Engineering chemistry II

ELECTRO CHEMISTRY

The m aterial gi ven below is for the purpose of understanding and enjoying the
beauty of electrochem istry. For the purpose of exam s, please m ake use of class notes
and text books.
IN TR O D U CTIO N
Electricity and chemical energy are two different forms of energy. One form can be
converted into the other. The study of such conversions and their applications is called
electrochemistry.
Electrochemistry is a part of physical chemistry and deals with the chemical changes
accompanying the passage of an electric current or the reverse process in which a
chemical reaction is used as the source of energy to produce an electric current.
Electrochemistry is the study of reactions in which charged particles (ions or
electrons) cross the interface between two phases of matter, typically a
metallic phase (the electrode) and a conductive solution, or electrolyte
CHEMISTRY AND ELECTRICITY
The connection between chemistry and electricity is a very old one, going back to Alessandro
voltas discovery, in 1793, that electricity could be produced by placing two dissimilar metals on
opposite sides of a moistened paper.

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I have the pleasure of communicating to you, Sir, and through you to the Royal Society, some
striking results at which I have arrived in pursuing my experiments on the electricity excited by the
simple mutual contact of metals of different sorts...

In 1800, Nicholson and Carlisle, using Volta's primitive battery as a source, showed
that an electric current could decompose water into oxygen and hydrogen. This was
the first proof that water is composed of hydrogen and oxygen.
This was surely one of the most significant experiments in the history of chemistry,
for it implied that the atoms of hydrogen and oxygen were associated with positive
and negative electric charges, which must be the source of the bonding forces
between them.
Humphrey Davey prepared the first elemental sodium by electrolysis of a sodium
hydroxide melt. Daveys former assistant Michael Faraday showed that the amount
of electricity passed through a solution and the amount of the products formed were
directly related.

English chemists John Daniell (left) and Michael Faraday (right) both credited as founders of
electrochemistry today.

In this chapter you will find answer to the following questions.

What
What
What
What

is a cell?
exactly is happening in a cell?
is the interaction between an electrode and an electrolyte?
makes an electrode behave as anode or cathode? Is it by its own nature?

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Or does the other electrode present has a role in it?

Why should there be two electrodes?
Why should we study electrochemistry? What are the applications?
Learning Objectives On completion of this chapter you will be able to:

1. Differentiate between single electrode potential and cell emf

2. Know how emf of a cell is determined experimentally.
3. Understand and appreciate the factors that determine a single electrode
potential and a cell emf.
4. Calculate the single electrode potential and cell emf under non standard
conditions, provided you know the values under standard conditions using
Nernst equation.
5. Decide which electrode in the given pair of electrodes will behave as anode
from its position in the electrochemical series.
6. Differentiate between electrochemical and electrolytic cells.
7. Differentiate between reversible and irreversible cells.
8. Know primary and secondary reference electrodes
9. Know how glass, known for its insulating properties, is made use of in
electrochemistry?
10. Know the application of electrochemistry in chemical quantitative analysis in
following redox reactions and precipitation reactions using a special
instrument called potentiometer.
The reactions in electrochemistry are carried out in cells. Cells consist of electrodes
and an electrolyte. An electrode is a rod made up of a conducting or
semiconducting material. Metal electrodes are often used. Electrolyte is either
molten salt or a salt solution. While electrodes are electronic conductors, the
electrolyte conducts electricity through ions or charged particles. You are familiar
with a variety of reactions such as neutralization reactions, double decompositions,
complexation , precipitation and redox reactions. The reactions that are dealt with in
electrochemistry are oxidation reduction or redox reactions. Oxidation refers to
loss of electrons and reduction refers to gain of electrons. Redox reactions are
essentially electron transfer reactions. These electron transfer reactions usually
occur at the interface between an electrode and an electrolyte solution in which the
electrode is dipped. The electrode at which oxidation occurs is called an anode and
the electrode at which reduction occurs is called cathode. The electrolyte solution
consists of ions. The positively charged ions move towards cathode, accept electrons
from the cathode and get reduced. So, positively charged ions are called cations.

