Unit 7 Electrochemistry-I

UNIT 7
Electrochemistry-I

Structure
7.1 Introduction Experimental Measurement of
EMF of Cell
Expected Learning Outcomes
7.6 Thermodynamics of Reversible
7.2 Electrochemical Cells
Cell
Galvanic Cells
Cell EMF and Spontaneity
Electrolytic cells
Cell EMF and Equilibrium Constant
7.3 Reversible and Irreversible
7.7 Nernst Equation
Cells
Applications of Nernst equation
7.4 Representing Electrochemical
Cells 7.8 Types of Electrodes
Cell Diagram and Cell Reaction 7.9 Summary
7.5 EMF of a Cell 7.10 Terminal Questions
Standard Reduction Potential 7.11 Answers

7.1 INTRODUCTION
In the previous two units you have learnt about different aspects of conduction
in electrolytic solutions. You would recall from Unit 5 that while discussing
about the mechanism of electrolytic conduction, we mentioned that when the
ions carrying current through the bulk of the electrolytic solution reach the
electrode, they undergo chemical reactions there. These reactions are
characteristic and depend on the nature of the electrolyte and the electrode. In
this and the next unit you would learn about electrochemical cells where we
would discuss the processes occurring at the electrodes in the cells and their
consequences.

In this unit dealing with first part of our discussion on electrochemistry we

would begin by introducing the domain of electrochemistry and discussing
electrochemical cells. Since most of the practical applications of
electrochemistry require electrochemical cells working reversibly so we would
clarify the meaning of reversible cells. This will be followed by discussion on
galvanic cells, their representation and writing cell reactions. Then we would
take up the concept of emf of a cell and its measurement. In this context we
would introduce the concepts of electrode potential; and standard electrode
176 potential.
Unit 7 Electrochemistry-I
We would then take up thermodynamic aspect of reversible cells. Herein, we
would take up the relationship between cell emf and thermodynamic
parameters like, Gibbs energy, equilibrium constant etc. We would also take
up Nernst equation and its applications before describing different types of
electrodes. In the next unit we would focus our discussion on the principles of
concentration cells, electrolytic cells, and applications of emf measurements.

Expected Learning Outcomes

After studying this unit, you should be able to:

❖ define electrochemistry and state it’s importance;

❖ differentiate between galvanic and electrolytic cells;

❖ differentiate between reversible and irreversible cells;

❖ describe a galvanic cell and explain its principle in terms of electrode

reactions;

❖ represent given galvanic cell in terms of cell diagram and write cell
reactions for it;

❖ explain the meaning and outline the significance of standard electrode

potential;

❖ define emf of a cell and calculate the same using standard electrode
potentials of the redox couples involved;

❖ describe the method for experimental measurement of cell emf;

❖ derive a relationship between cell emf and the Gibbs energy and predict
the spontaneity of cell reaction of a given galvanic cell;

❖ calculate the equilibrium constant of a redox reaction by using cell emf;

❖ write Nernst equations for half-cell reactions and cell reactions;

❖ outline the significance of Nernst equation and predict the spontaneity of

the cell reaction of a non-standard galvanic cell using the same;

❖ explain the principle of determination of pH of an aqueous solution using

emf measurement;

❖ list and describe different types of electrodes; and

❖ write the half-cell reactions and representations of different electrodes.

7.2 ELECTROCHEMICAL CELLS

As you are aware, electrochemistry is the branch of physical chemistry that
deals with the relationship between electricity, and chemical change in the
system. There are two possibilities where such a relationship exists; in one of
these, the spontaneous chemical reactions produce electricity and in the other,
we use electricity to bring about non-spontaneous chemical reactions. In 177
Block 2 Conductance and Electrochemistry
simple words, we can say that electrochemistry is the study of production of
electricity from energy released during spontaneous chemical reactions and
the use of electrical energy to make non-spontaneous reactions possible.

Further, you are also familiar with redox reactions-the chemical reactions that
involve transfer of electrons between two reactants participating in it. A cell in
which the progress of such an oxidation-reduction reaction is associated with
electric current is called an electrochemical cell. These are of two types. The
electrochemical cell in which the progress of a spontaneous chemical reaction
causes an electric current to flow is called a galvanic cell. On the other hand,
the electrochemical cell in which a current is passed by an external voltage, to
make an otherwise non-spontaneous chemical reaction to proceed is called an
electrolytic cell. An electrochemical cell typically consists of a solution of an
electrolyte and two electrodes at which oxidation and reduction processes
occur, respectively. The electrolyte usually is a solution of an acid, base or a
salt or a pure liquid. Here, in this unit we are going to take up the study of
galvanic cells. Let’s understand what are galvanic cells.

7.2.1 Galvanic Cells

In order to learn about galvanic cells, let us take up some simple experiments.
In the first experiment we take an aqueous solution of silver nitrate in a beaker
and dip a strip of copper in it. We would observe the following:

a) The part of copper strip dipped into the solution becomes thinner (some
copper metal is lost);

b) The colour of otherwise colourless solution becomes bluish;

c) A silvery layer is formed on the dipped copper strip

Expt.1: Copper strip d) The solution temperature increases slightly
in aqueous solution of
AgNO3 These observations can be explained in terms of the following changes

i) The copper atoms in the copper plate get oxidised to cupric ions releasing
two electrons, as per the following equation
Cu(s) → Cu2+(aq) + 2e− (Oxidation) …(7.1)

The blue colour of the solution is due to the formation of these cupric ions.

ii) The silver ions get reduced to silver metal by accepting the electrons
released by copper as per the following equation
2Ag+(aq) + 2e− → 2Ag(s) (Reduction) …(7.2)

The metallic silver so obtained is deposited on the copper plate.

The overall reaction can be given as the following redox reaction

Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) …(7.3)

In simpler words, we can say that copper metal has a greater tendency to get
oxidised and displaces silver ions from the solution and there is a transfer of
electrons from copper atom to silver ions. Let’s take the second experiment to
be a familiar one; dipping a zinc rod in an aqueous solution (blue coloured) of
178 Copper (II) sulphate. In this case, we observe the following
Unit 7 Electrochemistry-I
a) The part of zinc rod dipped into the solution becomes thinner (some zinc
metal is lost);

b) The colour of blue solution fades and eventually becomes colourless;

c) Reddish-brown solid (elemental copper) deposits on the surface of zinc

rod

d) The solution temperature increases slightly

These observations can be explained in terms of the following changes

i) The zinc atoms in the zinc rod get oxidised to zinc ions by releasing two
electrons, as per the following equation
−
Zn(s) → Zn2+(aq) + 2e (Oxidation) …(7.4)
Expt.2: Zinc strip in
This accounts for the thinning of zinc rod aqueous solution of
CuSO4
ii) The copper ions in the solution get reduced to copper metal by accepting
the electrons released by zinc atoms as per the following equation

Cu2+(aq) + 2e− → Cu(s) (Reduction) …(7.5)

This is results in the formation of reddish-brown solid on the surface of

zinc rod

The overall reaction can be given as the following redox reaction

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) …(7.6)

In simpler words, we can say that zinc metal has a greater tendency to get
oxidised and displaces copper ions from the solution and there is a transfer of
electrons from zinc atom to copper ions. In the third experiment we dip a strip
Expt.3: Copper strip
of copper in an aqueous solution of Zinc (II) nitrate. In this case, we do not
in aqueous solution of
observe any reaction. Zn (NO3)2
Cu(s) + Zn2+(aq) → No reaction …(7.7)

What do we conclude from these experiments? We conclude that the

experiment 1 and 2 involve spontaneous reactions as represented by the
Eqs.(7.3) and (7.6) whereas, the reaction between copper metal and zinc ions
(experiment 3) is not spontaneous. You know from your earlier studies on
chemical energetics that a spontaneous reaction is accompanied by a
decrease in Gibbs energy. This Gibbs energy change leads to a change in the
temperature of the solution in experiment 1 and 2.

Now, the question comes up is ‘can we use the Gibbs energy change in
spontaneous reactions for doing some work?” and if yes, ‘how do we do
so?’The answer is yes and we can do so by not allowing a direct transfer of
electrons between the reactants. Practically speaking, this can be achieved by
separating the process of release of electrons and their consumption i.e.,
separating zinc metal from the copper sulphate solution in experiment 2. Such
a set up is called a Galvanic or a voltaic cell. Let us learn about the
construction and working of Galvanic cells by taking the example of Daniell
Cell in which the redox reaction given by Eq.(7.6) takes place. 179
Block 2 Conductance and Electrochemistry
Daniell Cell

In order to separate the process of release of electrons and their consumption,

in Daniell cell we take two different electrodes. In one of the electrodeswe take
an aqueous solution of zinc sulphate in a beaker and dip a zinc strip or rod in
it. For the second electrode we take a copper rod or strip and dip it in an
aqueous solution of copper sulphate taken in a beaker. Let us see what
happens in these electrodes. We begin with zinc electrode.

In case of zinc electrode, the strip of zinc is dipped in a dilute solution of zinc
sulphate. As zinc sulphate is a strong electrolyte, it is fully dissociated, and
initially the solution contains equal number of positive (Zn2+) and negative
Galvanic cells are (SO42-) ions and the solution as such is neutral. Similarly, the metal strip can
named after an Italian
be visualised as an array of positively charged kernels in the sea of electron
anatomist Luigi
and the overall metal is also electroneutral.
Galvani, who
demonstrated that Now, since zinc is an electropositive element, some of the zinc atoms from the
passage of electricity
electrode’s surface lose electrons to the electrode and enter the solution as
caused frog muscles
Zn2+ ions, i.e., the zinc atoms get oxidized. As a consequence, the charge
to contract and two
different metals in balance in the metal is disturbed and the metal has a small excess of negative
contact with the charge. On the other hand, due to the release of zinc ions from metal to the
muscle tissue solution there is a small excess of positive charge in the solution. In time,
produce an electric some zinc ions may get attracted back to the negative metal and get deposited
current. on it by taking electrons from there, i.e., the zinc ions get reduced. At a certain
stage, the following redox equilibrium is established between the zinc strip and
the zinc ions.

