Electrode Potential

What is electrode potential?

When a metal is placed in a solution of its ions, the metal acquires either a positive or negative charge with respect to the solution.
On account of this, a definite potential difference is developed between the metal and the solution. This potential difference is called
electrode potential.
For example, when a plate of zinc is placed in a solution having Zn 2+ ions, it becomes negatively charged with respect to solution
and thus a potential difference is set up between zinc plate and the solution. This potential difference is termed the electrode
potential of zinc.
Similarly, when copper is placed in a solution having Cu 2+ ions, it becomes positively charged with respect to solution. A potential
difference is set up between the copper plate and the solution. The potential difference thus developed is termed as electrode
potential of copper. The potential difference is established due to the formation of electrical double layer at the
Following two changes occur when a metal rod is dipped in its salt solution,

) Oxidation: Metal ions pass from the electrode into solution leaving an excess of electrons and thus a negative

(a

charge on the electrode.

The conversion of metal atoms into metal ions by the attractive force of polar water molecules.
M Mn + neThe metal ions go into the solution and the electrons remain on the metal making it negatively charged. The tendency of the metal to
change into ions is known as electrolytic solution pressure.
(b)

Reduction: Metal ions in solution gain electrons from the electrode leaving a positive charge on the electrode. Metal

ions start depositing on the metal surface leading to a positive charge on the metal.
Mn+ + ne- M
In the beginning, both these changes occur with different speeds but soon an equilibrium is established.
M

Mn+ + ne-

In practice, one effect is greater than the other,

If first effect is greater than the second, the metal acquires a negative charge with respect to solution and
If the second is greater than the first, it acquires positive charge with respect to solution, thus in both the cases a potential difference
is set up.
The magnitude of the electrode potential of a metal is a measure of its relative tendency to lose or gain electrons, i.e., it is a
measure of the relative tendency to undergo oxidation (loss of electrons) or reduction (gain of electrons).

Depending on the nature of the metal electrode to lose or

gain electrons, the electrode potential may be of two types:

Oxidation potential: When electrode is negatively charged with respect to solution, i.e., it acts as anode.
Oxidation occurs.
M Mn+ + ne-

Reduction potential: When

electrode is positively charged with respect to solution, i.e., it acts as

cathode. Reduction occurs.

Mn+ + ne- M

It is not possible to measure the absolute value of the single electrode potential directly. Only the difference in potential
between two electrodes can be measured experimentally. It is, therefore, necessary to couple the electrode with another electrode

whose potential is known. This electrode is termed as reference electrode. The EMF of the resulting cell is measured

experimentally.
The EMF of the cell is equal to the sum of potentials on the two electrodes.

Emf of the cell = EAnode + ECathode = Oxidation potential of anode + Reduction potential of cathode

Knowing the value of reference electrode, the value of other electrode can be determined.

Standard Electrode Potential

In order to compare the electrode potentials of various electrodes, it is necessary to specify the concentration of the ions present in
solution in which the electrode is dipped and the temperature of the half-cell.
The potential difference developed between metal electrode and the solution of its ions of unit molarity (1M) at 25C (298 K) is
called standard electrode potential.
According to the IUPAC convention, the reduction potential alone be called as the electrode potential (E O), i.e., the given value of
electrode potential be regarded as reduction potential unless it is specifically mentioned that it is oxidation potential.
Standard reduction potential of an electrode means that reduction reaction is taking place at the electrode. If the reaction is reversed
and written as oxidation reaction, the numerical value of electrode potential will remain same but the sign of standard potential will
have to be reversed. Thus
Standard reduction potential = - (Standard oxidation potential)
or
Standard oxidation potential = - (Standard reduction potential)

Reference Electrode
( Standard Hydrogen Electrode, SHE)

Hydrogen electrode is the primary standard electrode.

It consists of a small platinum strip coated with platinum black as to adsorb hydrogen gas.

A platinum wire is welded to the platinum strip and sealed in a glass tube as to make contact with the outer circuit through
mercury.

The platinum strip and glass tube is surrounded by an outer glass tube which has an inlet for hydrogen gas at the top and
a number of holes at the base for the escape of excess of hydrogen gas.

The platinum strip is placed in an acid solution which has H+ ion concentration 1 M.

Pure hydrogen gas is circulated at one atmospheric pressure.

A part of the gas is adsorbed and the rest escapes through holes. This gives an equilibrium between the adsorbed

hydrogen and hydrogen ions in the solution.