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The negatively charged ions move towards anode, donate electrons to the electrode
and get oxidized. So, negatively charged ions are called anions.
ORIGIN OF SINGLE ELECTRODE POTENTIAL .
OXIDATION POTENTIAL AND REDUCTION POTENTIAL
Add a little common salt , i.e. sodium chloride to water taken in a beaker. What
happens to the salt? It dissolves.
Just dip a metal rod such as copper or zinc rod in water taken in a beaker. What
happens to the rod? Apparently nothing happens. The rod stays as it is. No change
is visible. But something not perceivable by eye, actually happens , when a metal
rod is dipped in water or preferably in its own salt solution.
Suppose, for example, that we immerse a piece of zinc metal in pure water. A small
number of zinc atoms go into solution as Zn ions, leaving their electrons behind in
the metal:
Zn(s) Zn2+ + 2e
As this process goes on, the electrons which remain in the zinc cause a negative
charge to build up within the metal which makes it increasingly difficult for
additional positive ions to leave the metallic phase. A similar buildup of positive
charge in the liquid phase adds to this inhibition. Very soon, therefore, the process
comes to a halt, resulting in a solution in which the concentration of Zn2+ is still
too low (around 1010 M) to be detected by ordinary chemical means.

Transport of zinc ions from the metal to water; the build-up of negative charge on the
metal and positive charge in the solution, soon brings the process to a halt. This is
because Nature seems to strongly discourage any process that would lead to an

excess of positive or negative charge in matter. Nature abides by electro-neutrality

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principle according to which bulk matter cannot have a chemically significant

imbalance of positive and negative ions.
Zinc metal is one phase. Water is another phase. If you consider the bulk metal , it
is neutral. Similarly the bulk water is also neutral. However, the transition region
between two phases consists of a region of charge imbalance known as the electric
double layer. One layer is that of zinc ions on the surface of the metal. The other
layer is that of polar water molecules with their negative end (oxygen) towards the
Zn2+ ions. If Zn is immersed in a salt solution, then the electrical double layer
consists of zinc (II) ions and the counter ions, for example, sulfate ions, if the salt is
zinc sulfate. The counter ions are not all in the same plane, however, because they
are held in a dynamic balance by electrostatic attraction and the tendency to diffuse
away. The counter ions form a diffuse layer. Their concentration is high near the
surface of the electrode and goes on decreasing towards the bulk of the solution.
Thus the surface charge forms one layer and the diffuse shielding charge forms the
other layer, hence the term double layer. The potential difference between the
two layers of the electrical double layer is called the potential difference at the
interface or the single electrode potential.
A model of the double layer with negative surface charge is shown below.

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The double layer has a certain structure. The Inner Helmholtz Plane (IHP) is the plane cutting
through the center of the adsorbed species. The Outer Helmholtz plane (OHP) is the plane cutting
through the positive ions at their position of closest approach.

Significance of single electrode potential.

The interfacial potential differences which develop in electrode-solution systems are
limited to only a few volts at most. This may not seem like very much until you
consider that this potential difference spans a very small distance. In the case of an
electrode immersed in a solution, this distance corresponds to the thin layer of water
molecules and ions that attach themselves to the electrode surface, normally only a
few atomic diameters. Thus a very small voltage can produce a very large potential
gradient. For example, a potential difference of one volt across a typical 108 cm
interfacial boundary amounts to a potential gradient of 100 million volts per
centimeter a very significant value indeed!
For an electrode reaction to occur, charged particles should cross the interface
between the metal and solution. Interfacial potential difference or Single Electrode
Potential play s a significant role then. The manipulation of the interfacial potential
difference affords an important way of exerting external control on an electrode
reaction.
Definition of single electrode potential.
The electrode potential of a metal is the measure of tendency of a metallic
electrode to lose or gain electrons, when it is in contact with a solution of its
own salt of unit molar concentration at 25oC.
The tendency of a metal to lose electrons is known as its oxidation potential.
Similarly, the tendency to accept electrons is called reduction potential. The value
of reduction potential is negative of its oxidation potential. Thus , if the oxidation
potential of an electrode is +x volt, then its reduction potential will be X volt.
Interfacial potential differences are not directly observable. The usual way of
measuring a potential difference between two points is to bring the two leads of a
voltmeter into contact with them. It's simple enough to touch one lead of the meter to
a metallic electrode, but there is no way you can connect the other lead to the
solution side of the interfacial region without introducing a second electrode with its
own interfacial potential, so you would be measuring the sum of two potential
differences. Thus single electrode potentials, as they are commonly known, are not

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directly measurable. What we can measure, and make much use of, are potential
differences between pairs of electrodes in electrochemical cells.
Summary
Electroneutrality principle - Bulk matter cannot have a chemically-significant unbalance of
positive and negative ions..
Interfacial potentials - these exist at all phase boundaries. In the case of a metal in contact with an
electrolyte solution, the interfacial region consists of an electric double layer.
The potential difference between a metal and the solution is almost entirely located across the very
thin double layer, leading to extremely large potential gradients in this region.

