This article presents the industrial and laboratory methodologies to prepare elemental

chlorine

Gas extraction

Chlorine can be manufactured by electrolysis of a sodium chloride solution (brine). The

production of chlorine results in the co-products caustic soda (sodium hydroxide,
(NaOH ) and hydrogen gas (H2). These two products, as well as chlorine itself, are
highly reactive. Chlorine can also be produced by the electrolysis of a solution of
potassium chloride, in which case the co-products are hydrogen and caustic potash
(potassium hydroxide). There are three industrial methods for the extraction of chlorine
by electrolysis of chloride solutions, all proceeding according to the following
equations:

Cathode: 2 H+ (aq) + 2 e− → H2 (g)

Anode: 2 Cl− (aq) → Cl2 (g) + 2 e−

Overall process: 2 NaCl (or KCl) + 2 H2O → Cl2 + H2 + 2 NaOH (or KOH)

Mercury cell electrolysis

Mercury cell electrolysis, also known as the Castner-Kellner process, was the first
method used at the end of the nineteenth century to produce chlorine on an industrial
scale. The "rocking" cells used have been improved over the years. Today, in the
"primary cell", titanium anodes (formerly graphite ones) are placed in a sodium (or
potassium) chloride solution flowing over a liquid mercury cathode. When a potential
difference is applied and current flows, chlorine is released at the titanium anode and
sodium (orpotassium) dissolves in the mercury cathode forming an amalgam. This
flows continuously into a separate reactor ("denuder" or "secondary cell"), where it is
usually converted back to mercury by reaction with water, producing hydrogen and
sodium (or potassium) hydroxide at a commercially useful concentration (50% by
weight). The mercury is then recycled to the primary cell.The mercury process is the
least energy-efficient of the three main technologies (mercury, diaphragm and
membrane) and there are also concerns about mercury emissions.

Diaphragm cell electrolysis (Bipolar)

In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a

cathode and an anode, preventing the chlorine forming at the anode from re-mixing
with thesodium hydroxide and the hydrogen formed at the cathode. This technology
was also developed at the end of the nineteenth century. There are several variants of
this process: the Le Sueur cell (1893), the Hargreaves-Bird cell (1901), the Gibbs cell
(1908), and the Townsend cell (1904). The cells vary in construction and placement of
the diaphragm, with some having the diaphragm in direct contact with the cathode.

The salt solution (brine) is continuously fed to the anode compartment and flows
through the diaphragm to the cathode compartment, where the caustic alkali is
produced and the brine is partially depleted. As a result, diaphragm methods produce
alkali that is quite dilute (about 12%) and of lower purity than do mercury cell methods.

Diaphragm cells are not burdened with the problem of preventing mercury discharge
into the environment; they also operate at a lower voltage, resulting in an energy
savings over the mercury cell method, but large amounts of steam are required if the
caustic has to be evaporated to the commercial concentration of 50%.Membrane cell
electrolysis

Development of this technology began in the 1970s. The electrolysis cell is divided into
two "sections" by a cation permeable membrane acting as an ion exchanger.
Saturatedsodium (or potassium) chloride solution is passed through the anode
compartment, leaving at a lower concentration. Sodium (or potassium) hydroxide
solution is circulated through the cathode compartment, exiting at a higher
concentration. A portion of the concentrated sodium hydroxide solution leaving the cell
is diverted as product, while the remainder is diluted with deionized water and passed
through the electrolysis apparatus again.

This method is more efficient than the diaphragm cell and produces very pure sodium
(or potassium) hydroxide at about 32% concentration, but requires very pure brine.
Membrane cell process for chloralkali production

Other electrolytic processes

Although a much lower production scale is involved, electrolytic diaphragm and

membrane technologies are also used industrially to recover chlorine from hydrochloric
acid solutions, producing hydrogen (but no caustic alkali) as a co-product.

Furthermore, electrolysis of fused chloride salts (Downs process) also enables chlorine
to be produced, in this case as a by-product of the manufacture of metallic sodium or
magnesium.