H2
2H+ + 2eThe temperature of the cell is maintained at 250C. By international agreement the standard hydrogen electrode is arbitrarily assigned
a potential of exactly 0.000 . .. volt.
The hydrogen electrode thus obtained forms one of two half-cells of a voltaic cell. When this half-cell is connected with any other
half-cell, a voltaic cell is constituted. The hydrogen electrode can act as cathode or anode with respect to other electrode.
SHE half reaction

Electrode potential

H2 2H+ + 2e-

0.0 V (Anode)

2H+ + 2e- H2

0.0 V (Cathode)

Measurement of Electrode Potential

The measurement of electrode potential of a given electrode is made by constituting a voltaic cell, i.e., by connecting it with a
standard hydrogen electrode (SHE) through a salt bridge.
1 M solution is used in hydrogen half-cell and the temperature is maintained at 25oC.

The EMF of the cell is measured either by a calibrated potentiometer or by a high resistance voltmeter, i.e., a valve voltmeter. The
reading of the voltmeter gives the electrode potential of the electrode in question with respect to the hydrogen electrode. The
standard electrode potential of a metal may be determined as it is the potential difference in volt developed in a cell consisting of two
electrodes: the pure metal is contact with a molar solution of one of its ions and the standard hydrogen electrode.

Refer to the following video for standard hydrogen electrode

Determination of standard electrode potential of Zn/Zn2+ electrode:

A zinc rod is dipped in 1 M zinc sulphate solution. This half-cell is combined with a standard hydrogen electrode through a
salt bridge.

Both the electrodes are connected with a voltmeter.

The deflection of the voltmeter indicates that current is flowing from hydrogen electrode to metal electrode or the electrons
are moving from zinc rod to hydrogen electrode.

The zinc electrode acts as an anode and the hydrogen electrode as cathode and the cell can be represented as
Cell Representation

Oxidation half

Reduction half

reaction

reaction

Zn|Zn2+ (aq)/Anode(-) || 2H(aq)|

Zn Zn2+ + 2e-

2H+ + 2e- H2

H2 (g)/Cathode (+)

The EMF of the cell is 0.76 volt

ECell = EoAnode + EoCathode

0.76 = EoAnode + 0 or EoAnode = +0.76 V

As the reaction on the anode is oxidation, i.e.,

Zn Zn2+ + 2e,

EoAnode is the standard oxidation potential of zinc. This potential is given the positive sign.

Eoox (Zn/Zn2+) = +0.76 volt

So standard reduction potential of Zn, i.e., Eo (Zn/Zn2+)

= Eoox = -(+0.76)

= -0.76 volt

The EMF of such a cell gives the positive value of standard oxidation potential of metal M. The standard reduction
potential (Eo) is obtained by reversing the sign of standard oxidation potential.

Determination of standard electrode potential of Cu2+/Cu, electrode:

A copper rod is dipped in 1 M solution of CuSO4. It is combined with hydrogen electrode through a salt bridge. Both the electrodes
joined through a voltmeter. The deflection of the voltmeter indicates that current is flowing from copper electrode towards hydrogen
electrode, i.e., the electrons ate moving from hydrogen to copper electrode. The hydrogen electrode acts as an anode and the
copper electrode as a cathode. The cell can be represented as
Cell Representation

Oxidation half reaction

Reduction half reaction

H2 (g)|2H+ (aq) ||Cu2+ (aq) |Cu

H2 2H+ + 2e-

Cu2+ 2e- Cu

The EMF of the cell is 0.34 volt.

EoCell = EoAnode + EoCathode

0.34 = 0 + EoCathode

Since the reaction on the cathode is reduction, i.e.,

Cu2+ + 2e- Cu, EoCathode is the standard reduction potential of copper. This is given the +ve sign.

E, i.e., standard reduction potential of Cu2+/Cu = 0.34 volt

So Ex (standard oxidation potential of copper) = -0.34 volt

The EMF of such a cell gives positive value of reduction potential of metal electrode. The standard oxidation potential of
this electrode is obtained by reversing the sign of standard reduction potential.

The EMFof such a cell gives the positive value of standard oxidation potential of metal M. The standard reduction
potential (E) is obtained by reversing the sign of standard oxidation potential.

It is thus concluded that at the metal electrode which acts as anode with respect to hydrogen electrode (cathode), the
reduction potential is given the minus sign and at the metal electrode which acts as cathode with respect to hydrogen electrode
(anode), the reduction potential is given the positive sign.

The standard electrode potentials (oxidation or reduction) of various elements can be measured by combining the
electrode in question with a standard hydrogen electrode and measuring the emf of the cell constituted.