Zn(s) ⇌ Zn2+(aq) + 2e− …(7.8)

Eventually, a potential develops between the negatively charged electrode and

the excess positive charge in the solution near the electrode. A system
The voltaic cell
containing a metal strip or rod dipped in a solution of its ions is called half-cell
involving zinc and
copper electrodes is (or electrode) and the potential developed is called half-cell potential (or
called a Daniell cell electrode potential). A similar process occurs in case where a copper strip is
after the English dipped in a solution of copper sulphate.
chemist John Daniell,
who developed it in Cu(s) ⇌ Cu2+(aq) + 2e− …(7.9)
1836.
Now, if we connect these two electrodes by a metal wire the electron would
flow from zinc electrode to copper electrode. We can say so on the basis of
experiment 2 and 3 described above. You would recall that in experiment 2
zinc could displace copper ions from solution but in experiment 3 it’s reverse
was not true. This implies that the potential of zinc to get oxidized is more than
that of copper. Alternatively, we can visualise that the voltage, or potential
difference, between the zinc rod and the zinc ions around it is more than that
between the copper rod and copper ions. This difference of voltages (or
potential differences) is the driving force for the transfer of electrons. It is like
the flow of water from a higher level to a lower level.

Further, this flow of electrons from zinc to copper would cause deposition of
copper on the copper electrode due to reduction of copper ions from the
solution. These conclusions are supported by the experimental observation
that in Daniell cell the mass of zinc electrode decreases whereas that of
180 copper electrode increases.
Unit 7 Electrochemistry-I
The reactions at the two electrodes would be:

Zn(s) → Zn2+(aq) + 2e− (Oxidation) …(7.4)

Cu2+(aq) + 2e− → Cu(s) (Reduction) …(7.5)

The overall reaction occurring in the cell can be obtained by adding Eq. (7.4)
and Eq. (7.5) to give
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) …(7.6)
Thus, the chemical change in the cell is basically an electron-transfer reaction.
As a result of the flow of electrons from zinc to copper electrode and the
accompanied reactions there will be an excess of positive charge around zinc
(due to excess Zn2+ ions) and excess of negative charge around copper
electrode (due to excess SO42− ions) as Cu2+ ions here get reduced.
Therefore, the process would stop very soon. For this process to continue we
need to connect the electrolytes in two half cells i.e., complete the electrical
circuit between the two solutions. In other words, the charge carried by the
electrons in the external circuit must be followed by a transport of ions
between the two half cells. That is, we must provide a way for ions to move
from one half cell to the other.

This is achieved by using a salt bridge to link the two electrolytic solutions.
The salt bridge is basically an inverted U-shaped tube containing a saturated
solution of an inert electrolyte like KCl, KNO3 or NaNO3 etc., whose ions are
neither involved in the net chemical change nor do these interact with the
electrodes. This solution is mixed with a gelatinous material, such as agar-
agar, so that it does not flow into the electrode compartments. Other way to do
so is to place a sintered disc on each end of the tube.

Once the two solutions are connected through the salt bridge, the excess
positive charge around the zinc electrode is neutralised by the transfer of
negative ions from the salt bridge and to a small extent by migration of zinc
ions to the salt bridge. Similarly, the excess negative charge around the
copper electrode is neutralized mainly by the transfer of positive ions from the
salt bridge and to a small extent by migration of sulphate ions to the salt
bridge. Due to the neutralisation of the charges around the electrodes, the
oxidation of zinc from the zinc electrode and reduction of copper ions on the
copper electrode resumes. The process of transfer of electrons from zinc to
copper electrode in the external circuit and transfer of ions across the
electrolytes resumes. A schematic diagram of Daniell cell constructed by using
salt bridge to connect the two electrolytes is given in Fig. (7.1)

Fig. 7.1: A schematic diagram of Daniell cell. 181

Block 2 Conductance and Electrochemistry
The function of salt bridge can be given as under:

a. It completes the cell circuit by connecting the electrolyte solutions of two

half cells.
b. It helps in maintaining the electrical neutrality of the solutions in the two
half cells.
c. It does not allow the transfer or diffusion of the electrolyte solution from
one half cell to the other.
d. It prevents the liquid-liquid junction potential i.e., the potential difference
that would develop between two electrolyte solutions if the two are
allowed to be in contact with each other. (you would learn about liquid
junction potential in the next unit.)

The half-cell in which the oxidation reaction takes place is called the anode,
and the half-cell involving the reduction reaction is called the cathode. The
two half-cells put together constitute a voltaic cell. Now, if we attach some
electrical device such as a lightbulb to the wire, connecting two electrodes we
can operate the device (the bulb glows). In other words, by separating the half-
reactions, we can extract work from the spontaneous electrochemical reaction.
Having learnt about the working of a galvanic cell using the example of Daniell
cell let’s learn about writing the cell reaction for a galvanic cell.

Example 7.1: Write down the cell reaction for the galvanic cell on the basis of
the observation that a strip of copper metal when placed in an
aqueous solution of silver nitrate, displaces silver ions from the
solution. However, its reverse is not true.
Solution: The given observation means that copper is more electropositive
than silver; i.e., it has a greater tendency to get oxidised; i.e., the
following reaction takes place at the anode
Cu(s) → Cu2+(aq) + 2e− (Oxidation)
We know that an oxidation reaction must be accompanied by a reduction
reaction; i.e., in the given system the silver ions get reduced to silver atoms.
Since each copper atom loses two electrons to form copper ion and each
silver ion requires just one electron to produce silver atom; therefore, for every
copper ion formed two silver atoms are deposited on the cathode as per the
following reaction

2Ag+(aq) + 2e− → 2Ag(s) (Reduction)

It is important to note Now, if we combine, copper and silver electrodes, they will form a galvanic cell
that while combining in which copper electrode would act as an anode whereas silver electrode will
the half-cell equations act as a cathode. Further, there will be a transfer of electrons from copper
to produce the overall electrode to silver electrode when the current is drawn from the cell. The
cell equation, we overall cell reaction can be obtained by adding the reactions occurring at
must ensure that the
anode (oxidation) and cathode (reduction) as follows:
number of electrons
involved in reduction At anode: Cu(s) → Cu2+(aq) + 2e− (Oxidation)
reaction are equal to
the number involved At cathode: 2Ag+(aq) + 2e− → 2Ag(s) (Reduction)
in oxidation reaction.
Cell reaction: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
182
Unit 7 Electrochemistry-I
On the basis of the above example, we can outline the procedure for writing
the cell reaction for a galvanic cell.

Step1: Write the hall-cell reaction taking place at the anode i.e., the oxidation
reaction

Step 2: Write the half-cell reaction taking place at the cathode i.e., the
reduction reaction

Step 3: Combine the above two half-cell reactions ensuring that the number of
electrons released at the anode is equal to the number of electrons
used at the cathode.

Having learnt about Galvanic or Voltaic cells in which we use the spontaneous
redox reactions to get useful electrical work let us learn about the cells in
which we use external potential to cause a non-spontaneous reaction.

7.2.2 Electrolytic Cells

As stated above, the electrochemical cells in which non-spontaneous
reactions are made to occur by causing a flow of electricity (electric current)
through the cell by using an outside source, such as a battery or a generator
are called electrolytic cells. In an electrolytic cell two electrodes are dipped into
a solution of an electrolyte taken in a container. These electrodes are then
connected to an external source of electricity. As a consequence, the ions in
the electrolyte move towards the oppositely charged electrode and undergo
chemical reactions on the electrodes. The movement of ions is an electric
current. The whole process is called electrolysis. A schematic diagram of an
electrolytic cell is given in Fig. (7.2).

Fig. 7.2: A schematic diagram of an electrolytic cell.

As in case of galvanic cells, the flow of current through the electrolyte is due to
the movement of ions to oppositely charged electrodes whereas in the
external circuit it is due to flow of electrons. We would discuss about
electrolytic cells in details in the next unit. For now, let us learn about the
reversible and irreversible cells. However, before that answer the following
simple question to assess your understanding of electrochemical cells.

SAQ 1
What are galvanic cells? It is observed that a strip of aluminum kept in a
solution of silver nitrate displaces silver ions from solution. Formulate the cell-
equation for a galvanic cell prepared by using aluminum and silver electrodes.
183
Block 2 Conductance and Electrochemistry

7.3 REVERSIBLE AND IRREVERSIBLE CELLS

As stated above, in galvanic cells the Gibbs energy change of the
spontaneous redox reaction causes the development of potential difference
across the electrodes and this can be used to get useful work. We can relate
other thermodynamic parameters with the potential difference and obtain their
values from electrochemical measurements. However, for this to be possible
the electrochemical cell must be reversible.

A reversible cell may be defined as the one in which the reactions are always
in state of equilibrium and only infinitesimally small currents are drawn from it.
A reversible cell must satisfy the following conditions.

i) If we connect an external source of emf to the cell such that the driving
force (applied voltage) and the opposing force (the cell potential
difference) are equal no reaction should occur in the cell

ii) If the applied voltage is infinitesimally smaller than the cell voltage, then
the cell reaction would occur to an infinitesimally small extent and
infinitesimally small current would flow from the cell to external source.

iii) If the applied voltage is infinitesimally greater than the cell voltage, then
the cell reaction would occur to an infinitesimally extent in the reverse
direction and infinitesimally small current would flow from the external
source to the cell

A cell not satisfying the above requirements is called an irreversible cell. Let
us take an example each of reversible and irreversible cells.

