Chapter 6: Electrochemical Cells (book: Maron Lando)

H & N Book
Chang Book
 (b) Notation (atkins)
In the notation for cells, phase boundaries are
denoted by a vertical bar. For example, the cell in Fig. 11
Fig. 7.11 is denoted
Pt(s)  H2(g)  HCl(aq)  AgCl(s)  Ag(s)

A liquid junction is denoted by …, so the cell

in Fig. 7.12, is denoted
Zn(s)  ZnSO4(aq)…CuSO4(aq)  Cu(s)

Fig. 12
 (b) Notation (atkins)
A double vertical line, , denotes an interface for
which it is assumed that the junction potential
has been eliminated. Thus the cell in Fig. 7.13 is
denoted
Zn(s)  ZnSO4(aq)  CuSO4(aq)  Cu(s)
An example of an electrolyte concentration cell in
which the liquid junction potential is assumed to be
eliminated is
Fig. 13
Pt(s)  H2(g)  HCl(aq, b1)  HCl(aq, b2)  H2(g)  Pt(s).
Nernst Equation
 Nernst Equation
Relationship between the emf of a galvanic cell and the concentrations
of reactants and products in a redox reaction under nonstandard-state
conditions. This equation is derived.
 Types of Half Cells/Types of electrodes (H & N book, Maron Lando)
The reaction taking place in an electrochemical cell may be split up into two reactions
at the two electrodes. Similarly, the cell may be split up into two half-cells, one at each
electrode; an electrode dipping into a solution is said to constitute a half-cell. Thus
in the Daniel cell Zn | Zn2+ and Cu | Cu2+ constitute two half-cells.
It is convenient to describe electrochemical processes in terms of half-cells, as
two half-cells can be suitably arranged to produce a desired reaction in a cell.
Various types of reactions may be made to
to occur electrochemically and various electrodes or half-cells may be used. Some of
these are described here.
Classification of Electrodes/Half-cells:
In electrochemical work the cells encountered involve various electrodes
depending on the purpose at hand. The more important of these may be
grouped into the following five types, namely:

1. Metal-metal Ion electrodes

2. Amalgam electrodes
3. Gas electrodes
4. Metal-insoluble salt electrodes
5. Oxidation-reduction electrodes
 Classification of Electrodes: Metal-metal Ion electrodes/Half-
cell
Electrodes of this type involve a metal in equilibrium with a solution of its
ions.
All these electrodes operate on the general reaction:

M = M+n + n-
for which the electrode potential equation is given by
RT
E E  0
ln a
nF
M M M n

Each of these electrodes is said to be reversible to its own 1ons; i.e., the potential
of each of these electrodes is sensitive to and is determined by the activities
of its own ions in the solution in which the metal is immersed. Thus, the zinc
electrode is reversible to zinc ions, the iron electrode to ferrous ions, the tin
electrode to stannous ions, etc.
 Amalgam Electrodes/Half-cell
It is quite common practice to substitute for the
pure metals in metal-metal ion electrodes solutions
of the metal in mercury,
namely, amalgams.
Amalgams of metals more active than
mercury behave essentially as do the pure metals, the
only difference, being that the activity
of the metal is lowered by dilution by the mercury.
An example is the Cd amalgam electrode used in the Weston standard cell (Section 15.5). As
shown in Figure 15.4 electrical contact is made by a platinum wire immersed in the amalgam.
The reaction is the same as in the metal-metal ion electrode. An amalgam electrode is of
importance in those cases where the metal is too reactive to be used in the pure form. A
sodium amalgam half-cell is represented as
Na – Hg(a1) | Na+(a2)
 Amalgam Electrodes
These amalgam electrodes are preferred frequently because equilibrium
can as a rule be established much more rapidly with them than with the pure
metals, and because they are more readily reversible.

Again, with metals such as sodium, potassium, or calcium the

activity in aqueous solutions is too great for direct use. However, by
converting these metals to amalgams the activity can be moderated
sufficiently to permit measurements in presence of water.
 Amalgam Electrodes
Still another factor in favor of the amalgams is that small quantities of impurities, which
may cause erratic behavior in pure metals, are often diluted enough by amalgamation to
yield satisfactory and reproducible results.