Some Other Reference Electrodes

Since a standard hydrogen electrode is difficult to prepare and maintain, it is usually replaced by other reference electrodes, which
are known as secondary reference electrodes. These are convenient to handle and are prepared easily. Two important secondary
reference electrodes are described here.

Calomel electrode:
It consists of mercury at the bottom over which a paste of mercury-mercurous chloride is placed. A solution of potassium chloride is
then placed over the paste. A platinum wire sealed in a glass tube helps in making the electrical contact. The electrode is connected
with the help of the side tube on the left through a salt bridge with the other electrode to make a complete cell.
The potential of the calomel electrode depends upon the concentration of the potassium chloride solution. If
potassium chloride solution is saturated, the electrode is known as saturated calomel electrode (SCE) and if the potassium chloride
solution is 1 N, the electrode is known as normal calomel electrode (NCE) while for 0.1 N potassium chloride solution, the
electrode is referred to as decinormal calomel electrode (DNCE). The electrode reaction when the electrode acts as cathode is:
1/2 Hg2Cl2 + e-

Hg + Cl-

The reduction potentials of the calomel electrodes on hydrogen scale at 298K are as follows:
Concentration of KCl

Reduction Potential

Saturated KCl

0.2415 V

1.0NKCl

0.2800 V

0.1NKCl

0.3338 V

The electrode potential of any other electrode on hydrogen scale can be measured when it is combined with calomel electrode. The
emf of such a cell is measured. From the value of electrode potential of calomel electrode, the electrode poten tial of the other
electrode can be evaluated.

Ferrous Ferric Electrode

An example is a Pt wire dipping in a solution containing ferrous and ferric ions. Such a cell is described as: Pt | Fe 2+ (C1), Fe3+ (C2)
The comma is used to separate two chemical species in the same solution. The electrode reaction is
Fe3+ + e Fe2+
The function of a Platinum wire is to pick up the electrons and provide electrical contact to the electrode.

Quin Hydrone Electrode :

Oxidation reduction electrodes can also be made with organic molecules that can exist in two different oxidation states.
A generally used material of this type is related to important biochemical oxidation reduction reactions, is the system of
hydroquinone, which can form the oxidation reduction system, between quinone (Q) and hydroquinone (QH 2).

The presence of a Pt electrode in a solution containing these two species again clearly provides an electrode that can donate or
accept electrons.
If

hydro

quinone is

represented

by

QH2 and

quinone

by

Q,

the

electrode

is

abbreviated

as

Pt.|QH2,Q,H+ (C)
This electrode is called a quin-hydrone electrode, because of the charged complex that is formed between QH 2 and Q.

Metal Metal ion Electrode :

An example of this is a metallic silver electrode in an AgNO 3 solution. The electrode is represented as Ag | Ag + (C) and the electrode
reaction is Ag+ + e Ag.
Note: Very active metals react directly with water itself and cannot be used for such electrodes.
Another example is Silver-silver chloride electrode
This is another widely used reference electrode. It is reversible and stable and can be combined with cells containing chlorides
without insetting liquid junctions.
Silver chloride is deposited electrolytically on a silver or platinum wire and it is then immersed in a solution containing chloride ions.
Its standard electrode potential with respect to the standard hydrogen electrode is 0.2224 V at 298 K. the electrode is represented
as: Ag|AgCl|Cl- and the electrode reaction is, AgCl+e- Ag + Cl-

Amalgam Electrode

In a variation of the previous electrode, the metal is in the form of an amalgam, i.e., it is dissolved in mercury, rather than in the pure
form. Electrical contact is made by a Pt wire dipping into the amalgam pool. The reaction is the same as in the metalmetal ion
electrode, with the Hg playing no role. A sodium amalgam electrode is represented as Na [ in Hg at C1] | Na+ (C2).

concentration cell

is a limited form of a galvanic cell that has two equivalent half-cells of the same

material differing only in concentrations. One can calculate the potential developed by such a cell using the Nernst Equation. A
concentration cell produces a small voltage as it attempts to reach equilibrium. This equilibrium occurs when the concentration of
reactant in both cells are equal. Because an order of magnitude concentration difference produces less than 30 millivolts at room
temperature, concentration cells are not typically used for energy storage.
Concentration cells generate electricity from the thermodynamic free energy that can be extracted from the difference in chemical
concentrations of reactants, in the same reaction. This energy is generated from thermal energy that the cells absorb as heat, as the
electricity flows. This generation of electricity from ambient thermal energy, without a temperature gradient, is possible because the
convergence of chemical concentrations in the two cells increases entropy, and this increase more than compensates for the
entropy decreased when heat is converted into electrical energy.
Concentration cell methods of chemical analysis compare a solution of known concentration with an unknown, determining the
concentration of the unknown via the Nernst Equation or comparison tables against a group of standards.
Concentration cell corrosion occurs when two or more areas of a metal surface are in contact with different concentrations of the
same solution. There are three general types of concentration cells:

Difference between primary and secondary cells

Primary Cell

Secondary Cell

Lower initial cost.