Concept Map

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ELECTRO CHEMISTRY

Engineering chemistry II

II .ELECTROCHEMICAL CELL.
It is physically impossible to measure the potential difference between a piece
of metal and the solution in which it is immersed. We can, however, measure the
difference between the potentials of two electrodes that dip into the same solution, or
more usefully, are in two different solutions. In the latter case, each electrodesolution pair constitutes an oxidation-reduction half cell, and we are measuring the
sum of the two half-cell potentials.

This arrangement is called a galvanic cell. A typical cell might consist of two pieces
of metal, one zinc and the other copper, each immersed in a solution containing a
dissolved salt of the corresponding metal. The two solutions are separated by a
porous barrier that prevents them from rapidly mixing but allows ions to diffuse
through. If we connect the zinc and copper by means of a metallic conductor, the
excess electrons that remain when Zn2+ ions emerge from the zinc in the left cell
would be able to flow through the external circuit and into the right electrode, where
they could be delivered to the Cu2+ ions which become "discharged", that is,
converted into Cu atoms at the surface of the copper electrode. The net reaction is
the oxidation of zinc by copper(II) ions:
Zn(s) + Cu2+ Zn2+ + Cu(s)

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but this time, the oxidation and reduction steps (half reactions) take place in separate
locations:
left electrode: Zn(s) Zn2+ + 2e

oxidation

right electrode: Cu2+ + 2e Cu(s)

reduction

Electrochemical cells allow measurement and control of a redox reaction.

Electrochemical cells are the ones in which a spontaneous chemical reaction
occurs. The decrease in free energy is converted to electrical energy. The
chemical energy is converted to electrical energy.
The reaction can be started and stopped by connecting or disconnecting the two
electrodes. If we place a variable resistance in the circuit, we can even control the
rate of the net cell reaction by simply turning a knob. By connecting a battery or
other source of current to the two electrodes, we can force the reaction to
proceed in its non-spontaneous, or reverse direction. In this case, the cell is
termed as electrolytic cell.
An electrolytic cell is the one in which a non-spontaneous chemical reaction is
brought about by supplying electrical energy; electrical energy is converted to
chemical energy.
By placing an ammeter in the external circuit, we can measure the amount of electric
charge that passes through the electrodes, and thus the number of moles of reactants
that get transformed into products in the cell reaction.
Electric charge q is measured in coulombs. The amount of charge carried by one
mole of electrons is known as the faraday, which we denote by F. Careful
experiments have determined that 1 F = 96467 c. For most purposes, you can simply
use 96,500 coulombs as the value of the faraday.
When we measure electric current, we are measuring the rate at which electric
charge is transported through the circuit. A current of one ampere corresponds to the
flow of one coulomb per second
Transport of charge within the cell

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For the cell to operate, not only must there be an external electrical circuit between
the two electrodes, but the two electrolytes (the solutions) must be in contact. The
need for this can be understood by considering what would happen if the two
solutions were physically separated. Positive charge (in the form of Zn2+) is added to
the electrolyte in the left compartment, and removed (as Cu2+) from the right side,
causing the solution in contact with the zinc to acquire a net positive charge, while a
net negative charge would build up in the solution on the copper side of the cell.
These violations of electro neutrality would make it more difficult (require more
work) to introduce additional Zn2+ ions into the positively-charged electrolyte or for
electrons to flow into the right compartment where they are needed to reduce the
Cu2+ ions, thus effectively stopping the reaction after only a chemically insignificant
amount has taken place.

In order to sustain the cell reaction, the charge carried by the electrons through the
external circuit must be accompanied by a compensating transport of ions between
the two cells. This means that we must provide a path for ions to move directly from
one cell to the other. This ionic transport involves not only the electro active species
Cu2+ and Zn2+, but also the counter ions, which in above example are nitrate, NO3.
Thus the positive charge resulting from the release of Zn2+ in the left compartment
could be compensated by the drift of these ions into the right side, or equally well by
diffusion of nitrate ions from the righ-hand cell to the left.
More detailed studies reveal that both processes occur, and that the relative amounts
of charge carried through the solution by positive and negative ions depends on their
relative mobilities, which express the velocity with which the ions are able to make
their way through the solution. Since negative ions tend to be larger than positive
ions, the latter tend to have higher mobilities and carry the larger fraction of charge.

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In the diagram below, sodium and sulfate ions serve the same function. (Neither of
these ions is able to undergo oxidation or reduction in the presence of water.)