Daniell cell discussed above is an example of a reversible cell. If we connect

an external source having slightly lower voltage than the cell, then the
In a typical galvanic following reaction would occur in the cell and a small amount of current would
cell, the half-cells flow from the cell to the external source.
consist of a metallic
electrode dipped into Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) …(7.6)
corresponding salt
solution. The metallic However, if the connected external source has slightly greater voltage than the
electrodes are cell, then the reaction occurring in the cell would get reversed and a small
connected externally amount of current would flow from the external source to the cell.
by a metallic wire and
electrolytes of the two Zn2+ (aq) + Cu(s) → Zn(s) + Cu2+ (aq) …(7.10)
half-cells are
connected internally On the other hand, if the applied external voltage is exactly equal to the cell
through a salt bridge voltage, there will be no reaction in the cell.

Let us now consider a cell containing zinc and silver electrodes dipped in a
solution of sulphuric acid taken in a container. On connecting the two
electrodes by a wire it is observed that zinc dissolves with the evolution of
hydrogen gas and zinc sulphate is formed in the solution. The change can be
represented as the following reaction:

Zn(s) + H2SO4 → ZnSO4 (aq) + H2(g) …(7.11)

On the other hand, if we connect the cell with an external source having
184 potential slightly greater than of the cell, we find that silver dissolves and
Unit 7 Electrochemistry-I
hydrogen is evolved at the zinc electrode. The change can be represented as
the following reaction:

2Ag(s) + H2SO4 → Ag2SO4 + H2(g) …(7.12)

Thus, we find that in this case, the condition of reversibility i.e., on applying an
external voltage greater than the cell voltage, the reaction should reverse is
not being followed. Therefore, it is an example of irreversible cell. In such a
case, we cannot relate the cell emf with thermodynamic properties.

7.4 REPRESENTING GALVANIC CELLS

In our discussion above, we used the example of Daniell cell to describe the
formation and the functioning of a galvanic cell. In principle, we can create any
number of galvanic cells by using combinations of two different metal
electrodes. However, in order to learn about or describe different galvanic cells
we do not need to draw sketches like the one given in Fig. (7.1); we use a
symbolic representation for these. Such a representation is called a cell
diagram or cell notation. There are certain rules (conventions) that need to
be followed while writing the cell diagram for a given galvanic cell. Let us learn
about these rules by using the example of Daniell cell as follows:

i) The anode, the electrode at which oxidation occurs, is placed at the left
side of the diagram and the cathode, the electrode at which reduction
occurs, is placed at the right side of the diagram i.e.,

Zn(s)| Zn 2 + || Cu2 + | Cu(s) …(7.13) In case of cells with

transference;
Here, a single vertical line indicates the boundary separating species in involving the
different phases in a given electrode (half-cell). The double vertical line development of liquid
indicates the salt bridge. [Sometimes, a single broken (dashed) vertical junction potential a
line is used to represent a porous boundary, or some other means of broken vertical line is
preventing the electrolytes from mixing while allowing ion to flow.] used in place of two
vertical lines to
ii) The concentrations or activities of aqueous solutions are written in indicate the porous
parentheses after the symbol of the ions in the cell notation boundary.

Zn(s) | Zn2+ (aq,1M) || Cu2+ (aq,1M) | Cu(s) …(7.14)

iii) Sometimes, the electrolyte used in the salt bridge is also indicated. In such
a case the cell diagram for Daniell cell becomes,

Zn(s) | Zn2+ (aq,1M) | KCl(satd.) | Cu2+ (aq,1M) | Cu(s) …(7.15)

It is important to note that that the spectator ions, (the counter ions of the
electrolytes) that are present in the system but do not participate in the cell
reaction, are not shown in the cell diagram.

7.4.1 Cell Diagram and Cell Reaction

The representation of a galvanic cell in terms of cell diagram is quite
convenient way of expressing the cell. It is but natural that the cell diagram
and the reaction taking place in the cell are related. In principle, we should be
able to write the cell notation from the cell reaction and also, we should be 185
Block 2 Conductance and Electrochemistry
able to work out the cell reaction from the cell notation. Let us first learn how to
You may note here write cell diagram from the cell reaction. You know that a cell reaction is
that left and right here basically a redox reaction; and is a combination of two half-cell reactions. In
refer to the way the the process of writing cell diagram from cell reaction the first step is to identify
electrode is and write the two half-cell reactions. Once that is done then the process
represented in the cell
becomes quite straight forward. Let us take an example to understand it.
diagram. It has
nothing to do with the
Example 7.2: Write the cell diagram for a galvanic cell in which the following
physical location of
the two electrodes in
reaction takes place.
the actual galvanic
Cell reaction: Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)
cell.
Assume that potassium nitrate is used as electrolyte in the salt bridge and the
concentrations of zinc ions and silver ions are c1 and c2 respectively.

Solution: As stated above, the first step in the process of writing cell diagram
from cell reaction is to separate the two half-cell reactions. This
basically means that we need to identify the species undergoing
oxidation and reduction, respectively.

Here, we see that the metallic zinc is getting oxidised and the silver ions are
getting reduced to silver metal. So, we can write the oxidation and reduction
half-cell reactions as

Oxidation: Zn(s) → Zn2+(aq) + 2e−

Reduction: 2Ag+(aq) + 2e− → 2Ag(s)

We place the anode at the left side and the cathode, at the right side of the
diagram by separating different phases of the two half-cells by a single vertical
line and by representing the salt bridge by a double vertical line as follows.

Zn(s) | Zn2+ (aq) || Ag+ (aq) | Ag(s)

Note that the physical states of different species are indicated in the
parenthesis. As the concentrations of the ions are given, we include them as

Zn(s) | Zn2+ (aq, c1) || Ag+ (aq, c2 ) | Ag(s)

Further, as the electrolyte used in the salt bridge is also given, we include that
also in the cell notation as follows

Zn(s) | Zn2+ (aq, c1) | KNO 3 (satd.) | Ag+ (aq, c2 ) | Ag(s)

This is the required cell diagram for the given galvanic cell

Having learnt to write cell diagram from the cell reaction let us now learn to
write cell reaction on the basis of the cell diagram. We will again take an
example to do so.

Example 7.3: Write the balanced cell reaction for the galvanic cell represented
by the following cell diagram.

Sn(s) | Sn2+ (aq) || Ag+ (aq) | Ag(s)

186
Unit 7 Electrochemistry-I
Solution: As we know that the balanced cell reaction for a galvanic cell can be
obtained by adding the oxidation and reduction reactions in such a
way that total number of electrons lost and gained are equal.

Further, we know that in a cell diagram the electrode on which the oxidation
occurs is given on the left and the electrode at which reduction takes place is
given on the right. Therefore, in this case tin is undergoing oxidation whereas
silver ions are getting reduced. The corresponding equations can be written as
Oxidation: Sn(s) → Sn2+(aq) + 2e−
Reduction: Ag+(aq) + e− → Ag(s)
We find that tin atom gives two electrons while getting oxidised and a silver ion
needs just one electron to be reduced. So, to balance the electrons we
multiply the reduction equation by 2 to get,
2Ag+(aq) + 2e− → 2Ag(s)

We can get the cell reaction by adding the oxidation and reduction equations
as follows
Oxidation: Sn(s) → Sn2+(aq) + 2e−
Reduction: 2Ag+(aq) + 2e− → 2Ag(s)

Cell reaction: Sn(s) + 2Ag+(aq) → Sn2+(aq) + 2Ag(s)

Having learnt about galvanic cells, their working and representation let us now
learn about the emf of the cell. However, before that solve the following simple
question to assess your understanding.

SAQ 2
What is a cell diagram? Write the cell diagram for a galvanic cell in which the
following reaction takes place.
Fe(s) + Cd2+(aq) → Fe2+(aq) + Cd(s)

7.5 EMF OF A CELL

As discussed above, in galvanic cells there is a transfer of electrons from the
negative electrode (anode)to the positive electrode (cathode). This transfer of
electrons causes a current to flow from the electrode at higher potential to the
one at lower potential. This difference between the electrode potentials of the
electrodes when no current is drawn through the cell is known as the cell
electromotive force (emf) and is expressed in volts. In terms of the cell
notation in which the anode is written on the left and the cathode on the right
we can write, the standard cell emf as
0
Ecell = ER0 − EL0 …(7.16)

Where, E R0 and EL0 are the standard electrode potentials of the cathode and
the anode, respectively. In order to understand and determine emf of a cell we 187
Block 2 Conductance and Electrochemistry
need to first understand the meaning and significance of electrode potential
also conventionally expressed as reduction potential

7.5.1 Standard Electrode Potential

Let us recall from above, that when a metal (e.g., Zn or Cu) is placed in an
aqueous solution of its salt, some kind of charge separation develops between
the metal and nearby solution. The equilibrium processes can be represented
by the equations like,

Zn(s) ⇌ Zn2+(aq) + 2e− …(7.8)

Cu(s) ⇌ Cu2+(aq) + 2e− …(7.9)

The charge separation leads to development of a potential difference and this

is called electrode potential or half-cell potential. When all the species
involved in a half-cell are at unit concentration (in case a gas appears in the
electrode reaction, then it is to be at a pressure of 105 Pa), then the electrode
potential is known as standard electrode potential.

Determination of Standard Reduction Potentials

The potential of an individual electrode or half-cell cannot be measured. If we

try to measure the half-cell potential using a voltmeter, we will place one of the
test leads on the metal and the other in the adjoining solution. The moment we
place the metallic test lead in the solution a new half-cell comes into the
existence. As a consequence, the measured potential will not be that of the
half-cell being measured. However, we can measure the difference between
the two half-cell potentials that gives the emf of the cell. This can be measured
with the help of a potentiometer.

For Daniell cell, the cell emf is found to be 1.11 V. This is the difference
between the potential of the zinc half-cell (anode) and copper half-cell
(cathode). The question comes is that how do we find out the potential of
individual half cells? As stated above, we cannot directly measure the potential
of a half-cell, so we need to combine the half cell with some electrode (or half-
cell) for which the potential is zero. In other words, we need to have a
reference, like we take the temperature at the freezing point of water to be
zero-degree Celsius.