As an example of electrodes in this class may be taken the lead amalgam

electrode, consisting of the lead amalgam, written Pb(Hg), dipping into a
solution of plumbous ions, namely, Pb(Hg) | Pb+2(apb+2).
For this electrode the reaction is
Pb(Hg) = Pb+2(apb+2) + 2e- (36)
And hence the electrode potential Ea is given by
RT a
E E  ln0 Pb 2

2F a
a Pb

Pb
 Amalgam Electrodes
Pb(Hg) = Pb+2(apb+2) + 2e- (1)
And hence the electrode potential Ea is given by
RT a
E E  ln
0 Pb 2

(2)
2F a
a Pb

Pb
where EPb is the standard electrode potential of the pure lead electrode, aPb+2 is the activity of
0

plumbous ions in solution, and aPb is the activity of metallic lead in the amalgam. In general
aPb is not unity. The usual procedure is to write Eq. (2) as
 RT  RT
E  E  0
ln a   ln a
 2F  2F
a Pb Pb Pb 2

RT
E  0
ln a (3)
2F
a Pb 2
Amalgam Electrodes where Ea0 is the standard potential of the given amalgam, and
to evaluate Ea0 first. Then, in order to transform Ea0 to EPb0, the
RT
E E 
a
0
ln a (3) emf of the amalgam measured against pure lead when both are
2F immersed in a solution of plumbous ions of the same
a Pb 2

concentration. Since for pure lead the single

electrode potential equation is
RT
E E 
Pb ln a 0

2F
Pb Pb 2

while for the amalgam it is Eq. (3), the difference in potential E between the lead and
amalgam electrodes follows as E E  E Pb a

RT RT
 E  0
ln a    E  ln a  0

 2F   2F 
Pb Pb 2 a Pb 2

E  E
0 0

Pb a
(4)
Amalgam
Electrodes E E  E Pb a

 RT   RT
 E  0
ln a    E  ln a 
0

 2F   2F 
Pb Pb 2 a Pb 2

E  E
0

Pb (4)
0

Consequently, with E and Ea0 known EPb0 may be evaluated, and the emf data
obtained with the amalgam may be reduced to the pure metal.
Thus Carmody found that for the particular lead amalgam he employed in his
studies the standard potential of Pb(Hg) / Pb+2 was 0.1207 volt at 250C, while the emf
of a cell composed of this amalgam and pure lead in a solution of plumbous ions (E)
was 0.0058 volt. The standard potential of the Pb/Pb+2 electrode at 250C is then
E E  E
0

Pb
0

0.0058  0.1207
0.1265volt
 Gas Electrodes/Half-cell
Gas electrodes consist of a gas bubbling about an inert metal wire or foil
immersed in a solution containing ions to which the gas is reversible. The
function of the metal wire or foil, which usually is platinized platinum, is to
facilitate establishment of equilibrium between the gas and its ions and to
serve as the electric contact for the electrode.
These electrodes are prepared by dipping a foil of an
inert metal like platinum or gold in a solution and
bubbling the gas over the surface of the foil. An example
is the hydrogen electrode represented as
Pt,H2 (P atm) | H+(a).
 Gas Electrodes
It consists of a platinized (platinum foil on which
platinum has been deposited electrolytically)
platinum foil dipped into a solution containing
hydrogen ions and a stream of hydrogen gas at a
pressure P atm is bubbled through the solution on the
surface of platinum. The arrangement is shown in
Figure 15.6. Usually the vessel is open to the
atmosphere so that the gas is at atmospheric
pressure. The reaction at the hydrogen gas electrode
may be written as
 Gas Electrodes

Among the gas electrodes are the hydrogen electrode which is reversible
to hydrogen ions, the chlorine electrode reversible to chloride ions, and
the oxygen electrode whose emf depends on the activity of hydroxyl ions.