Other methods

Before electrolytic methods were used for chlorine production, the direct oxidation of
hydrogen chloride with oxygen or air was exercised in the Deacon process:

4 HCl + O2 → 2 Cl2 + 2 H2O

This reaction is accomplished with the use of copper(II) chloride (CuCl2) as a catalyst
and is performed at high temperature (about 400 °C). The amount of extracted chlorine
is approximately 80%. Due to the extremely corrosive reaction mixture, industrial use of
this method is difficult and several pilot trials failed in the past. Nevertheless, recent
developments are promising. Recently Sumitomo patented a catalyst for the Deacon
process using ruthenium(IV) oxide (RuO2). Another earlier process to produce chlorine
was to heat brine with acid and manganese dioxide.

2 NaCl + 2H2SO4 + MnO2 → Na2SO4 + MnSO4 + 2 H2O + Cl2

Using this process, chemist Carl Wilhelm Scheele was the first to isolate chlorine in a
laboratory. The manganese can be recovered by the Weldon process.[10]

Small amounts of chlorine gas can be made in the laboratory by putting concentrated
hydrochloric acid in a flask with a side arm and rubber tubing attached. Manganese
dioxide is then added and the flask stoppered. The reaction is not greatly exothermic.
As chlorine is denser than air, it can be easily collected by placing the tube inside a flask
where it will displace the air. Once full, the collecting flask can be stoppered.

Another method for producing small amounts of chlorine gas in a lab is by adding
concentrated hydrochloric acid (typically about 5M) to sodium hypochlorite or sodium
chlorate solution. Potassium permanganate can be used to generate chlorine gas when
added to hydrochloric acid.

Industrial production

Large-scale production of chlorine involves several steps and many pieces of

equipment. The description below is typical of a membrane plant. The plant also
simultaneously produces sodium hydroxide (caustic soda) and hydrogen gas. A typical
plant consists of brine production/treatment, cell operations, chlorine cooling & drying,
chlorine compression & liquefaction, liquid chlorine storage & loading, caustic
handling, evaporation, storage & loading and hydrogen handling.

Brine

Key to the production of chlorine is the operation of the brine saturation/treatment

system. Maintaining a properly saturated solution with the correct purity is vital,
especially formembrane cells. Many plants have a salt pile which is sprayed with
recycled brine. Others have slurry tanks that are fed raw salt. ditionally filtered before
entering ion exchangersto further remove impurities. At several points in this process,
the brine is tested for hardness and strength.

After the ion exchangers, the brine is considered pure, and is transferred to storage
tanks to be pumped into the cell room. Brine,, is heated to the correct temperature to
control exit brine temperatures according to the electrical load. Brine exiting the cell
room must be treated to remove residual chlorine and control pH levels before being
returned to thesaturation stage. This can be accomplished via dechlorination

towers with acid and sodium bisulfite addition. Failure to remove chlorine can result in
damage to the cells. Brine should be monitored for accumulation of both chlorate anions
and sulfate anions, and either have a treatment system in pl ace, or purging of the
brineloop to maintain safe levels, since chlorate anions can diffuse through the
membranes and contaminate the caustic, while sulfate anions can damage the anode
surface coating.

Cell room

The building that houses the many electrolytic cells is usually called a cell room or cell
house, although some plants are built outdoors. This building contains support
structures for the cells, connections for supplying electrical power to the cells and
piping for the fluids. Monitoring and control of the temperatures of the feed caustic and
brine is done to control exit temperatures. Also monitored are the voltages of each cell
which vary with the electrical load on the cell room that is used to control the rate of
production. Monitoring and control of the pressures in the chlorine and hydrogen
headers is also done via pressure control valves.

Direct current is supplied via a rectified power source. Plant load is controlled by
varying the current to the cells. As the current is increased, flow rates for brine and
caustic and deionized water are increased, while lowering the feed temperatures.

Cooling and drying

Chlorine gas exiting the cell line must be cooled and dried since the exit gas can be over
80°C and contains moisture that allows chlorine gas to be corrosive to iron piping.
Cooling the gas allows for a large amount of moisture from the brine to condense out
of the gas stream. Cooling also improves the efficiency of both the compression and
theliquefaction stage that follows. Chlorine exiting is ideally between 18°C and 25°C.
After cooling the gas stream passes through a series of towers with counter flowing
sulfuric acid. These towers progressively remove any remaining moisture from the
chlorine gas. After exiting the drying towers the chlorine is filtered to remove any
remaining sulfuric acid.

