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) Oxidation: Metal ions pass from the electrode into solution leaving an excess of electrons and thus a negative
(a
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-
Oxidation potential: When electrode is negatively charged with respect to solution, i.e., it acts as anode.
Oxidation occurs.
M Mn+ + ne-
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.
Reference Electrode
( Standard Hydrogen Electrode, SHE)
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.
A part of the gas is adsorbed and the rest escapes through holes. This gives an equilibrium between the adsorbed
Electrode potential
H2 2H+ + 2e-
0.0 V (Anode)
2H+ + 2e- H2
0.0 V (Cathode)
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.
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.
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
2H+ + 2e- H2
H2 (g)/Cathode (+)
EoAnode is the standard oxidation potential of zinc. This potential is given the positive sign.
= -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.
H2 2H+ + 2e-
Cu2+ 2e- Cu
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.
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.
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.
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.
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:
Secondary Cell
Disposable.
Disposable.
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
Robust.
Tolerant to overcharging.
Applications
Submarines
Lighting
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.
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.
3.
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.
3.
4.
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.
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 .