The standard hydrogen electrode (SHE) is taken to be such a reference

whose potential is arbitrarily taken to be equal to zero volt at all temperatures.
The SHE consists of a platinum electrode (coated with platinum black) is
partially dipped in a 1M HCl solution and pure hydrogen gas is bubbled
through it. The pressure of hydrogen gas is maintained at 105 Pa. Now, to
measure the electrode potential of the given half-cell, it is combined with the
Schematic diagram of SHE to form a galvanic cell. It’s emf is then measured with the help of a
standard hydrogen potentiometer. The value so obtained gives the potential of the given half-cell.
electrode In the hydrogen electrode either the protons are reduced, or hydrogen
molecules are oxidized at the Pt surface according to the following equation:

2H+ (aq) + 2e− ⇌ H2 (g) …(7.17)

As a matter of convention, the standard hydrogen electrode is always taken as
188
the electrode on the left of the cell diagram (anode) and the electrode under
Unit 7 Electrochemistry-I
consideration on the right (cathode). In other words, there is oxidation at the
hydrogen electrode and reduction at the half-cell being measured. The cell
diagram for the combination of SHE and zinc electrode would then be,

Pt,H2 | H+ (c = 1) | Zn 2 + (c = 1) | Zn …(7.18)

For such a combination of zinc electrode, and SHE the half-cell reactions can
be written as The measured
potential of the cell
Anode: H2 (g) → 2H+ (aq) + 2e− …(7.19) between a redox
couple (under
Cathode: Zn2+ (aq) + 2e− → Zn(s) …(7.4) standard conditions;
solutes at 1 M
Adding the two equations we get the overall cell reaction as concentration, gases
at 101.3 kPa) and
Zn2+ (aq) + H2 (g) → Zn(s) + H+ (aq) …(7.20)
standard hydrogen
electrode is called the
The measured potential of the cell containing zinc electrode and hydrogen
standard reduction
electrode is found to be 0.77 V. However, it is observed that the zinc electrode potential or standard
starts to dissolve to give Zn2+ and the concentration of H+ ions in the hydrogen electrode potential.
electrode decreases (You may recall from your earlier studies that if we place
a piece of zinc metal in an acid, it displaces hydrogen ions and H2 gas is
evolved). This suggests that the zinc electrode is acting as anode whereas
A half-cell that takes
hydrogen electrode acts as cathode. In other words, we can say that the
electrons from the
reaction as given in Eq. (7.20) is not spontaneous. The spontaneous cell standard hydrogen
reaction is as follows cell is assigned a
positive value of E0,
Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g) …(7.21) and one that donates
electrons to the
And the cell diagram for this galvanic cell can be given as follows:
hydrogen electrode, a
Zn(s) | Zn2+ (aq, c = 1) | H+ (aq, c = 1) | H2, Pt …(7.22) negative value.

As we have reversed the reaction, the sign of the potential would also be
reversed, i.e.,

Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g) E 0 = −0.77 V …(7.23)

It is important to note here that though we have reversed the sign, the
absolute value of the potential difference as measured would still be 0.77. The
half-cell reactions would be

Anode: Zn(s) → Zn2+ (aq) + 2e− E 0 = −0.77 V …(7.4)

Cathode: 2H+ (aq) + 2e− → H2 (g) E 0 = 0.00 V …(7.24)

As mentioned before, the standard cell emf is always taken as

0
Ecell = ER0 − EL0 …(7.16)

Substituting the values, we get

0
Ecell = 000 − (−0.77) = 0.77V …(7.25)

Now, if we take a combination of copper electrode (under standard conditions)

with SHE and measure the cell potential we get a value of 0.34 V. Here, Cu2+
ions would get reduced to copper metal (i.e., copper electrode would act as 189
Block 2 Conductance and Electrochemistry
cathode) whereas hydrogen gas would get oxidised to hydrogen ions
(i.e., hydrogen electrode would act as anode) i.e., the following half-cell
reactions would occur.
You may note here
Anode: H2 (g) → 2H+ (aq) + 2e− E 0 = 0.00 V …(7.19)
that the half-reactions
are written to show
Cathode: Cu2+ (aq) → Cu(s) E 0 = 0.34V …(7.5)
the oxidation and
reductions taking
The overall cell reaction and the cell notation would be as follows
place at the anode
and cathode, Cu2+ (aq) + H2 (g) → Cu(s) + 2H+ (aq) …(7.26)
respectively. The
overall cell reaction is Pt, H2 (g) | H+ (aq,a = 1) || Cu2+ (aq. a = 1) | Cu(s) …(7.27)
obtained as the sum
of the two half- The corresponding standard cell emf would be
reactions. However,
0
the cell potential is Ecell = ER0 − EL0 …(7.16)
the difference
between the reduction Substituting the values, we get
potentials of the two
0
redox couples. Ecell = 0.34 − (0.00) = 0.34 V …(7.28)

Different electrodes or redox couples are arranged in terms of decreasing

value of their standard electrode potentials as given in Table 7.1. This
arrangement is referred to as electrochemical series. A negative value of the
electrode potential means that the redox couple is a stronger reducing agent
than the H+/H2 couple whereas a positive value conveys that the redox couple
is a weaker reducing agent than the H+/H2 couple. In other words, the redox
couples below hydrogen in the series would reduce hydrogen ions to hydrogen
gas i.e., they will displace hydrogen ions from acid solutions. On the other
hand, the redox couples higher than hydrogen in the series will not be able to
displace hydrogen ions from an acid solution.

You may note that the electrodes or the half-cell reactions are arranged in
order of their decreasing E 0 values and can be used to predict the relative
strengths of various oxidants and reductants. In general, we can say that a
species on the left side of a half reaction (i.e., the oxidised form) will
spontaneously oxidise any species on the right side of another half-reaction
that lies above it in the table. Similarly, any species on the right side of a half-
reaction (i.e., the reduced form) will spontaneously reduce any species on the
left side of another half-reaction that lies below it in the table.

In the event of an electrochemical cell constructed by the combination of any

two electrodes; the electrode with a higher value of electrode potential, E 0
would act as cathode and the one with a lower value would act as anode. If we
make a galvanic cell by combining zinc electrode and copper electrode (i.e.,
make Daniell cell); there would be oxidation at the zinc electrode (anode,
lower E 0 ) and reduction at the copper electrode (cathode, higher E 0 ). The
cell would be represented as

Zn(s) | Zn2+ (c = 1) || Cu2 (c = 1) | Cu … (7.6)

The standard cell emf for the cell can be obtained by using Eq. (7.16).
0
190
Ecell = 0.34 − (−0.77) = 1.11V …(7.29)
Unit 7 Electrochemistry-I
0
Table 7.1: Standard electrode potentials (E ) for some redox half-cell
reactions at 298 K

Reduction half-reactions E0, Volts

Oxidising agent Reducing agent

F2 (g) + 2e− ⇌ 2F − (aq) +2.65

S2O82− (aq) + 2e− ⇌ 2SO24− (aq) +2.01

Ce 4 + (aq) + e − ⇌ Ce 3+ (aq) +1.44

O2 + H+ (aq) + 4e− ⇌ 2H2O(I) +1.23

Br2 (g) + 2e− ⇌ 2Br(aq) +1.07

Ag + (aq) + e − ⇌ Ag(s) +0.80

Fe3 + (aq) + e − ⇌ Fe2+ (aq) +0.77

Cu 2 + (aq) + 2e − ⇌ Cu(s) +0.34

Sn4 + (aq) + 2e − ⇌ Sn2+ (aq) +0.15

2H+ (aq) + 2e − ⇌ H2 (g) 0.00

Pb2 + (aq) + 2e − ⇌ Pb(s) −0.13

Sn2 + (aq) + 2e − ⇌ Sn(s) −0.14

Ni2 + (aq) + 2e − ⇌ Ni(s) −0.25

Cd2 + (aq) + 2e − ⇌ Cd(s) −0.40

Cr 3 + (aq) + 3e − ⇌ Cr(s) −0.42

Cr 3 + (aq) + e − ⇌ Cr 2+ (aq) −0.424

Zn 2 + (aq) + 2e − ⇌ Zn(s) −0.77

Al3 + (aq) + 3e − ⇌ Al(s) −1.66

Mg2+ (aq) + 2e− ⇌ Mg(s) −2.38

Be2 + (aq) + 2e − ⇌ Be(s) −1.99

K + (aq) + e − ⇌ K(s) −2.92

Li + (aq) + e − ⇌ Li(s) −3.04

Having learnt about the meaning and significance of cell emf, let us now learn
how do we actually measure the cell emf. However, before that answer the
following simple question to assess your understanding. 191
Block 2 Conductance and Electrochemistry

SAQ 3
The cell reaction for a galvanic cell is given below
Sn(s) + 2Ag+ (aq) → Sn2+ (aq) + 2Ag(s)
a) Write the half-cell reactions at the anode and the cathode
b) Calculate the value of cell emf under standard conditions

7.5.2 Experimental Measurement of EMF

The emf of a cell is usually measured with a potentiometer. The ends of a
uniform wire (XY) of high resistance is connected to a cell (C) of large emf.
Then we connect one electrode of the test cell, T (whose emf has to be
measured) to one end (X) of the wire and the second electrode is connected to
a sliding contact through a galvanometer to detect the flow of current as
shown in the Fig. (7.3).

Fig. 7.3: A schematic diagram of potentiometer setup for measuring cell emf.

In the event of measurement of emf of the cell T, the sliding contact connected
to the second terminal of the galvanometer is moved along the wire XY till we
reach a point, Z where the galvanometer shows zero current flow. At this
stage, the potential from cell C across the segment XZ is exactly balanced by
the emf of cell T.