In the simplest cells, the barrier between the two solutions can be a porous
membrane, but for precise measurements, a more complicated arrangement, known
as a salt bridge, is used. The salt bridge consists of an intermediate compartment
filled with a concentrated solution of KCl and fitted with porous barriers at each end.
The purpose of the salt bridge is to minimize the natural potential difference, known
as the junction potential, that develops (as mentioned in the previous section) when
any two phases (such as the two solutions) are in contact. This potential difference
would combine with the two half-cell potentials so as introduce a degree of
uncertainty into any measurement of the cell potential. With the salt bridge, we have
two liquid junction potentials instead of one, but they tend to cancel each other out.
Cell description conventions
In order to make it easier to describe a given electrochemical cell, a special symbolic
notation has been adopted. A simple notation that is used to give the important
information about a galvanic cell is called a cell diagram.

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Engineering chemistry II

A galvanic cell (sometimes more appropriately called a voltaic cell) consists of two
half-cells joined by a salt bridge or some other path that allows ions to pass between
the two sides in order to maintain electro neutrality.
The conventional way of representing an electrochemical cell of any kind is to write
the oxidation half reaction on the left and the reduction on the right. Thus for the
reaction
Zn(s) + Cu2+ Zn2+ + Cu(s)
we write
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
in which the single vertical bars represent phase boundaries. The double bar denotes
a liquid-liquid boundary which in laboratory cells consists of a salt bridge or in ionpermeable barrier. If the net cell reaction were written in reverse, the cell notation
would become
Cu(s) | Cu2+(aq) || Zn 2+(aq) | Zn (s)
Remember: the Reduction process is always shown on the Right.
The cell diagram of the Daniel cell described above is given below.
Zn(s) | Zn2+(aq, 1.00 M) || Cu2+(aq 1.00 M) | Cu(s)
1
1.
2.
3.
4.
5.
6.
7.

Anode
Electrolyte in the anodic half cell
Concentration of Zn2+ electrolyte in the half cell
Salt bridge
Electrolyte the cathodic half cell
Concentration of Cu2+ electrolyte in the half cell.
Cathode

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Types of electrodes. Depending on the species involved in electron transfer

reactions at the metal-electrolyte interface, the following types of electrodes are
known.
1. Metal-metal ion electrode. The following diagram shows the electron transfer
between a metal ion and the electrode.

In the example of the Zn/Cu cell we have been using, the electrode reaction
involves a metal and its hydrated cation; we call such electrodes metal-metal ion
electrodes. There are a number of other kinds of electrodes which are widely
encountered in electrochemistry and analytical chemistry.

Ion-ion electrodes
Many electrode reactions involve only ionic species, such as Fe2+ and Fe3+. If
neither of the electroactive species is a metal, some other metal must serve as a
conduit for the supply or removal of electrons from the system. In order to avoid
complications that would arise from electrode reactions involving this metal, a
relatively inert substance such as platinum is commonly used. Such a half cell
would be represented as
3+
2+
Pt(s) | Fe (aq), Fe (aq) || ...
and the half-cell reaction would be

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Fe2+(aq) Fe3+ (aq) + e.

Gas electrodes
Some electrode reactions involve a gaseous species such as H2, O2, or Cl2. Such
reactions must also be carried out on the surface of an electrochemically inert
conductor such as platinum. A typical reaction of considerable commercial
importance is

Cl (aq) Cl2(g) + e
Similar reactions involving the oxidation of Br2 or I2 also take place at platinum
surfaces.

Insolublesalt electrodes
A typical electrode of this kind consists of a silver wire covered with a thin
coating of silver chloride, which is insoluble in water. The electrode reaction
consists in the oxidation and reduction of the silver:

AgCl(s) + e Ag(s) + Cl (aq)

The half cell would be represented as

... || Cl (aq) | AgCl (s) | Ag (s)

Reference half-cells.
The fact that individual half-cell potentials are not directly measurable does
not prevent us from defining and working with them. Although we cannot
determine the absolute value of a half-cell potential, we can still measure its
value in relation to the potentials of other half cells. In particular, if we adopt
a reference half-cell whose potential is arbitrarily defined as zero, and
measure the potentials of various other electrode systems against this
reference cell, we are in effect measuring the half-cell potentials on a scale
that is relative to the potential of the reference cell. The reference cell that
has universally been adopted for this purpose is the hydrogen half-cell
Pt | H2(g) | H+(aq) || ...

in which hydrogen gas is allowed to bubble over a platinum electrode having a

specially treated surface which catalyzes the reaction
H2(g) H+ + e

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When this electrode is operated under standard conditions of 1 atm

H2 pressure, 25C, and pH = 0, it becomes the standard hydrogen electrode,
sometimes abbreviated SHE. It is the primary reference electrode.

Drawbacks of SHE Standard Hydrogen Electrode. The SHE is seldom used in

routine electrochemical measurements because it is more difficult to prepare; the platinum surface
has to be specially treated by preliminary electrolysis. Also, there is need for a supply of hydrogen
gas which makes it somewhat cumbersome and hazardous.

