Notes for study

Lecture 1
Your reference Electrochemistry from
Atkins (Physical Chemistry Book)

1
Learning Objectives
What are some of the key things we learned from this lecture?

Types of electrochemical cells.

How to measure Standard electrode potential.

reference electrode.

How to measure the electrode potential from the Nernst

equation.

Factors affecting the reduction potential.

2
13-1
 Electrochemical cell

An electrochemical cell is a device used for generating an

electromotive force (voltage) and current from chemical reactions,
(galvanic, voltaic cell).

or the reverse, inducing a chemical reaction by a flow of current,

(electrolytic).

The current is caused by the reactions releasing and accepting

electrons at the different ends of a conductor.
 There are two types of electrochemical cells:
Electrolytic cell,
(electrical Energy chem. Energy)

Galvanic cell (voltaic),

(chemical energy) electrical energy)
In an electrochemical cell, an electric potential is created between
two dissimilar electrodes (mostly made of metals). This potential is a
measure of the energy per unit charge which is available from the
oxidation/reduction reactions to drive the reaction. It is customary
to visualize the cell reaction in terms of two half-reactions, an
oxidation half-reaction and a reduction half-reaction.

Reduced species oxidized species + ne-

Oxidation at anode
Oxidized species + ne- reduced species
Reduction at cathode
 2- Galvanic Cells
In redox reaction, electrons are transferred from the oxidized species to the reduced
species.

Imagine separating the two 1/2 cells physically, then providing a conduit through
which the electrons travel from one cell to the other.

8H+ + MnO4- + 5e Mn2+ + 4H2O

Fe2+ Fe3+ + e- x5
We need to complete the circuit by allowing positive ions to flow as well.

We do this using a salt bridge which will allow charge neutrality in each cell to be
maintained.

Salt bridge/porous disk: allows for ion migration such

that the solutions will remain neutral.
 Galvanic Cell

Electrochemical cell in which chemical reactions are used to

create spontaneous current (electron) flow

 Standard electrode potential (E
(E0 )
If the concentration of the components of the cell
are unity (1M), measured at 250c
The potential is called standard potential.

It is not possible to measure the absolute

potential of an electrode, but it could be
measured relative to a standard reference
electrode.
 How to measure E0 standard electrode potential?
Suppose we have Cu rod
immersed in its ions (half cells).
In order to measure potential of
an electrode, it must be
connected to another electrode
(half cell) having known constant
potential called reference
electrode and we use
Normal (standard) Hydrogen
Electrode.
So an electric current will flow from that having a higher potential
to the other one, this current is called e.m.f. Which is the algebric
difference of the electrode potential of the two half cells.

If the reference electrode has a potential equal to zero,

therefore, so the e.m.f. measured will be equal to E0
Reference Electrodes
 What is Normal Hydrogen Electrode (NHE)?
It consists of a piece of platinium foil coated electrolytically
with platinum black and immersed in a solution of HCl
(normal solu).
Hydrogen gas at pressure of 1 atmosphere is passed.
Platinum black layer absorbs a large amount of H2
Pt wire
and can be considered as a bar of H2.
H+ + e- H2 Glass tube to (1 atm)
Under fixed conditions: contain H2 (g)
1 atm pressure
Normal solution of HCl
The potential is assumed to be zero.
By connecting the electrode of unknown
potential to NHE, the E0 can be measured
by a potentiometer.
(1 N)
Bubbles of H2 (g)
Standard electrode potential E0: Is the e.m.f. produced when
a half cell consisiting of an element immersed in one molar
solution of its ions is coupled with NHE.
By measuring E0 for all elements and arrange into a series
known as Electrochemical Series :Starting from
E0 = -ve value, to System E0
Zn/Zn2+ -0.76
hydrogen where E0 = zero, then to
Fe/Fe2+ -0.44
E0 = +ve value Sn/Sn2+ -0.13
H2(pt)/H+ 0
Cu/Cu2+ +0.34
From this series we can conclude that:
1- The greater the ve value of E0, the greater the tendency of the
metal to pass into ionic state (oxidized) i.e. E0 is a quantitative
measure of the ability of the element to lose electrons giving its
ions.
2- Metal with more negative potential will displace any other metal
below it in the series from its solution.