Compression and liquefaction

Several methods of compression may be used: liquid ring, reciprocating, or centrifugal.

The chlorine gas is compressed at this stage and may be further cooled by inter- and
after-coolers. After compression it flows to the liquefiers, where it is cooled enough to
liquefy. Non condensible gases and remaining chlorine gas are vented off as part of the
pressure control of the liquefaction systems. These gases are routed to a gas scrubber,
producing sodium hypochlorite, or used in the production of hydrochloric acid (by
combustion with hydrogen) or ethylene dichloride (by reaction with ethylene).

Storage and loading

Liquid chlorine is typically gravity-fed to storage tanks. It can be loaded into rail or
road tankers via pumps or padded with compressed dry gas.

Caustic handling, evaporation, storage and loading

Caustic, fed to the cell room flows in a loop that is simultaneously bled off to storage
with a part diluted with deionized water and returned to the cell line for strengthening
within the cells. The caustic exiting the cell line must be monitored for strength, to
maintain safe concentrations. Too strong or too weak a solution may damage the
membranes. Membrane cells typically produce caustic in the range of 30% to 33% by
weight. The feed caustic flow is heated at low electrical loads to control its exit
temperature. Higher loads require the caustic to be cooled, to maintain correct exit
temperatures. The caustic exiting to storage is pulled from a storage tank and may be
diluted for sale to customers who require weak caustic or for use on site. Another
stream may be pumped into a multiple effect evaporator set to produce commercial
50% caustic. Rail cars and tanker trucks are loaded at loading stations via pumps.
Hydrogen handling

Hydrogen produced may be vented unprocessed directly to the atmosphere or cooled,

compressed and dried for use in other processes on site or sold to a customer via
pipeline, cylinders or trucks. Some possible uses include the manufacture of
hydrochloric acid or hydrogen peroxide, as well as desulfurization of petroleum oils, or
use as a fuel in boilersor fuel cells. For example, in Porsgrunn the byproduct is used for
the hydrogen fueling station at Hynor.[citation needed]Energy consumptionProduction
of chlorine is extremely energy intensive. Energy consumption per unit weight of
product is not far below that for iron and steel manufacture and greater than for the
production of glass or cement.

Since electricity is an indispensable raw material for the production of chlorine, the
energy consumption corresponding to the electrochemical reaction cannot be reduced.
Energy savings arise primarily through applying more efficient technologies and
reducing ancillary energy use.

3.1.1 Sodium hydroxide

Sodium hydroxide, also known as caustic soda or, is an inorganic compound with
the chemical formula NaOH. It is a white solid and
highly caustic metallic base and alkali salt which is available in pellets, flakes, granules,
and as prepared solutions at a number of different concentrations. Sodium hydroxide
forms an approximately 50% (by weight) saturated solution with water.

Sodium hydroxide is soluble in water, ethanol and methanol. This alkali is deliquescent
and readily absorbs moisture and carbon dioxide in air.

Sodium hydroxide is used in many industries, mostly as a strong chemical base in the
manufacture of pulp and paper, textiles ,drinking water, soaps and detergents and as a
drain cleaner. Worldwide production in 2004 was approximately 60 million tonnes,
while demand was 51 million tonnes.

Physical properties

Pure sodium hydroxide is a whitish solid, sold in pellets, flakes, and granular form, as
well as in solution. It is highly soluble in water, with a lower solubility in ethanol and
methanol, but is insoluble in ether and other non-polar solvents.

Similar to the hydration of sulfuric acid, dissolution of solid sodium hydroxide in water
is a highly exothermic reaction in which a large amount of heat is liberated, posing a
threat to safety through the possibility of splashing. The resulting solution is usually
colourless and odorless with slippery feeling upon contact in common with other
alkalis.
Chemical properties

Reaction with acids

Sodium hydroxide reacts with protic acids to produce water and the corresponding
salts. For example, when sodium hydroxide reacts with hydrochloric acid, sodium
chloride is formed

:NaOH (aq) + HCl(aq) → NaCl(aq) + H2O(l)

In general, such neutralization reactions are represented by one simple net ionic
equation:

OH−(aq) + H+(aq) → H2O(l)

This type of reaction with a strong acid releases heat, and hence is exothermic. Such
acid-base reactions can also be used for titrations. However, sodium hydroxide is not
used as a primary standard because it is hygroscopic and absorbs carbon dioxide from
air.

