions to iron (III) ions, or will iron (III) ions

oxidize manganese(II) ions to permanganate
ions in acidic solution?
2. Can Cr2O72 (in acidic medium) oxidize H2O2
to O2?

ELECTROLYTIC CELL
Electrical energy is used to force

nonspontaneous chemical reactions to occur.

The process is called electrolysis.
Two examples of commercial electrolytic

reactions are:
1. The electroplating of jewelry and auto parts.
2. The electrolysis of chemical compounds.

Electrolysi
s of Molten
NaCl

ELECTROLYSIS OF MOLTEN NaCl

A nonspontaneous redox reaction that

occurs:

2 Cl Cl 2(g) 2 e
-

Anode reaction

Cathode reaction 2 Na e - Na

Cell reaction 2 Cl 2 Na Cl 2 g 2 Na
-

QUANTITATIVE ANALYSIS OF
ELECTROLYSIS
Faradays Law - The amount of substance
undergoing chemical reaction at each
electrode during electrolysis is directly
proportional to the amount of electricity
that passes through the electrolytic cell.
A faraday is the amount of electricity that

reduces one equivalent of a species at the

cathode and oxidizes one equivalent of a
species at the anode.

QUANTITATIVE ANALYSIS OF
ELECTROLYSIS

A coulomb is the amount of charge that

passes a given point when a current of one
ampere (A) flows for one second.
1 A = 1 C/second
1 F = 96,485 C

Counting Electrons:
Coulometry and Faradays Law

Law states that during

ofFaradays
Electrolysis

electrolysis, one faraday of electricity

(96,485 coulombs) reduces and oxidizes,
respectively, one equivalent of the
oxidizing agent and the reducing agent.
This corresponds to the passage of one
mole of electrons through the electrolytic
cell.
Example:
Mg+2 + 2e Mg

2 F = 1 mol Mg+2

Electrolysis and Mass Changes

charge (C) = current (A) x time (s)
1 mole e- = 96,485 C

EXERCISE
1. Calculate the mass of palladium (Pd)

produced by the reduction of palladium

(II) ions during the passage of 3.20
amperes of current through a solution of
palladium (II) sulfate for 30.0 minutes.
2. A constant current is passed through an
electrolytic cell containing molten MgCl2
for 18hours. If 4.8 x 105g of Cl2 are
obtained, what is the current in ampere?
3. 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?

Concept Check
An unknown metal (M) is electrolyzed. It
took 52.8 sec for a current of 2.00 amp to
plate 0.0719 g of the metal from a
solution containing M(NO3)3.
What is the metal?
gold (Au)
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