However, though the first two electrodes can be made reversible, no suitable
electrode material has so far been found which can catalyze satisfactorily
the establishment of equilibrium between oxygen and hydroxyl ions.
Whatever precise information is available on the latter electrode has been obtained
not by direct emf measurements, but by calculation from suitable standard
free energy data obtained from various other sources.
 Gas Electrodes
The fundamental reaction for the hydrogen electrode is

1/2H2(g, PH2) = H+(aH+) + e-

Since the activity of hydrogen gas at relatively low pressures is equal

to the pressure PH , of the gas in atmospheres, the single electrode potential of
2
the hydrogen electrode must be determined both by the pressure
of the hydrogen about the electrode, and the activity of hydrogen ions in solution;
namely,
RT a
E E  0
ln H

F P
H2 H2 1/ 2

H2
Gas RT a
Electrodes E E  ln 0 H

F P
H2 H2 1/ 2

H2

But i.e., the emf of the hydrogen electrode at 1 atm hydrogen pressure
and at unit activity of hydrogen ions, is the reference of all single electrode
emf measurements and is taken by definition to be zero at all temperatures.
Consequently, Eq. (2) becomes
RT a
E  ln H

F P
H2 1/ 2

H2

RT RT
 ln a  ln P 1/ 2

F F
H H2

Further, when the pressure of hydrogen is 1 atm, lnPH21/2 = 0. Then

RT
E  ln a
F
H2 H
Gas Electrodes

RT
E  ln a
F
H2 H

and the hydrogen electrode becomes strictly dependent only on the activity of
hydrogen ions in solution, i.e., the pH. This use of the hydrogen electrode for
pH measurements will be discussed later. The chlorine electrode shows similar
behavior.
 Gas Electrodes
The chlorine electrode shows similar behavior. For this elecrode the reduction
reaction is
1/2Cl2(g, PCl2) + e- = Cl-(aCl-)

And hence the emf is given by

RT a
E E  ln
0 Cl 

F P
Cl 2 Cl 2 1/ 2

Cl 2

However. ECl20, is not zero, but is in fact equal to 1.3595 volts at 25°C.
 Metal- Insoluble Salt Electrodes /Half-cell
Electrodes of this type are extremely important in electrochemistry and they are
encountered very frequently. In this category fall the various calomel electrodes,
the silver-silver chloride electrode, the lead-lead sulfate electrode, the silver-
silver bromide electrode, and others.

The common characteristic of electrodes in this class is that they all

consist of a metal in contact with one of its difficultly soluble salts and a
solution containing the ion present in the salt other than the metal.
For instance, a silver-silver chloride electrode is composed of a silver
wire coated with silver chloride and immersed in a solution of chloride ions.
Again, the lead-lead sulfate electrode may be either pure lead or a lead
amalgam covered with crystals of lead sulfate and surrounded by solutions of
sulfates.

In all instances these electrodes are reversible to the ions other than those of
the metal present in the insoluble salt.

Thus the calomel and silver-silver chloride electrodes are reversible

to chloride ions, the lead-lead sulfate electrode to
sulfate ions, the silver-silver bromide electrode to bromide ions, etc. Why
this is so may be seen from the following discussion of the silver-silver
chloride electrode, a typical member of this class. (a)
 Consider a silver electrode dipping into a solution containing
chloride ions and saturated with silver chloride. If we imagine this electrode to
act as an ordinary metal-metal ion electrode, silver ions will pass from the
electrode into the solution according to the reaction
Ag(s) = Ag+ + e- (a)
However, since the solution is saturated with silver chloride, introduction of
any silver ions will upset the requirements of the solubility product
principle for this salt. Consequently, in order to re-establish the solubility
equilibrium, silver ions will have to combine with chloride ions to precipitate
solid silver chloride according to the relation

Ag+ + CI- = AgCI(s) (b)