Reaction with acidic oxides

Sodium hydroxide also reacts with acidic oxides, such as sulfur dioxide. Such reactions
are often used to "scrub" harmful acidic gases (like SO 2 and H2S) produced in the
burning of coal and thus prevent their release into the atmosphere. For example,

2 NaOH + CO2 → Na2CO3 + H2O

Reaction with amphoteric metals and oxides

Glass reacts slowly with aqueous sodium hydroxide solutions at ambient temperatures
to form soluble silicates. Because of this, glass joints and stopcocks exposed to sodium
hydroxide have a tendency to "freeze". Flasks and glass-lined chemical reactors are
damaged by long exposure to hot sodium hydroxide, which also frosts the glass.
Sodium hydroxide does not attack iron since iron does not have amphoteric properties
(i.e., it only dissolves in acid, not base). A few transition metals, however, may react
vigorously with sodium hydroxide.

In 1986, an aluminium road tanker in the UK was mistakenly used to transport 25%
sodium hydroxide solution, causing pressurization of the contents and damage to the
tanker. The pressurization was due to the hydrogen gas which is produced in the
reaction between sodium hydroxide and aluminium:

2 Al + 2 NaOH + 6 H2O → 2 Na[Al(OH)4] + 3 H2

Precipitant

Unlike sodium hydroxide, the hydroxides of most transition metals are insoluble, and
therefore sodium hydroxide can be used to precipitate transition metal hydroxides. The
following colours are observed: blue-copper, green-iron(II), yellow/brown-iron(III).
Zinc and lead salts dissolve in excess sodium hydroxide to give a clear solution of
Na2ZnO2 or Na2PbO2.

Aluminium hydroxide is used as a gelatinous flocculant to filter out particulate matter

in water treatment. Aluminium hydroxide is prepared at the treatment plant from
aluminium sulfate by reacting it with sodium hydroxide.

Al2(SO4)3 + 6 NaOH → 2 Al(OH)3 + 3 Na2SO4

Saponification

Sodium hydroxide can be used for the base-driven hydrolysis of esters (as in
saponification), amides and alkyl halides. However, the limited solubility of sodium
hydroxide in organic solvents means that the more soluble potassium hydroxide (KOH)
is often preferred.Production

Sodium hydroxide is industrially produced as a 50% solution by variations of the

electrolytic chloralkali process. Chlorine gas is also produced in this process. Solid
sodium hydroxide is obtained from this solution by the evaporation of water. Solid
sodium hydroxide is most commonly sold as flakes, prills, and cast blocks.
In 2004, world production was estimated at 60 million dry metric tonnes of sodium
hydroxide, and demand was estimated at 51 million tonnes. In 1998, total world
production was around 45 million tonnes. North America and Asia collectively
contributed around 14 million tonnes, while Europe produced around 10 million
tonnes. In the United States, the major producer of sodium hydroxide is the Dow
Chemical Company, which has annual production around 3.7 million tonnes from sites
at Freeport, Texas, and Plaquemine, Louisiana. Other major US producers include
OxyChem, PPG, Olin, Pioneer Companies, Inc. (PIONA, which was purchased by Olin),
and Formosa. All of these companies use thechloralkali process.

Historically, sodium hydroxide was produced by treating sodium carbonate with

calcium hydroxide in a metathesis reaction. (Sodium hydroxide is soluble while calcium
carbonate is not.) This process was called causticizing.[12]Ca(OH)2(aq) + Na2CO3(s) →
CaCO3↓ + 2 NaOH(aq)

This process was superseded by the Solvay process in the late 19th century, which was
in turn supplanted by the chloralkali process which we use today.

Sodium hydroxide is also produced by combining pure sodium metal with water. The
byproducts are hydrogen gas and heat, often resulting in a flame, making this a
common demonstration of the reactivity of alkali metals in academic environments;
however, it is not commercially viable, as the isolation of sodium metal is typically
performed by reduction or electrolysis of sodium compounds including sodium
hydroxide.

Uses

Canister of sodium hydroxide.