Then we take another cell A, of accurately known emf EA and replace cell T
with cell A and once again the point (now Z’) where the galvanometer shows
zero current flow is located. Under these conditions we can write,
ET XZ
= …(7.30)
E A XZ '

Using the values of XZ and XZ’ along with the known emf of the cell, A we can
determine the emf of the given cell T.

7.6 THERMODYNAMICS OF REVERSIBLE CELLS

The measured values of the emf of reversible cells can provide us useful
thermodynamic parameters of the cell reaction occurring in them. This linkage
between the cell emf and thermodynamic parameters like, Gibbs energy
change (and hence spontaneity) and equilibrium constant are very significant
from the point of view of applications of emf measurements. Let us explore
192 these linkages.
Unit 7 Electrochemistry-I
7.6.1 Cell EMF and Spontaneity
You have learnt that in galvanic cells the Gibbs energy of the spontaneous
redox reaction is extracted as work. This work is electrical in nature and is due
to the movement of ions. Conventional current moves from a point of higher
potential to a point of lower potential. Electrons move in opposite direction.
This work done due to the moving charges depends on the difference in the
electrode potentials (Ecell), the number (n) of moles of electrons being
transferred, and the charge per mole of the electrons (F). We can write,
w elec = −nFEcell …(7.31)

The negative sign in this relation indicates that the work is done by the system.
Now since this work is equal to the change in Gibbs energy of reaction i.e.,
we can write,
w elec = Δr G = −nFEcell …(7.32)

Thus, Δr G = −nFEcell …(7.33)

It is an important relation that connects the Gibbs energy change with the cell
emf. Since, n, and F (Faraday’s constant), both are positive, we can conclude
(from Eq. (7.33)) that a galvanic cell for which E cell is positive, the cell reaction
would be spontaneous (as rG will be negative). For the cell under standard
conditions we can write,

r G0 = −nFEcell
0
…(7.34)
0
We can therefore say that if the value of Ecell for a cell is positive, then the
reaction written as discussed above will occur spontaneously. On the other
0
hand, if the value of Ecell is negative, it means that the reaction for the cell (as
constructed) is not spontaneous, and under standard conditions it will not
occur as written. It would be spontaneous in the opposite direction. However,
the reaction as written can be made to occur with a sufficient input of electrical
energy, i.e., we make it happen electrolytically. Let us take an example to see
how we can use electrochemical series to predict whether a given redox
reaction would be spontaneous or not.

Example 7.4: Predict, using data from Table 7.1, whether the following redox
reaction would be spontaneous or not under standard
conditions.

3Ni(s) + 2Al3+ (aq) → 3Ni2+ (aq) + 2Al(s)

Solution: The first step is to identify the species getting oxidised and reduced
respectively and to write two half reactions. We find here that nickel
is getting oxidised whereas aluminum ions are getting reduced. The
corresponding half-cell reactions would be

Oxidation: Ni(s) → Ni2+(aq) + 2e− E 0 = −0.25 V

Reduction: Al3+(aq) + 3e− → Al(s) E 0 = −1.66 V 193

Block 2 Conductance and Electrochemistry
The reduction potentials for Ni / Ni and Al / Al3+ redox couples, as given in
2+

Table 7.1, are −0.25 and −1.66 respectively

We find that nickel atom gives two electrons while getting oxidised and an
You may note that we
have suitably aluminum ion needs three electrons to be reduced. So, to balance the
multiplied the electrons we multiply the oxidation reaction by 3 and the reduction reaction by
oxidation and 2 to get,
reduction reactions to
Oxidation: 3Ni(s) → 3Ni2+(aq) + 6e− E 0 = −0.25 V
balance the electrons,
the corresponding Reduction: 2Al3+(aq) + 6e− → 2Al(s) E 0 = −1.66 V
reduction potentials
are not multiplied. We know that
0
Ecell = ER0 − EL0

Substituting the values, we get

0
Ecell = −1.66 − (−0.25) = −1.41V

As the cell emf is found to be negative it means that the reaction as written will
not be spontaneous.

As we have seen above that the Gibbs energy change for a reaction and the
0
Ecell for a galvanic cell are related so we can calculate the Gibbs energy
change for a redox reaction by measuring the standard cell emf of the galvanic
cell based on the reaction. Let us learn it with the help of an example,

Example 7.5: Calculate the Gibbs energy change for the reaction taking place
in the galvanic cell formed by combining copper electrode with
hydrogen electrode.
Solution: We start with writing the cell notation for the given galvanic cell.
The half-cell reactions, as discussed before, can be written as
Anode: H2 (g) → 2H+ (aq) + 2e− E 0 = 0.00V

Cathode: Cu2+ (aq) + 2e− → Cu(s) E 0 = 0.34V

The overall cell reaction and the cell notation would be

H2 (g) + Cu2+ (aq) → Cu(s) + 2H+ (aq)

Pt, H2 (g) | H+ (aq,c = 1) || Cu2+ (aq,c = 1) | Cu(s)

The corresponding standard cell emf would be

0
Ecell = ER0 − EL0

Substituting the values, we get

0
Ecell = 0.34 − (0.00) = 0.34 V

As per Eq. (7.34) the standard Gibb’s energy change is given as

r G0 = −nFEcell
0

The value of n=2 here, as two electrons are getting transferred from copper to
194 hydrogen ions in the cell reaction.
Unit 7 Electrochemistry-I
Substituting the values, we get

r G0 = −2  96485 C mol −1  0.34 V

r G0 = −65.61kJmol −1

You may note here that for the given cell we could write the half-cell reactions
as follows also

1
Anode: H2 (g) → H+ (aq) + e− E 0 = 0.00 V
2

1 2+ 1
Cathode: Cu (aq) + e− → Cu(s) E 0 = 0.34 V
2 2

In such a case the value of n=1 and the calculated value of Gibbs energy
change would be

r G0 = −1 96485 C mol −1  0.34 V

r G0 = −328 kJmol −1

This value of Gibbs energy change would be for one mole of the following cell
reaction.

1 1 1
H2 (g) + Cu2+ (aq) → H+ (aq) + Cu(s)
2 2 2

Whereas the value (= −65.6 kJ mol−1) we calculated above was for one mole
of the following reaction

H2 (g) + Cu2 + (aq) → 2H+ (aq) + Cu(s)

You may take a note of the fact that the Gibbs energy we get from the
measurement of the cell emf would depend on the number of electrons
participating in the reaction. This in turn, would depend on the way we write
the electrode reactions.

7.6.2 Cell EMF and Equilibrium Constant

We have just related the cell emf with the Gibbs energy of the redox reaction
occurring in a galvanic cell in terms of the following equation,

r G0 = −nFEcell
0
…(7.34)

You would recall from your earlier studies on chemical energetics that the
Gibbs energy change and the equilibrium constant of a reaction are related as

r G0 = −RT ln K …(7.35)

We can use these two expressions to relate the cell emf and the equilibrium
constant as follows
0
− RT ln K = −nFEcell …(7.36) 195
Block 2 Conductance and Electrochemistry
Rearranging, we get
nF 0 0 RT
ln K = Ecell or Ecell = ln K …(7.37)
RT nF

This is an important relation that facilitates the determination of equilibrium

constant of a redox reaction by measuring the emf of the corresponding
galvanic cell. Let us take an example to understand this application of emf
measurement.

Example 7.6: Calculate the equilibrium constant for the cell reaction for
Daniell cell working under standard conditions.
Solution: The Daniell cell under standard conditions can be represented as
Zn(s) | Zn2+ (c = 1) || Cu2+ (c = 1) | Cu

The corresponding half-cell reactions are

Anode: Zn(s) ⇌ Zn2+ (aq) + 2e− E 0 = −0.77

Cathode: Cu2+ (aq) + 2e− ⇌ Cu(s) E 0 = 0.34

The standard cell emf for the cell can be obtained by using Eq. (7.16).
0
Ecell = 0.34 − (0.77) = 1.11V
We know from Eq. (7.33) that
nF 0
ln K = Ecell
RT
Substituting the values,
2  96485 C mol −1
ln K =  1.11V
8.314 JK −1mol −1  298.15 K
Solving, we get
K = 1037.52 = 3.3  1037
Thus, the equilibrium constant for the reaction occurring in Daniell cell under
standard conditions would be, 3.3  1037

You have learnt that the value of standard cell emf for a voltaic cell can
provide useful thermodynamic data like, the Gibbs energy change and
equilibrium constant. However, what if the cell is not operating under standard
conditions? We need to use Nernst equation under these conditions. Let us
learn about the Nernst equation-an important equation in electrochemistry.
However, before that solve the following simple questions to gauge your
understanding.

SAQ 4
The cell reaction for a galvanic cell is given below
2Al(s) + 3Sn2+ (aq) → 2Al3+ (aq) + 3Sn(s)
a) Write the half-cell reactions at the anode and the cathode
b) Predict whether the given cell reaction be spontaneous; use data from
Table 7.1.
196
Unit 7 Electrochemistry-I

SAQ 5
Calculate the equilibrium constant for the reaction occurring in the following
voltaic cell. (Use data from Table 7.1).