Moreover, as the over-all electrode reaction is the sum of all processes

occurring at the electrode, the over-all electrode reaction will have to be the
sum of (a) and (b), or Ag(s) = Ag+ + e-
Ag+ + CI- = AgCI(s)
Ag(s) + CI- = AgCI(s) + e-
 The electrode reaction only involves the
concentration of Cl-. The above reaction
shows how an electron can be released
or taken up in such an electrode.
For Ag-AgCl electrode the electrode reaction is the electrode potential
equation is
Ag(s) + CI- = AgCI(s) + e-
For this reaction the electrode potential equation is
0 RT 1
E Ag  AgCl E Ag  AgCl  ln
F aCl 
and hence this electrode is reversible to chloride ions.
Another example of metal insoluble salt
electrode is the mercury, mercurous
sulphate electrode
Hg, Hg2SO4(s) | SO42-(c) used in the
standard Western cell.
Metal- Insoluble Salt Electrodes Types of Half Cells (H & N book)

Calomel Electrode/metal-insoluble salt electrode

Because of experimental difficulties

involved in the preparation and use of
the standard hydrogen electrode,
secondary reference electrodes have been
compared with the former and are widely
Fig. Saturated calomel electrode used. Among these are the three calomel
electrode.
Metal- Insoluble Salt Electrodes Types of Half Cells (H & N book)

Calomel electrodes, whose emf depends on the

process spontaneous with respect to the hydrogen
electrode reaction

Hg2Cl2(s) +2e- = 2Hg(l) + 2CI- (C = x)

Here x is 0.I N and 1 N potassium chloride for the

Fig. Saturated calomel electrode 0.1 N and 1 N calomel electrodes and a saturated
potassium chloride solution for the saturated
calomel electrode. A form of these electrodes is
shown in Figure 14. 4.
Metal- Insoluble Salt Electrodes Types of Half Cells (H & N book)
The electrode consists of a glass vessel A to which
are attached the sidearm B for making electrical
contact and the arm C for insertion in any desired
solution. Into the bottom of A is sealed a platinum
wire over which are placed in turn a layer of
specially purified mercury, a paste of mercury and
Hg2Cl2 (calomel) and then the appropriate
potassium chloride solution saturated with calomel
so as to fill the cell and the arm C.

Fig. Saturated calomel electrode

Metal- Insoluble Salt Electrodes Types of Half Cells (H & N book)

In the 0.1 N calomel this solution is 0.1 N

potassium chloride, in the 1 N calomel it
is 1 N potassium chloride, and in the
saturated calomel it is an aqueous solution
saturated with both potassium chloride
and mercurous chloride (calomel).
In the latter electrode some crystals of
potassium chloride are also placed over
Fig. Saturated calomel electrode
the mercury-mercurous chloride paste in
order to keep the solution saturated at all The electrode which is represented as
temperatures. A more convenient Hg, Hg Cl (s)/Cl-(c) is shown in Figure 14.4.
2 2
commercial form of these electrodes is
also available.
 Metal- Insoluble Salt Electrodes
In an analogous manner may be deduced the reactions for other .
electrodes of this type. Thus we find for the calomel electrode

2Hg(l) + 2CI- = Hg2Cl2(s) + 2e-

Metal- Insoluble Salt Electrodes.

for the lead-lead sulfate electrode

Pb(s) + SO42- = PbSO4(s) + 2e-

and for the silver-silver bromide electrode

Ag(s) + Br- = AgBr(s) + e-

 Oxidation-Reduction Electrodes/Half-cell
Although every electrode reaction involves an oxidation or a
reduction, the term oxidation-reduction electrodes is used to designate
electrodes in which the emf results from the presence of ions of a
substance in two different stages of oxidation.
When a platinum wire is inserted into a solution containing both
ferrous and ferric ions it is found that the wire acquires a potential.
The same is true of solutions of cerous-ceric
ions, stannous-stannic ions, manganous-permanganate ions, etc. These
electrode emf's arise from the tendency of ions in one state of
oxidation to pass over into a second more stable state.
 Oxidation-Reduction Electrodes
The function of the platinum wire is merely to "pick up" the potential
corresponding to this tendency toward a free energy decrease, and to
serve as the electrical contact of the electrode. The general reaction
for all electrodes of the oxidation-reduction type may be written as
n1  n2
A (a1 )  n  A (a2 ) (1)