Secondary reference electrodes. The major requirements of a reference

electrode are that it be easy to prepare and maintain, and that its potential be
stable. The last requirement essentially means that the concentration of any ionic
species involved in the electrode reaction . The most common way of accomplishing

this is to use an electrode reaction involving a saturated solution of an insoluble salt of the
ion. One such system, the silver-silver chloride electrode .

Ag | AgCl(s) | Cl (aq) || ...

Ag(s) + Cl (aq) AgCl(s) + e

This electrode usually takes the form of a piece of silver wire coated with AgCl. The coating is
done by making the silver the anode in an electrolytic cell containing HCl; the Ag+ ions
combine with Cl ions as fast as they are formed at the silver surface.
The other common reference electrode is the calomel electrode; calomel is the common name
for mercury(I) chloride.
2+

Hg | Hg (aq) | KCl || ... Hg(l) + Cl HgCl2(s) + e

The potentials of both of these electrodes have been very accurately determined against the
hydrogen electrode..

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ELECTRO CHEMISTRY

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Measurement of electrode potentials.

In order to measure the relative potential of some other electrode couple
M2+/M, we can set up a cell
Pt | H2(g) | H+ || M2+ (aq) | M(s)

whose net reaction is

H2(g) + M2+(aq) 2H+ + M(s)
the potential difference between the platinum and M electrodes will be
Ecell = VM Vsolution + Vsolution V

Pt

but since the difference Vsolution V Pt is by definition zero for the hydrogen
half-cell, the cell potential we measure corresponds to
Ecell = VM Vsolution
which is just the potential (relative to that of the SHE) of the half-cell whose
reaction is
M2+ + 2e M(s)

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The cell diagram of the above cell is as follows.

Pt | H2(g) | H+ || Cu2+ (aq) | Cu(s)

Eocell
Eocell

=
=

Eocathode - Eoanode
EoCu(II)/Cu(0) - EoSHE

Eocell

EoCu(II)/Cu(0) - 0

Eocell

EoCu(II)/Cu(0)

Experimental Determination of cell emf by potentiometric method.

The electromotive force (emf) of a cell is its terminal voltage when no current is
flowing through it. The terminal voltage of a cell is the potential difference between its
electrodes. A voltmeter cannot be used to measure the emf of a cell because a voltmeter
draws some current from the cell. To measure a cell's emf a potentiometer is used since
in a potentiometer measurement no current is flowing. It employs a null method of
measuring potential difference, so that when a balance is reached and the reading is
being taken, no current is drawn from the source to be measured. The cell emf is
opposed by an external emf so that no current flows through the cell. This principle is
called Poggendorfs compensation principle.

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This is the basic circuit diagram for a potentiometer. Point C is the sliding contact
which can be adjusted for zero current deflection through the galvanometer.
In this method (refer to Figure above) a uniform, bare slide wire AB is connected across
the power supply. If you were to connect a voltmeter between the + power supply
terminal and point A you would measure essentially zero volts. If you were to now
connect the voltmeter between the + power supply and point B you would measure a
voltage equal to the terminal voltage of the power supply which is approximately 2.5
volts. The potential relative to point A then varies from zero at A to approximately 2.5
volts at B.
The cell whose emf is to be determined is then connected so that its emf opposes the
potential along the wire. At some point C the potential difference between A and C is
exactly equal to the emf of the cell so that if the other terminal of the cell is connected
to the point C, no current will flow. The calibration procedure is to locate this point C
using a standard cell whose emf is accurately known (emf = 1.0186 volts). You then
know that at this point C the potential difference relative to point A is exactly 1.0186
volts.
Since the wire is uniform, the length of wire spanned is proportional to the potential
drop and the wire can now be calibrated in volts per cm. The emf of an unknown cell is
then found by finding a new point C whose potential is exactly equal to the emf of the
unknown cell and multiplying this new distance AC times the calibration factor
determined using the standard cell.
It is crucial in this experiment that the current flowing through wire AB remain constant
throughout the experiment. If the current varies then the potential at all points along the
wire will vary and you cannot trust your calibration. An ammeter is included in series
with wire AB so that you can monitor this current. (See Figure 2.) The circuits used in
this experiment are shown below in Figures 2 and 3.