Higher Initial Cost

Higher life-cycle cost ($/kWh).

Lower life-cycle cost ($/kWh) if

charging in convenient and
inexpensive

Disposable.

Regular maintenance required.

Disposable.

Periodic recharging required.

Replacement readily available.

Replacements while available,

are not produced in the same
sheer numbers as primary
batteries. May need to be preordered.

Typically lighter and smaller thus traditionally more

suited for portable applications.

Traditionally less suited for

portable applications, although
recent advances in Lithium
battery technology have lead to
the development of
smaller/lighter secondary
batteries.

Longer service per charge and good

Relative to primary battery

systems, traditional secondary
batteries (particularly aqueous
secondary batteries) exhibit
inferior charge retention.

Not ideally suited for heavy load/high rate discharge high

performance.

Superior high discharge rate

performance at heavy loads

Not ideally suited for , emergency backup, hybrid battery,

and high cost military applications.

Ideally suited for load-leveling,

emergency backup, hybrid
battery and high cost military
applications

Traditionally limited to specific

applications.

The overall inherent versatility

of secondary battery systems
allows its use and continuing
research for a large spectrum of
applications.

What is the difference between primary and secondary cells?

Primary cells are batteries that are not easily recharged after use, while secondary cells are those which can
be recharged. Usually, primary cells are discarded after a single use, while secondary cells are used over and over
again.
Primary cells usually lack a free-flowing electrolyte; instead, they hold the electrolyte inside solid devices called
separators. Because they lack a significant quantity of liquid electrolyte, such batteries are often called dry cells. By
contrast, secondary cells usually contain a liquid electrolyte, earning them the name wet cells.
After secondary cells have completely discharged, they can be recharged and used again. By pumping electric
current through the cell in the opposite direction that it normally flows, the cell can be recharged for additional use.
Examples of primary cells include the types of batteries used for childrens toys, radios and similar consumer
electronics products. By contrast, car batteries and standby power sources are usually secondary cells.
Because they require a liquid electrolyte, secondary cells are usually larger than primary cells. Primary cells are often
less expensive than secondary cells as well, because they require fewer components and their construction is
simpler. Often, secondary cells require additional maintenance, while the low cost of primary cells means that
maintenance is not necessary.
Reference:

Advantages

Reliable. Over 140 years of development.

Robust.

Tolerant to overcharging.

Low internal impedance.

Can deliver very high currents.

Indefinite shelf life if stored without electrolyte.

Can be left on trickle or float charge for prolonged periods.

Wide range of sizes and capacities available.

The worlds most recycled product.

Applications

Automotive and traction applications.

Standby/Back-up/Emergency power for electrical installations.

Submarines

UPS (Uninterruptible Power Supplies)

Lighting

High current drain applications.

Sealed battery types available for use in portable equipment.

Costs

Low cost

Flooded lead acid cells are one of the least expensive sources of battery power available.

Deep cycle cells may cost up to double the price of the equivalent flooded cells.

Varieties of Lead Acid Batteries

Lead Calcium Batteries | Lead acid batteries with electrodes modified by the addition of Calcium providing the following advantages:
1.

More resistant to corrosion, overcharging, gassing, water usage, and self-discharge, all of which shorten battery life.

2.

Larger electrolyte reserve area above the plates.

3.

Higher Cold Cranking Amp ratings.

4.

Little or No maintenance.

Lead Antimony Batteries | Lead acid batteries with electrodes modified by the addition of Antimony providing the following advantages:

1.

Improved mechanical strength of electrodes important for EV and deep discharge applications

2.

Reduced internal heat and water loss.

3.

Longer service life than Calcium batteries.

4.

Easier to recharge when completely discharged.

5.

Lower cost.

Valve Regulated Lead Acid (VRLA) Batteries | Also called Sealed Lead Acid (SLA) batteries.

This construction is designed to prevent electrolyte loss through evaporation, spillage and gassing and this in turn prolongs the life of the battery and
eases maintenance. Instead of simple vent caps on the cells to let gas escape, VRLA have pressure valves that open only under extreme conditions.
Valve-regulated batteries also need an electrolyte design that reduces gassing by impeding the release to the atmosphere of the oxygen and hydrogen
generated by the galvanic action of the battery during charging. This usually involves a catalyst that causes the hydrogen and oxygen to recombine into
water and is called a recombinant system. Because spillage of the acid electrolyte is eliminated the batteries are also safer.