where n1 is the valence in the higher stage of oxidation, n 2 that in the

lower, while n = n1 – n2 is the valence change attending the electrode process.
From Eq. (1) the general emf equation follows as
RT a
E E  ln
0 2

nF a 1
 Oxidation-Reduction Electrodes
RT a
E E  0
ln 2

nF a 1

i.e., the emf of oxidation-reduction electrodes depends on the ratio of the

activities of the two ions. Thus, for the ferric-ferrous electrode, designated
symbolically as Pt | Fe+3, Fe+2, the electrode reaction is
3 2
Fe (aFe3 )  e Fe (aFe2 )
And the electrode emf is given by RT a
E E  0
ln Fe 2

F a Fe 3
Oxidation-Reduction Electrodes

In Table 13-3 are given E0 values for several

Electrodes of this type at 250C.
 standard electrode potential (E°)
In electrochemistry, standard electrode potential (E°) is defined as the
measure of the individual potential of a reversible electrode at standard
state with ions at an effective concentration of 1mol dm −3 at the pressure of
1 atm.

The standard reduction potential (E0) is measured under standard conditions:

25°C, a 1 activity for each ion participating in the reaction, a partial pressure
of 1 bar for each gas that is part of the reaction, and metals in their pure
state.
The standard reduction potential is defined relative to a
standard hydrogen electrode (SHE) reference electrode, which is arbitrarily
given a potential of 0.00 V. However, because these can also be referred to
as "redox potentials", the terms "reduction potentials" and "oxidation
potentials" are preferred by the IUPAC.
 standard electrode potential (E°)
Redox potential (also known as oxidation / reduction potential,
'ORP', or, E0', or) is a measure of the tendency of a chemical species to
acquire electrons from or lose electrons to an electrode and thereby be
reduced or oxidised respectively. Redox potential is measured in volts (V),
or millivolts (mV). Each species has its own intrinsic redox potential; for
example, the more positive the reduction potential (reduction potential is
more often used due to general formalism in electrochemistry), the greater
the species' affinity for electrons and tendency to be reduced. ORP can
reflect the antimicrobial potential of the water.
 standard electrode potential (E°) (Values)

Various electrodes in their standard forms, i.e. using solutions of ions of

concentration 1.0 mol L-1 and gases at one atm pressure as the case may be
are combined with the standard hydrogen electrode to form cells.
The potentials of the cells are measured with a high resistance voltmeter
or other means. Remembering that the potential of the standard hydrogen
electrode is 0.00 volt the reading in the instrument directly gives the
standard potential of the electrode. All values are then converted into
reduction potential and are tabulated as in a Table 15.l (Book: H & N).
standard electrode potential (E°)
All values are (Values)
then converted
into reduction
potential and
are tabulated as
in a Table 15.l
(Book: H &
N).
standard electrode potential (E°)
All values (Values)
are then
converted
into
reduction
potential
and are
tabulated
as in a
Table 15.l
(Book: H
& N).
The superscript “°” denotes standard-state
conditions, and E° is the standard reduction
potential, or the voltage associated with a
reduction reaction at an electrode when all
solutes are 1 M and all gases are at 1 atm. Thus,
the standard reduction potential of the hydrogen
electrode is defined as zero. The hydrogen
electrode is called the standard hydrogen
electrode (SHE).
We can use the SHE to measure the potentials of other kinds of electrodes.
For example, Figure 19.4(a) shows a galvanic cell with a zinc electrode and a
SHE. In this case, the zinc electrode is the anode and the SHE is the cathode.
We deduce this fact from the decrease in mass of the zinc electrode during
the operation of the cell, which is consistent with the loss of zinc to the
solution caused by the oxidation reaction:

As mentioned earlier, the Pt electrode provides the surface on

which the reduction takes place. When all the reactants are in
their standard states (that is, H2 at 1 atm, H1 and Zn21 ions at 1
M), the emf of the cell is 0.76 V at 25°C, We can write the half-
cell reactions as follows:
The standard electrode potential of copper can be obtained in a
similar fashion, by using a cell with a copper electrode and a
SHE [Figure 19.4(b)]. In this case, the copper electrode is the
cathode because its mass increases during the operation of the
cell, as is consistent with the reduction reaction:
Uses of Standard Potential Values (book: H & N)
Uses of Standard Potential Values (book: H & N)
 Uses of Standard Potential Values (book: H & N)

The E0cell is negative. Hence the electrode reactions as written do not take place. Rather
the reaction will go in the opposite direction so that Cu2+(aq)| Cu(s) acts as the anode
and the Ag(s)|Ag+(aq) as the cathode when the E0cell will be +0.46 V.
Two important poinis should be noted:
(a) Whether an electrode reaction is oxidation or reduction, for the purpose of
calculation of the cell potential using the equation above reduction potential
must always used.
 Uses of Standard Potential Values (book: H & N)

The E0cell is negative. Hence the electrode reactions as written do not take place. Rather
the reaction will go in the opposite direction so that Cu2+(aq)| Cu(s) acts as the anode
and the Ag(s) | Ag+(aq) as the cathode when the E0cell will be +0.46 V.
Two important poinis should be noted:

(a) Whether an electrode reaction is oxidation or reduction, for the purpose of

calculation of the cell potential using the equation above reduction potential
must always used.

(b) The potential used in the calculation is the value given in the Table and is
independent of the number of electron transfer involved.
Summary of Rules. Before proceeding we shall summarize the various
rules introduced above with respect to cell reactions and emf's. These are:

1. Any cell reaction is the sum of the single electrode reactions as

they occur in the cell.
(a) At the negative electrode the reaction is an oxidation.
(b) At the positive electrode the reaction is a reduction.

2. The total cell emf is the algebraic sum of the single electrode
potentials provided each emf is affixed with the sign corresponding
to the reaction as it actually takes place at the electrode.
Summary of Rules. Before proceeding we shall summarize the various
rules introduced above with respect to cell reactions and emf's. These are:

3. If any cell is written down with the negative electrode on the left, so
that electrons flow through the external circuit from left to right, the
cell reaction deduced by rule 1 will be the spontaneous process, and
the emf deduced by rule 2 for the cell will be positive.

4. If the wrong assumption be made with respect to the polarity of the

electrodes, rule 3 will yield a negative emf corresponding to the
nonspontaneous reaction. To obtain the spontaneous reaction and its
emf, all that need be done is to reverse the reaction and change the sign
of the emf without changing its magnitude.
 Equation (1) and Cell emf’s/Maron Lando Book

Again for the reduction at the calomel electrode

the reaction is

(1) (4a)
Consider now the cell
and the single electrode potential is
(2)
(4b)
In this cell the zinc electrode is negative, and undergoes the
oxidation reaction On adding Eqs. (3a) and (4a) we find the cell reaction to be
(3a)
(5a)
for which the electrode emf is given by
And similarly on adding Eqs. (3b) and (4b) the cell emf
(3b) follows as

Instead of approaching the cell emf through the single electrode potentials,
We may apply Eq. () directly to the cell reaction given in Eq. ().
(5b)
(6)
 Equation (1) and Cell emf’s/Maron Lando Book

Again for the reduction at the calomel electrode

the reaction is

(1) (4a)
Consider now the cell
and the single electrode potential is
(2)
(4b)
In this cell the zinc electrode is negative, and undergoes the
oxidation reaction On adding Eqs. (3a) and (4a) we find the cell reaction to be
(3a)
(5a)
for which the electrode emf is given by
And similarly on adding Eqs. (3b) and (4b) the cell emf
(3b) follows as

Instead of approaching the cell emf through the single electrode potentials,
We may apply Eq. () directly to the cell reaction given in Eq. ().
(5b)
(6)