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In this photograph, the apparatus used for the potentiometer is shown: an adjustable
resistor, test cell, standard cell, galvanometer, ammeter, direct-current source, and the
bare wire above a meter stick along which the potential drop is measured

Here s is the standard cell (emf = 1.0186 volts), and x is the unknown cell whose
emf is to be measured. G is the galvanometer which has an internal resistor R1 in series
with the meter to decrease its sensitivity. Once the potentiometer is balanced by
adjusting point C until there is no deflection of G, switch K1 (a pushbutton on top of the
galvanometer) is closed to increase the sensitivity of G by shorting out R1. Point C is
then further adjusted with K1 closed until there is no deflection of G.
Since the electromotive force of the standard cell is equal to the potential drop in the
length of wire spanned (measured from A) for a condition of balance and the same is
true for the unknown cell, the emf of each cell is proportional to the lengths of wire
spanned. Thus

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and the unknown emf is given by

where x is the unknown emf and, s is the emf of the standard cell, Lx is the length of
wire (AC) used for balancing the unknown cell, and Ls is the length of wire used for
balancing with the standard cell.
Electrochemical series
Standard [reduction] potentials, the potentials measured under the standard
conditions of 1M concentration of the electrolyte at 25oC , are commonly
denoted by the symbol E. E values for hundreds of electrodes have been
determined (mostly in the period 1925-45, during which time they were
referred to as "oxidation potentials") and are usually tabulated in order of
increasing tendency to accept electrons (increasing oxidizing power.) The
series obtained by arranging the half cells in the order of increasing standard
reduction potentials is called electrochemical series.

Table 2: some standard

reduction potentials
Note particularly that

This table includes metallic

as well as non-metallic
substances, and it is
quantitative.
The more negative the
half-cell EMF, the greater
the tendency of the
reductant to donate
electrons, and the smaller
the tendency of the
oxidant to accept
electrons.

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oxidant
(electron acceptor)

reductant
(electron donor)

Na+

Na(s)

2.71

2+

Zn(s)

.76

2+

Fe(s)

.44

2+

Cd(s)

.40

2+

Pb(s)

.126

Zn
Fe

Cd
Pb

2H

H2(g)

AgCl(s)
Hg2Cl2(s)
Cu

Ag(s) + Cl (aq)

0.000
+.222

2Cl (aq) + 2Hg( ) +.268

2+

I2(s)
3+

Fe

Ag

E, volts

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Cu(s)

+.337

+.535

2+

Fe

+.771

Ag(s)

+.799

2I

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A species in the leftmost

column can act as an
oxidizing agent to any
species above it in the
reductant column.

O2(g) + 4H+

2 H2O( )

Cl2(g)

2 Cl

+1.23
+1.36

Oxidants such as Cl2 that

are below H2O will tend to
decompose water.

Given the E values for two half reactions, you can easily predict the potential
difference of the corresponding cell: simply add the reduction potential of the
reduction half-cell to the negative of the reduction potential (that is, to the
oxidation potential) of the oxidation reaction.

Problem Example 1
Find the standard potential of the cell
Cu(s) | Cu2+ || Cl | AgCl(s) | Ag(s)

and predict the direction of electron flow when the two electrodes are
connected.
Solution: The above notation represents a cell in which metallic copper
undergoes oxidation, delivering electrons to a reactant on the right, which
gets reduced. But what species actually receives the electron? It cannot
be Ag, because metallic elements do not form negative ions. The only
reducible species on the right is the Ag+ contained within the insoluble salt
AgCl. Reduction of this ion to metallic Ag is accompanied by a release of
Cl ions into the solution. The two half-reactions and their standard
potentials are
Cu(s) Cu2+(aq) + 2 e

(+0.337) v

AgCl(s) + e Ag(s) + Cl(aq)

+0.222 v

Note that because Cu is being oxidized (rather than reduced), we take

the negative of the standard reduction potential.

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Multiplying the second equation (but not its reduction potential) by 2 in

order to balance electrons, we have the net reaction
2 AgCl(s) + Cu(s) 2 Ag(s) + Cl(aq) + Cu2+(aq)
Combining the two half-cell potentials shown above, the net cell potential
is
Ecell = (0.337 + 0.222) v = 0.115 v
Because this potential is negative, we know that the net cell reaction (and,
of course, the two half reactions) proceed in the reverse directions to those
depicted above. Thus when the two electrode are connected, electrons
pass from the silver electrode through the external circuit to the copper
electrode. Note that this corresponds to the rule in noted in Table 2
above: AgCl acts as an oxidizing agent (electron sink) to metallic
copper which appears below it in the reductant column.
If you are wondering wny we did not multiply E the for the Cu2+/Cu couple
by two, the reason for this will be explained in the next section.