Fe(s) | Fe2+ (aq,c = 1) || Cd2+ (aq,c = 1) | Cd(s)

7.7 NERNST EQUATION AND ITS APPLICATIONS

The discussion above has been on the standard electrode potential i.e., the
standard reduction potential of a redox couple when all the species are at
standard conditions (1 M concentrations / 1 bar pressure). However, in real
systems, the conditions may not be standard, therefore, the electrode
potential/ cell emf would be different. In such cases the actual potential of the
redox couple would depend on the standard electrode potential and the actual
concentrations of the species involved. The relationship between the actual
electrode potential and standard electrode potential for a given redox couple
was formulated by Walther Nernst. It is expressed in terms of an equation
called Nernst equation which can be derived on the basis of the relationship
between the Gibbs energy change and the cell emf as given in Eq. (7.33) and
Eq. (7.34). We can rewrite the equations as
 r G = −nFEcell …(7.33)

r G0 = −nFEcell
0
…(7.34)

Further, you would recall from the course BCHCT-133 that the Gibbs energy
change under standard and non-standard conditions are related as

r G = r G0 + RT ln Q …(7.38)

Where, Q is the reaction quotient; R is gas constant and T is the absolute

temperature. Substituting expressions for Gibbs energy changes we get,
0 0
− nFEcell = −nFEcell + RT ln Q …(7.39)

Dividing the expression by −nF on both sides we get

0 RT
E cell = E cell − ln Q …(7.40)
nF

This is the Nernst equation. Here, R is the gas constant, T is the absolute
temperature, n is the number of electrons participating in the reaction, and F is
the Faraday’s constant. Substituting these values and converting natural
logarithm to the one to the base 10 we get

0 8.314 JK −1 mol −1 298.15 K

Ecell = Ecell −  2.303 log Q …(7.41)
n  96485 C mo l −1

Simplifying, we get

0 0.0592
Ecell = Ecell − log Q …(7.42)
n 197
Block 2 Conductance and Electrochemistry
Nernst Equation for Electrode (half-cell) Reactions

Let us consider the following electrode reaction,

Mn+ (aq) + ne − → M(s) …(7.43)

The electrode potential of the electrode at any concentration measured with

respect to standard hydrogen electrode will be given by the following equation
0.0592 [M]
EMn + /M = EM0 n + / M − log n+
…(7.44)
n [M ]

The logarithm term is the ratio of the concentrations of the reduced and
oxidised forms of the species. As the concentration (rather activities) for pure
solids and liquids are taken as 1, the equation becomes,
0.0592 1
EMn + /M = EM0 n + / M − log n+
…(7.45)
n [M ]

As an example, for copper electrode, the Nernst equation at 298 K would be

0.0592 1
0
ECu2+ / Cu = ECu2+ − log 2+
…(7.46)
/ Cu 2 [Cu (aq)]

7.7.1 Applications of Nernst Equation

The Nernst equation finds extensive applications in analytical chemistry and
life processes. Electrochemical cells are extensively used for calculating the
pH of solutions, solubility product, equilibrium constant and other
thermodynamic properties. In all these applications of electrochemical cells the
Nernst equation has a role to play. We will take up following simple common
applications

• Determination of equilibrium constant

• Determination of cell emf under non-standard conditions

• Predicting spontaneity of a cell reactions under non-standard conditions

• Determination of pH value of a solution

• Determination of Ksp of a sparingly soluble salt

Let us take up these applications with the help of examples.

Determination of equilibrium constant

Once again, you may recall from your earlier study about chemical equilibrium
that at equilibrium, Q =K and rG = 0 which means that Ecell = 0.

Substituting in Eq. (7.40), we get

0 RT nF 0
0 = Ecell − ln K ➔ ln K = Ecell …(7.47)
nF RT

Which is the same expression we got before, Eq. (7.37). In other words, we
can determine the equilibrium constant from cell emf measurement. In
example 7.6 you have seen how this equation can be used to determine the
198 equilibrium constant of a redox reaction.
Unit 7 Electrochemistry-I
Determination of cell emf under non-standard conditions

If a galvanic cell is working under standard conditions, then its emf can be
easily obtained by using the standard electrode potentials of the redox couples
involved. The Nernst equation allows to do the same when the cell is working
under non-standard conditions say the concentrations (activities) of the ions
are different from unity.

Let us understand it with the help of an example.

Example 7.7: Calculate the emf of the galvanic cell given by the following cell
0 0
diagram. (Given: ENi2+
/Ni
= −0.25 and EPb 2+
/Pb
= −0.13)

Ni(s) | Ni 2+ (aq,c = 0.03 M) || Pb2+ (aq,c = 0.30) | Pb(s)

Solution: We know that according to the Nernst equation,

0 0.0592
Ecell = Ecell − n
log Q

0
Therefore, to calculate the value of E cell we need to know Ecell and Q. To
0
calculate the value of Ecell we would proceed as in Example 7.4. We note here
that nickel is getting oxidised whereas lead ions are getting reduced. The
corresponding half-cell reactions would be

Oxidation: Ni(s) → Ni 2+ (aq) + 2e − E 0 = −0.25 V

Reduction: Pb 2+ (aq) + 2e − → Pb(s) E 0 = −0.13 V

The cell reaction would be

Ni(s) + Pb 2+ (aq) → Ni 2+ ( aq) + Pb(s)

We know that
0 0 0
Ecell = ERight − ELef t

Substituting the values, we get

0
Ecell = −0.13 − ( −0.25) = 0.12 V

You would recall from your earlier study on chemical equilibrium that the
reaction quotient,Q for a reaction has the same expression as that of
equilibrium constant but the concentrations are not at equilibrium. So for the
cell reaction given above, we can write

[Ni 2 + ]
Q=
[Pb 2 + ]

Note here that in this expression we have not included the concentrations of
solid lead and nickle as these are taken as 1. Substituting the standard cell
emf, value of Q and the number of electrons (n) in the nernst equation we get

[Ni2 + ]
Ecell = 0.12 − 0.0592 log =
2 [Pb2 + ] 199
Block 2 Conductance and Electrochemistry
Substituting the given concentrations of ions, we get

Ecell = 0.12 − 0.0592

2
log 00..03
30

Simplifying, we get

Ecell = 0.1496 V

As the cell emf is found to be positive it means that the reaction as written will
be spontaneous under given conditions.

Predicting spontaneity of a cell reactions under non-standard conditions

You have learnt above that the cell emf is directly related to the Gibbs energy
change and the expressions for the cells under standard and non-standard
conditions are as given below

r G0 = −nFEcell
0
…(7.33)

 r G = −nFEcell …(7.34)

You have learnt about the determination of E cell for a voltaic cell under
nonstandard conditions in example 7.7. Once its value is known it can be used
to get the Gibbs energy change for the reaction. The algebraic sign of either
the cell emf or of Gibbs energy change can be used to predict the spontaneity
of a cell reaction under non-standard conditions.

Determination of pH value of a solution

You know that the pH value is a measure of the concentration of hydrogen

ions in an aqueous solution. In other words, if we can measure the
concentration of hydrogen ions in a solution, we can in principle determine its
pH value. Now the question is can we use the emf measurement to find the pH
of a solution? The answer is yes. We can do so by making the given solution a
hydrogen electrode by dipping a platinum electrode in it and bubbling
hydrogen gas around it at a pressure of 1 bar. This hydrogen electrode can be
combined with another electrode to form a galvanic cell. As the concentration
of hydrogen ions in the given solution is different from standard conditions, the
cell so formed will be under non-standard conditions. The measured emf of
such a cell can then be used to determine the concentration of hydrogen ions
and hence the pH of the solution. Let us understand it with the help of an
example.

Example 7.8: The aqueous solution of an acid is provided with a platinum

electrode around which hydrogen gas is bubbled at a pressure
of 1 bar. The hydrogen electrode so obtained is combined with a
standard zinc electrode to construct a galvanic cell. If the emf of
the cell at 298 K is found to be 0.39 V, find the pH of the
0
solution. (Given: EZn 2 + / Zn = −0.77 V )

Solution: The cell can be represented as

Zn(s) | Zn2+ (aq,c = 1) || H+ (aq,c = ?) | H2 (g),Pt E = 0.39 V

200
Unit 7 Electrochemistry-I
The corresponding cell reaction would be

Zn(s) + 2H+ (aq) → Zn2+ (aq) + H2 (g)

The standard cell emf would be

0
Ecell = 0.00 − (−0.77) = +0.77 V

The Nernst equation for the cell can be written on the basis of cell reaction as
[ Zn2 + ] pH
0
Ecell = Ecell − 0.0592 log 2
n [Zn][H+ ] 2

As the concentration of pure solids is taken as 1 and p H2 = 1 bar we can write,

2+
0
Ecell = Ecell − 0.0592 log [ Zn+ ]
n [H ] 2

Since we have standard zinc electrode, [Zn 2 + ] = 1M, substituting the values,

[ 1]
0.39 = 0.77 − 0.0592 log
2 [H+ ] 2

Rearranging we write,
[ 1]
− 0.38 = − 0.0592 log =
0.0592
log [ H + ] 2
2 [H+ ] 2 2

− 0.38 = 0.0592 log [ H+ ]  0.38 = −0.0592 log [ H+ ]

0.38
 0.38 = 0.0592 pH  pH = 0.0592
= 6.42

Thus, the pH of given solution is calculated to be 6.42

Determination of Ksp of a sparingly soluble salt

You have learnt about the solubility and solubility product of sparingly soluble
salts in BCHCT-133 course. You would recall that these salts have extremely
low solubility. The dissolved part of the sparingly soluble salt in its solution can
be considered to be fully dissociated. The product of the molar concentrations
of the constituent ions in solution, each raised to the power of its stoichiometric
coefficient in the solubility equilibrium is called solubility product. The emf
measurement can be used to determine the solubility product of a sparingly
soluble salt. The principle of such a determination is similar to that of the
determination of pH of an aqueous solution explained above. Let’s understand
it with the help of an example.