AGM Absorbed Glass Mat Battery | Also known as Absorptive Glass Micro-Fibre
Used in VRLA batteries the Boron Silicate fibreglass mat which acts as the separator between the electrodes and absorbs the free electrolyte acting
like a sponge. Its purpose is to promote recombination of the hydrogen and oxygen given off during the charging process. No silica gel is necessary.
The fibreglass matt absorbs and immobilises the acid in the matt but keeps it in a liquid rather than a gel form. In this way the acid is more readily
available to the plates allowing faster reactions between the acid and the plate material allowing higher charge/discharge rates as well as deep cycling.
This construction is very robust and able to withstand severe shock and vibration and the cells will not leak even if the case is cracked.
AGM batteries are also sometimes called starved electrolyte or dry, because the fibreglass mat is only 95% saturated with Sulfuric acid and there is
no excess liquid.

Gel Cell
This is an alternative recombinant technology to also used in VRLA batteries to promote recombination of the gases produced during charging. It also
reduces the possibility of spillage of the electrolyte. Prone to damage if gassing is allowed to occur, hence charging rates may be limited. They must be
charged at a slower rate (C/20) to prevent excess gas from damaging the cells. They cannot be fast charged on a conventional automotive charger or
they may be permanently damaged.

SLI Batteries (Starting Lighting and Ignition)

This is the typical automotive battery application. Automotive batteries are designed to be fully charged when starting the car; after starting the vehicle,
the lost charge, typically 2% to 5% of the charge, is replaced by the alternator and the battery remains fully charged. These batteries are not designed
to be discharged below 50% Depth of Discharge (DOD) and discharging below these levels can damage the plates and shorten battery life.

Deep Cycle Batteries

Marine applications, golf buggies, fork lift trucks and electric vehicles use deep cycle batteries which are designed to be completely discharged before
recharging. Because charging causes excessive heat which can warp the plates, thicker and stronger or solid plate grids are used for deep cycling
applications. Normal automotive batteries are not designed for repeated deep cycling and use thinner plates with a greater surface area to achieve
high current carrying capacity.

Lead Storage Battery

Lead-acid batteries provide high currents and store charge for long periods of
time, making them essential for vehicles.

KEY POINTS

Lead-acid batteries, also known as lead storage batteries, can store a lot of charge and
provide high current for short periods of time. However, they have a limited life, are heavy to
ship, and contain toxic materials.

The basic design of lead acid batteries has not changed significantly since 1859 when Plant
designed them, although some improvements were made by Faure.

Lead acid batteries are capable of being recharged, which is important for their use in cars.
The discharge and charge reactions are the reverse of each other.

Discharging the stored energy relies on both the positive and negative plates become lead (II)
sulfate and the electrolyte losing much of its dissolved sulfuric acid. Charging occurs when the
charging source removes electrons from the positive plate and introduces them to the negative
plate.

lignosulfonate
Water-soluble anionic polyelectrolyte polymers: they are byproducts from the production of wood
pulp using sulfite pulping.

A lead storage battery, also known as a lead-acid battery, is the oldest type of rechargeable battery
and one of the most common energy storage devices. The batteries were invented in 1859 by French
physicist Gaston Plant. They are used in a variety of applications. Most people are accustomed to
using them in vehicles, where they have the ability to provide high currents for cranking power. For
remote power systems, deep discharge batteries are used. Unlike car starter batteries which are used
to provide high current for very short periods, deep discharge batteries are designed to hold larger
amounts of energy for longer periods of time. Although batteries are reliable, they have a limited life,
are heavy to ship, and contain toxic materials that require specific removal methods at the end of
their useful life. Remote applications usually require larger batteries that have higher amounts of
lead and more room for electrolytes. Lead-acid batteries have moderate power density and good
response time. Depending on the power conversion technology incorporated, batteries can go from
accepting energy to supplying energy instantaneously. Lead-acid batteries are affected
by temperatureand must be maintained well in order to achieve maximum life expectancy.
In Plant's design of the lead-acid cell, the positive and negative plates were made out of two spirals
of lead foil, separated with a sheet of cloth and coiled up. The cells initially had low capacity. A slow
process of "forming" was required to corrode the lead foils, creating lead dioxide on the plates and
roughening them to increase surface area. Initially this process used electricity from primary
batteries. When generators became available after 1870, the cost of the production of batteries
greatly declined. Plant plates are still used in some stationary applications where the plates are
mechanically grooved to increase their surface area .