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Cell potentials and free energy

From the above, it should be apparent that the potential difference between
the electrodes of a cell is a measure of the tendency for the cell reaction to
take place: the more positive the cell potential, the greater the tendency for
the reaction to proceed to the right. But we already know that the standard
free energy change expresses the tendency for any kind of process to occur
under the conditions of constant temperature and pressure. Thus G
and Emeasure the same thing, and are related in a simple way:
G = nFE

(2)

... or in more detail (see below for explanations of the units given for voltage)

A few remarks are in order about this very fundamental and important
relation:

The negative sign on the right indicates that a positive cell potential (according to the
sign convention discussed previously) implies a negative free energy change, and thus
that the cell reaction will spontaneously proceed to the right.
Electrical work is done when an electric charge q moves through a potential difference
V. The right side of Eq. 2 refers to the movement of n moles of charge across the cell
potential E, and thus has the dimensions of work.
The value of G expresses the maximum useful work that a system can do on the
surroundings. "Useful" work is that which can be extracted from the cell by electrical
means to operate a lamp or some other external device. This excludes any P-V work
that is simply a consequence of volume change (which could conceivably be put to
some use!) and which would be performed in any case, even if the reactants were
combined directly. This quantity of work G can only be extracted from the system
under the limiting conditions of a thermodynamically reversible change, which for an
electrochemical cell implies zero current. The more rapidly the cell operates, the less
electrical work it can supply.

If F is expressed in coulombs per mole of electrons, the electrical work is in joules

per mole. To relate these units to electrical units, recall that the coulomb is one

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amp-sec, and that power, which is the rate at which work is done, is measured in
watts, which is the product of amps and volts.
1 J = 1 watt-sec = 1 (amp-sec) volts

Thus the volt has the dimensions of joules/coulomb the energy produced per
quantity of charge passing through the cell. Because voltage is the quotient of
two extensive quantities, it is itself intensive. When we multiply the anodic and
cathodic half-reactions by the stoichiometric factors required to ensure that each
involves the same quantity of charge, the free energy change and the number of
coulombs both increase by the same factor, leaving the potential (voltage)
unchanged. This explains why we do not have to multiply the Es of the anode
and cathode reactions by stoichiometric factors when we are finding the potential
of a complete cell.

If Eq. 2 is solved for E, we have

This states explicitly that the cell potential is a measure of the free energy
change per mole of electrons transferred, which is a brief re-statement of the
principle explained immediately above.
To see this more clearly, consider the cell
Cu(s) | Cu2+ || Cl | AgCl(s) | Ag(s)

for which we list the standard reduction potentials and Gs of the halfreactions:
reaction

-nFE= G

cathode: 2 [AgCl(s) + e Ag(s) + Cl ]

+.222 v

42800 J

anode: Cu(s) Cu2+ + 2 e

(+.337) v

+65000 J

.115 v

+22200 J

net: 2 Ag(s) + 2 Cl(aq) + Cu2+(aq) AgCl(s) + Cu(s)

cell: Cu(s) | Cu2+(aq) || AgCl(s) | Cl(aq) | Ag(s)

Here we multiply the cathodic reaction by two in order to balance the charge.
Because the anodic reaction is written as an oxidation, we reverse the sign of
its E and obtainEcell = Eright Eleft = .115 volt for the cell potential. The
negative cell potential tells us that this reaction will not proceed
spontaneously.

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When the electrons don't cancel out

Note, however, that if we are combining two half reactions to obtain a third
half reaction, theE values are not additive, since this third half-reaction is not
accompanied by another half reaction that causes the charges to cancel. Free
energies are always additive, so we combine them, and use G = nFE to
find the cell potential.

Problem Example 2
Calculate E for the electrode Fe3+/Fe(s) from the standard potential of the
couples Fe3+/Fe2+ and Fe2+/Fe(s)
Solution: Tabulate the values and calculate the Gs as follows:
(i)
(ii)
(iii)

Fe3+ + e Fe2+
2+

Fe

+ 2 e Fe(s)

3+

Fe

+ 3 e Fe(s)

E1 = .771 v , G1 = .771 F
E2= .440 v , G2 = +.880 F
E3 = ? , G3 = +.109 F

The free energy for half-reaction (iii) is .109nF, so E3 = .109/3 =

.036 v

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.
.