Example 7.9: A silver-silver ion electrode formed by dipping a silver rod in a

saturated solution of AgCl showed a potential of 0.50 V when
combined with a standard hydrogen electrode. Calculate the
0
solubility product of AgCl. (Given: EAg+ / Ag = 0.80 V)

Solution: We know that for AgCl, Ksp = [Ag+] [Cl−]

Also, we know that the concentration of silver ions and chloride ions will be
equal. If the solubility of the salt is ‘s’, then the concentrations of silver and
chloride ions would be s mol dm−3 each. 201
Block 2 Conductance and Electrochemistry
We can write

K sp = s 2 mol 2 dm −6

Thus, if we know the concentration of silver ions in the solution, we can find
the solubility product. The concentration of the silver ions can be obtained
from the emf of given cell. The cell can be represented as

Pt, H2 (g) | H+ (aq,c = 1) || Ag+ (aq,c = ?) | Ag(s) E = 0.50 V

The standard cell emf would be

0
E cell = 0.80 V − ( 0.00 V ) = +0.80 V

The cell reaction would be

Ag+ (aq) + 1/2H2 (g) → Ag(s) + H+ (aq)

We can write the Nernst equation as

[ Ag ] [ H+ ]
0
Ecell = Ecell = − 0.0592 log
n [ Ag + ] p1/ 2
H2

As the concentration of pure solids is taken as 1, and for standard hydrogen

electrode the concentration of hydrogen ions is 1M and the pressure of
hydrogen gas is pH 2 = 1bar we can write,

0
Ecell = Ecell = − 0.0592 log 1
n [ Ag+ ]

Substituting the values,

0.50 = 0.80 − 0.0592 log 1

n [ Ag+ ]

Simplifying, we get
−0.30
log [ Ag + ] = 0.0592
− 5.07  [ Ag + ] = 8.5  10 −6 mol dm−3

Substituting in the solubility product expression, we get

 K sp = (8.5  10−6 )2 = 7.225  10−11 mol 2 dm−6

Thus, the solubility product of silver chloride is calculated to be

= 7.225  10−11 mol 2 dm−6

Having learnt about the Nernst equation and its applications, let’s now take up
different types of electrodes used in electrochemical cells. However, before
that solve the following simple questions to assess your understanding.

SAQ 6
Will the following reaction as written, be spontaneous if the concentrations of
Fe2+and Cd2+ ions are 1.00 M and 0.20 M respectively? ( Use Table 7.1)

Cd(s) + Fe2+(aq) → Cd2+(aq) + Fe(s)

202
Unit 7 Electrochemistry-I

SAQ 7
The emf of a voltaic cell containing copper and silver electrodes is found to be
0.40 V. If the concentration of silver ions is 0.70 M, calculate the concentration
of copper ions. ( Use Table 7.1)

7.8 TYPES OF ELECTRODES

A large number of different types of electrodes are employed in the
electrochemical cells. These are classified as

• Gas electrodes
• Metal-metal ion electrodes
• Metal-sparingly soluble salt electrode
• Redox electrodes
• Amalgam electrodes
• Membrane electrodes
Let’s learn about these types of electrodes with their representative examples.

Gas electrodes: These consist of a gas bubbled around an inert metal rod /
strip like platinized platinum dipped in a solution containing ions to which the
gas is reversible. Over a period of time, the gas gets adsorbed on the inert
metal and an equilibrium is established between the gas and its own ions in
the solution. Standard hydrogen electrode, about which you have learnt above
is an important example of this class. The reduction half-cell reaction for
hydrogen electrode and its representation is given as

H+ (aq) + e− ⇌
1
H ( g)
2 2
…(7.48)

Pt, H2 (g)| H+ (aq, c = 1)| …(7.49)

The potential of the gas electrode depends on the pressure of the gas, and the
concentration of the ions in solution. For hydrogen gas electrode, the Nernst
equation can be written as
p1/2
0 0.0592 H
E =E − 1
log c 2 …(7.50)
H+

Since for standard hydrogen electrode, E0 is taken as zero, we can write

p 1/2 c +
0.0592 H
E=− log c 2  E = 0.0592 log H
…(7.51)
1
H+ p 1/2
H2

Other commonly used gas electrodes, their representation and half-cell

reactions are given below.

Gas electrode Half-cell reaction Representation

Oxygen 1
O ( g) + H 2 O + 2e − ⇌ 2OH- ( aq) Pt,O2 (g)1bar | OH− (aq, c = 1)|
2 2
electrode
Chlorine 1
Cl2 (g) + 2e − ⇌ Cl− (aq) Pt, O2 (g)1bar | Cl− (aq, c = 1) |
2
electrode 203
Block 2 Conductance and Electrochemistry
Metal-metal ion electrode

It is the one of the most commonly used categories of electrodes. A metal-

metal ion electrode typically consists of a metal strip /rod in contact with a
solution of its own ions to which the electrode is reversible. The half-cell
reaction for such an electrode can be given as

Mn+ (aq) + ne − → M(s) …(7.43)

A standard metal-metal ion electrode is represented as

Mn+ (s) | Mn+ ( aq, c = 1) | …(7.52)

The potential of metal-metal ion electrode depends on the concentration of the

metal ions in the solution and the temperature. The Nernst equation for the
electrode can be given as

E Mn+ / M = E M0 n+ /M − 0.0592 log 1

…(7.53)
n [Mn + ]

Zn | Zn2+; Cu | Cu2+; Pb | Pb2+and Ag | Ag+; are common examples of metal-

metal ion electrodes.

Amalgam electrode

In case of certain metals it is not possible to use pure metal as it can react with
water, e.g., potassium. In such cases, an amalgam of the metal is used and
the electrodes are called amalgam electrodes. Electrical contact is made by
a platinum wire dipped into the amalgam pool. For example, the potassium
amalgam electrode can be represented as

Pt (s) | K (Hg) | K + (aq) | …(7.54)

The potential of amalgam electrodes depend on the concentration (activity) of

the metal in the amalgam. The potential of amalgam electrode can be given as

0.0592 [ M( Hg )]
E Mn+ /M = E M0 n+ /M − log …(7.55)
n [ Mn + ]

The amalgam electrodes have an added advantage as these attain equilibrium

relatively easily as compared to pure metal electrodes.

Metal –sparingly soluble salt electrode: such an electrode consists of a

metal in contact with one of its sparingly soluble salts and a salt solution
containing negative ion common with the salt. The electrode reaction involves
a reversible reaction between the metal and the negative ion to form sparingly
soluble salt accompanied by the liberation of electrons. Calomel electrode and
silver-silver chloride electrodes are common examples of this type of
electrodes.

The calomel electrode consists of mercury (Hg) in contact with its insoluble
salt, mercurous chloride (Hg2Cl2) and a solution of KCl. The electrode is
represented as

204 Hg( l ) | Hg 2Cl2 (s)| Cl− (aq, c = 1) | …(7.56)

Unit 7 Electrochemistry-I
The calomel electrode is reversible to chloride ions and its potential depends
on the concentration of chloride ions. However, if we take a saturated solution
of KCl then it’s half-cell potential becomes constant (0.2682 V) and the
electrode is called Saturated Calomel Electrode (SCE). As a consequence, it
is commonly used as a reference electrode. The SCE is represented as

Hg( l ) | Hg 2Cl2 (s)| Cl− (aq, satd.) | …(7.57)

When used as a cathode in a galvanic cell, the mercurous chloride is reduced

to mercury as per the following equation

Hg 2Cl2 (s) + 2e− → Hg (l ) + 2Cl− …(7.58)

As it is inconvenient to use standard hydrogen electrode, the saturated

calomel electrode is commonly employed as a reference electrode in
electrochemical work. Once it has been calibrated against the SHE, it can be
used to determine the standard electrode potentials of many other electrodes

Redox electrodes

This type of electrodes consists of an inert metal like platinum in contact with
an aqueous solution of the ions of an element in different oxidation state. The
metal electrode does not react with the species in solution, it merely acts as a
carrier of electrons. A system in which a platinum electrode is dipped in an
aqueous solution containing ferrous and ferric ions is one of the most
commonly used redox electrode.

The half-cell reaction, and electrode representation for it can be given as

Fe3 + (aq) + e− → Fe2+ (aq) …(7.59)

Pt(s) | Fe3 + (aq,c = c1); Fe2+ (aq,c = c2 ) | …(7.60)

The potential of such an electrode depends on the ratio of the concentrations

of the metal ions in the two different oxidation states. For the Ferric/ferrous ion
electrode, we can write

0 0.0592 [Fe2 + ]
EFe3 + /Fe2 + = EFe3+
/Fe2 +
− log …(7.61)
1 [Fe3 + ]

Membrane electrodes

In this type of electrode two solutions having different concentrations of the

same salt are separated by a membrane that is selectively permeable to one
of the ions of the salt. This ion would tend to diffuse through the membrane
whereas the other ion will not be able to do so. As a consequence, a potential
develops across the membrane. A glass electrode used for the measurement
of pH of aqueous solutions is one of the most common examples of this class.
You would learn in detail about glass electrode in the next unit when we would
take up pH determination as an application of emf measurements.

Let us now sum up what we have discussed in this unit. However, before that
solve the following simple question to assess your understanding. 205
Block 2 Conductance and Electrochemistry

SAQ 8
A redox electrode contains aqueous solution of Sn4+ and Sn2+ ions in which a
platinum rod is dipped.
a) Write the electrode reaction
b) Give the half-cell representation
c) Using data from Table 7.1 calculate the potential of the electrode if the
concentrations of stannous and stannic ions are 0.50M and 0.25 M
respectively.

7.9 SUMMARY
In this first unit on electrochemistry, we started by introducing the domain of
electrochemistry as the one that deals with the study of production of
electricity from energy released during spontaneous chemical reactions and
also the use of electrical energy to make non-spontaneous reactions possible.
Thereafter, we took up electrochemical cells wherein we talked about Galvanic
and electrolytic cells. Since our main focus in this unit was on galvanic cells
we explained different aspects of galvanic cells by taking Daniell cell as a
representative example. This was followed by differentiating between
reversible and irreversible cells.
The next topic we took up was the representation of galvanic cells wherein we
talked about writing cell-notation or cell diagram for a given galvanic cell, and
its relationship with the cell reaction. This was followed by the concept of emf
of the cell and its measurement. In this context we introduced the concepts of
electrode potential; standard electrode potential and cell emf etc. Thereafter,
we explained the relationship between cell emf and thermodynamic
parameters like, Gibbs energy, equilibrium constant etc. We also discussed
about the Nernst equation and its applications. Towards the end of the unit we
described different types of electrodes used and also explained the reactions
taking place in them along with their advantages.

7.10 TERMINAL QUESTIONS

1. Write the cell diagram for a galvanic cell in which the following reaction
takes place.

Cell reaction: Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)

Assume that potassium nitrate is used as electrolyte in the salt bridge and
the concentrations of zinc ions and silver ions are c1 and c2, respectively.

2. Calculate the emf of a Daniell cell in which the concentration of zinc ions in
zinc electrode and copper ions in copper electrode are 0.050 and 0.025 M
respectively.

3. The cell reaction for a galvanic cell is given below

Ni(s) + 2Ag+ (aq) →Ni2+ (aq) + 2Ag(s)

206 a) Write the half-cell reactions at the anode and the cathode
Unit 7 Electrochemistry-I
b) Calculate the value of standard cell emf

c) Predict whether the cell reaction given above is spontaneous or not

4. The standard electrode potential of zinc electrode is −0.77V. Calculate the

potential of zinc electrode containing 2M aqueous solution at 300K

5. The cell reaction for a galvanic cell is given below

Cd(s) + Pb2+(aq) →Cd2+(aq) + Pb(s)

a) Write the half-cell reactions at the anode and the cathode

b) Calculate the value of cell emf under standard conditions

c) Calculate the cell emf if the concentrations of cadmium and zinc ions
are 0.02 M and 0.2 M respectively.

7.11 ANSWERS
Self Assessement Questions
1. Galvanic cells are the electrochemical cells in which the Gibbs energy
change of the redox reaction is utilised to perform electrical work.

As the silver ions are getting displaced this means that these ions are
getting reduced. Further, since the reduction must be accompanied by
oxidation, the aluminium metal would get oxidised to give aluminum ions.
Therefore, if a galvanic cell is formed by using aluminum and silver
electrodes, the aluminium electrode would act as anode whereas silver
electrode would act as cathode. The cell reaction can be given as

3Ag + (aq) + Al(s) → 3Ag(s) + Al 3 +

2. A cell-diagram is a shorthand notation (a symbolic representation) of an

electrochemical cell. The cell-diagram of the galvanic cell in which the
given reaction takes place will be

Fe(s)| Fe2 (aq)|| Cd2+ (aq)| Cd(s)

3. In the given reaction tin is getting oxidised and silver ions are getting
reduced. The half-cell reactions at the anode and cathode would be

Anode: Sn(s) → Sn2+ (aq) + 2e− E 0 = −0.14 V

Cathode: 2Ag+ (aq) + 2e− → 2Ag(s) E 0 = 0.80 V

(You may note here that we have multiplied the cathodic equation by 2 to
balance electrons but we have not multiplied the half-cell potential)
0 0 0
We know that Ecell = Ecathode − Eanode

Substituting the values from Table 7.1, we get

0
Ecell = 0.80 − ( −0.14) = 0.94 V
207
Block 2 Conductance and Electrochemistry
4. In the given reaction aluminum is getting oxidised and tin ions are getting
reduced. The half-cell reactions at the anode and cathode would be

Anode: 2Al(s) → 2Al3 (aq) + 6e− E 0 = −0.166 V

Cathode: 3Sn2+ (aq) + 6e− → 3Sn(s) E 0 = −0.14 V

(You may note here that we have multiplied the cathodic reaction by 3 and
the anodic reaction by 2 to balance electrons but we have not multiplied
the half-cell potential)
0 0 0
We know that Ecell = Ecathode − Eanode

Substituting the values from Table 7.1, we get

0
Ecell = −0.14 − (−1.66) = 1.80 V

Since the standard cell emf is found to be positive, the cell reaction is
spontaneous.
5. The half-cell reactions for the given voltaic cell can be given as

Anode: Fe(s) → Fe2+ (aq) + 2e− E 0 = −0.41V

Cathode: Cd 2 + (aq) + 2e − → Cd ( s ) E 0 = −0.40 V

The standard cell emf for the cell can be obtained by using the following
equation
0 0 0
Ecell = Ecathode − Eanode

Substituting the values, we get

0
Ecell = −0.40 − (−0.41) = 0.01V

We know that,
nF 0
ln K = Ecell
RT
Substituting the values,

2  96485 C mol −1
ln K =  0.01V
8.314 JK −1mol −1  298.15 K

Solving, we get K = 100.338 = 2.17

Thus, the equilibrium constant for the reaction occurring in the given
voltaic cell under standard conditions would be, K = 2.17

6. As the given voltaic cell is not under standard conditions, we would need
to use Nernst equation to calculate cell emf.
We know that according to Nernst equation

0 0.0592
Ecell = Ecell − log Q
n
0
First, we calculate Ecell

208 For the given cell, the half-cell reactions can be written as
Unit 7 Electrochemistry-I
2+ 2+ − 0
Anode: Cd (s) → Cd (aq) + 2e E = −0.40 V

Cathode: Fe(aq) + 2e− → Fe(s) E 0 = −0.41V

0
The value of Ecell would be

0
Ecell = 0.40 − (−0.41) = 0.01V

For the given cell reaction, the reaction quotient, Q would be

[Cd2 + ] 0.2
Q= = = 0 .2
[Fe2 + ] 1.0

Substituting the standard cell emf, value of Q and the number of electrons
(n) in the nernst equation we get

0.0592
Ecell = 0.01 − log 0.2
2
0
Simplifying, we get Ecell = 0.03

As the cell emf is found to be positive it means that the reaction as written
will be spontaneous under given conditions.

7. From Table 7.1 we observe that the standard electrode potential of silver
electrode (0.80 V) is more positive than that of copper electrode (0.34 V).
This implies that there will be reduction at the silver electrode (cathode)
and oxidation at copper electrode (anode). We can write the half-cell
reactions as

Anode: Cu(s) → Cu2+ (aq) + 2e− E 0 = 0.34 V

Cathode: 2Ag+ (aq) + 2e− → 2Ag(s) E 0 = −0.80 V

0
The value of Ecell would be

0
Ecell = 0.80 − (0.34) = 0.46 V

As the cell is not under standard conditions, we use Nernst equation, i.e.,
0
Ecell = Ecell − 0.0592
n
log Q

Substituting the given value of cell emf along with the computed standard
cell emf, we get

[ Cu 2 + ]
0.40 = 0.46 − 0.0592 log
2 [Ag + ] 2

Substituting the concentration of silver ions and simplifying we get

[Cu2+ ]
 2.027 = log
0.0049

Solving, we get [Cu2 + ] = 0.52 M 209

Block 2 Conductance and Electrochemistry
8. The electrode reaction can be written as

Sn4 + (aq) + 2e− → Sn2 (aq)

The corresponding half-cell can be represented as

Pt(s),Sn4 + (aq),Sn2+ (aq) |

From Table 7.1 we can see that the standard electrode potential is
+0.15 V

The half-cell potential under given conditions can be obtained by using

Nernst equation,

0.0592 [Sn 2 + ]
E = E0 − log
n [Sn 4 + ]

Substituting the values

0.0592 0.50
E = 0.15 − log
2 0.25

Simplifying, we get, E = 0.141 V

Terminal Questions
1. The cell diagram for the given galvanic cell would be

Zn(s) | Zn2+ (aq, c = c1) | KNO 3 (satd.)| Ag+ (aq, c = c2 ) | Ag(s)

2. The cell diagram for the Daniell cell under standard conditions can be
written as

Zn(s) | Zn2+ (aq, c = 1) || Cu2+ (aq, c = 1) | Cu(s)

0
The standard cell emf, E cell can be obtained as
0
Ecell = 0.34 − (−0.77) = 1.11V

The cell potential of the Daniell cell under given conditions can be
obtained by using Nernst equation

0.0592 [Zn2 + ]
E = 1.11 − log
2 [Cu2 + ]

Substituting the given concentrations, we get

0.0592 [0.050]
E = 1.11− log
2 [0.025]

Solving, we get E = 1.101 V

3. For the given galvanic cell

a) The half-cell reactions can be written as

Anode: Ni(s) → Ni 2 + (aq) + 2e−

210 Cathode: 2Ag+ (aq) + 2e− → 2Ag(s)

Unit 7 Electrochemistry-I

b) The standard cell emf can be obtained as

0 0 0
Ecell = Ecathode − Eanode

Substituting the values from Table 7.1, we get

0
Ecell = 0.80 − ( −0.25) = 1.05 V

c) As the value of the cell potential is positive, the reaction as written is

spontaneous.

4. We know that the potential of an electrode under non-standard conditions

can be obtained by using Nernst equation, viz.,

RT
E = E0 − ln Q
nF

For zinc electrode, the half-cell reaction is

Zn2+ (aq) + 2e− → Zn(s) E 0 = −0.77 V

Substituting in the Nernst equation, we write

8.31JK −1 mol −1  300 K 1

E = −0.77 − −1
2.303 log
2  96485 C mol [ Zn 2 + ]

1
E = −0.77 − 0.02977 log
[Zn2+ ]

Substituting the value of concentration of zinc ions, we get

1
E = −0.77 − 0.02977 log = −0.761V
2

5. For the given galvanic cell

a) The half-cell reactions can be written as

Anode: Cd (s) → Cd2+ (aq) + 2e−

Cathode: Pb2+ (aq) 2e− → Pb (s)

b) The standard cell emf can be obtained as

0 0 0
Ecell = Ecathode − Eanode

Substituting the values from Table 7.1, we get

0
Ecell = −0.13 − (−0.40) = 0.27 V

c) As the cell is not under standard conditions, we use Nernst equation

to obtain cell emf. i.e.,
0
Ecell = Ecell − 0.0592
n
log Q
211
Block 2 Conductance and Electrochemistry

For the given cell, the equation becomes

[ Cd2 + ]
0
E cell = E cell − 0.0592 log
2 [Pb 2 + ]

Substituting the values, we get

Ecell = 0.27 − 0.0592

2
log 00..20
02
= 0.30 V

212