How cell potentials depend on

concentrations
The standard cell potentials we discussed in a previous section refer to cells in
which all dissolved substances are at unit activity, which essentially means an
"effective concentration" of 1M. Similarly, any gases that take part in an
electrode reaction are at an effective pressure (known as the fugacity) of 1
atm. If these concentrations or pressures have other values, the cell potential
will change in a manner that can be predicted from the principles you already
know.
Suppose, for example, that we reduce the concentration of Zn2+ in the Zn/Cu
cell from its standard effective value of 1M to an to a much smaller value:
Zn(s) | Zn2+(aq, .001M) || Cu2+(aq) | Cu(s)

This will reduce the value of Q for the cell reaction

Zn(s) + Cu2+ Zn2+ + Cu(s)
thus making it more spontaneous, or "driving it to the right" as the Le
Chtelier principlewould predict, and making its free energy change G more
negative than G, so that Ewould be more positive than E.
The relation between the actual cell potential E and the standard potential E
is developed in the following way. We begin with the equation derived
previously which relates the standard free energy change (for the complete
conversion of products into reactants) to the standard potential
G = nFE
By analogy we can write the more general equation
G = nFE
which expresses the change in free energy for any extent of reaction that is,
for any value of the reaction quotient Q. We now substitute these into the
expression that relates G and G which you will recall from the chapter on
chemical equilibrium:

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G = G + RT ln Q
which gives
nFE = nFE + RT ln Q
which can be rearranged to

This is the very important Nernst equation which relates the cell potential to
the standard potential and to the activities of the electroactive species. Notice
that the cell potential will be the same as E only if Q is unity. The Nernst
equation is more commonly written in base-10 log form and for 25C:

Significance of the Nernst eqation

The Nernst equation tells us that a half-cell potential will change by 59
millivolts per 10-fold change in the concentration of a substance involved in a
one-electron oxidation or reduction; for two-electron processes, the variation
will be 28 millivolts per decade concentration change. Thus for the dissolution
of metallic copper
Cu(s) Cu2+ + 2e
the potential
E = ( 0.337) .0295 log [Cu2+]
becomes more positive (the reaction has a greater tendency to take place) as
the cupric ion concentration decreases. This, of course, is exactly what the Le
Chtelier Principle predicts; the more dilute the product, the greater the
extent of the reaction.

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below 106 M.

The Nernst equation works only in dilute ionic solutions

Ions of opposite charge tend to associate into loosely-bound ion pairs in more
concentrated solutions, thus reducing the number of ions that are free to
donate or accept electrons at an electrode. For this reason, the Nernst
equation cannot accurately predict half-cell potentials for solutions in which
the total ionic concentration exceeds about 103 M.

How the cell

potential really depends on
concentration!
The Nernst equation accurately
predicts cell potentials only when the
equilibrium quotient term Q is
expressed in activities. Ionic activities
depart increasingly from
concentrations when the latter exceed
104 to 105 M, depending on the sizes
and charges of the ions.

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Activities and activity coefficients

If the Nernst equation is applied to more concentrated solutions, the terms in
the reaction quotient Q must be expressed in "effective concentrations"
or activities of the electroactive ionic species. The activity coefficient
(gamma) relates the concentration of an ion to its activity a in a given
solution through the relation a = c. Since electrode potentials measure
activities directly, activity coefficients can be determined by carrying out
appropriate EMF measurements on cells in which the concentration of the ion
of interest is known. The resulting Es can then be used to convert
concentrations into activities for use in other calculations involving equilibrium
constants.

Concentration cells
From your study of thermodynamics you may recall that the process
solute (concentrated) solute (dilute)
is accompanied by a fall in free energy, and therefore is capable of doing work on the
surroundings; all that is required is some practical way of capturing this work. One
way of doing this is by means of a concentration cell such as
Cu(s) | CuNO3(.1 M) || CuNO3(.01 M) | Cu(s)
cathode: Cu2+(.1 M) + 2e Cu(s)
anode: Cu(s) Cu2+(.01 M) + 2e
net: Cu2+(.1 M) Cu2+(.01 M)
which represents the transport of cupric ion from a region of higher concentration to
one of lower concentration.
The driving force for this process is the free energy change G associated with the
concentration gradient (C2 C1), sometimes known as the free energy of dilution:
Gdilution = RT ln(C2 C1)
Note, however, that Cu2+ ions need not physically move between the two
compartments; electron flow through the external circuit creates a "virtual" flow as
copper ions are created in the low-concentration side and discharged at the opposite
electrode. Nitrate ions must also pass between the cells to maintain electroneutrality.
The Nernst equation for this cell is

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E = E - (0.059/N) log Q = 0 - 0.29 log 0.1 = +0.285 v

Note that E for a concentration cell is always zero, since this would be the potential
of a cell in which the electroactive species are at unit activity in both compartments.

Concept Map

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Reference.
The material has been taken from the following reference by Dr.Stephan
Lower of Simon Fraser University. Virtual textbook page is very colourful and
informative. Students! You would enjoy going through that. Kindly do so.

2005 by Stephen Lower - Simon Fraser University - Burnaby/Vancouver Canada; Last

modifed 6-03-2007

For information about this Web site or to contact the author, please go to the Chem1
Virtual Textbook page

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