Sodium hydroxide is a popular strong base used in the industry. Around 56% of
sodium hydroxide produced is used by the industry, 25% of which is used in paper
industry. Sodium hydroxide is also used in manufacturing of sodium salts and
detergents, pH regulation, and organic synthesis. It is used in the Bayer process of
aluminium production. In bulk, it is most often handled as an aqueous solution, since
solutions are cheaper and easier to handle.

Sodium hydroxide is used in many scenarios where it is desirable to increase the

alkalinity of a mixture, or to neutralize acids.

For example, in petroleum industry, sodium hydroxide is used as an additive in drilling

mud to increase alkalinity in bentonite mud systems, to increase the mud viscosity, and
to neutralise any acid gas (such as hydrogen sulfide and carbon dioxide) which may be
encountered in the geological formation as drilling progresses.

Poor quality crude oil can be treated with sodium hydroxide to remove sulfurous
impurities in a process known as caustic washing. As above, sodium hydroxide reacts
with weak acids such as hydrogen sulfide and mercaptans to give the non-volatile
sodium salts which can be removed. The waste which is formed is toxic and difficult to
deal with, and the process is banned in many countries because of this. In 2006,
Trafigura used the process and then dumped the waste in Africa.

Chemical pulping

Sodium hydroxide is also widely used in pulping of wood for making paper or

regenerated fibers. Along with sodium sulfide, sodium hydroxide is a key component
of the white liquor solution used to separate lignin from cellulose fibers in the kraft
process. It also plays a key role in several later stages of the process of bleaching the
brown pulp resulting from the pulping process. These stages include oxygen
delignification, oxidative extraction, and simple extraction, all of which require a strong
alkaline environment with a pH > 10.5 at the end of the stages.

Tissue digestion

In a similar fashion, sodium hydroxide is used to digest tissues, such as in a process that
was used with farm animals at one time. This process involved placing a carcass into a
sealed chamber, then adding a mixture of sodium hydroxide and water (which breaks
the chemical bonds that keep the flesh intact). This eventually turns the body into a
liquid with coffee-like appearance, and the only solid that remains are bone hulls, which
could be crushed between one's fingertips. Sodium hydroxide is frequently used in the
process of decomposing roadkill dumped in landfills by animal disposal contractors.
Due to its low cost and availability, it has been used to dispose of corpses by criminals.
Italian serial killer Leonarda Cianciulli used this chemical to turn dead bodies into
soap.In Mexico, a man who w orked for drug cartels admitted disposing over 300
bodies with it.

Dissolving amphoteric metals and compounds

Strong bases attack aluminium. Sodium hydroxide reacts with aluminium and water to
release hydrogen gas. The aluminium takes the oxygen atom from sodium hydroxide,
which in turn takes the oxygen atom from the water, and releases the two hydrogen
atoms, The reaction thus produces hydrogen gas and sodium aluminate. In this
reaction, sodium hydroxide acts as an agent to make the solution alkaline, which
aluminium can dissolve in. This reaction can be useful in etching, removing anodizing,
or converting a polished surface to a satin-like finish, but without further passivation
such as anodizing or alodining the surface may become degraded, either under normal
use or in severe atmospheric conditions.

In the Bayer process, sodium hydroxide is used in the refining of alumina containing
ores (bauxite) to produce alumina (aluminium oxide) which is the raw material used to
producealuminium metal via the electrolytic Hall-Héroult process. Since the alumina is
amphoteric, it dissolves in the sodium hydroxide, leaving impurities less soluble at high
pH such asiron oxides behind in the form of a highly alkaline red mud.

Other amphoteric metals are zinc and lead which dissolve in concentrated sodium
hydroxide solutions to give sodium zincate and sodium plumbate respectively.

Esterification and transesterification reagent

Sodium hydroxide is traditionally used in soap making (cold process soap,
saponification). It was made in the nineteenth century for a hard surface rather than
liquid product because it was easier to store and transport.

For the manufacture of biodiesel, sodium hydroxide is used as a catalyst for the
transesterification of methanol and triglycerides. This only works with anhydrous
sodium hydroxide, because combined with water the fat would turn into soap, which
would be tainted with methanol. NaOH is used more often than potassium hydroxide
because it is cheaper and a smaller quantity is needed.

Sodium hydroxide is also being used experimentally in a new technology to create

synthetic gasoline.

Food preparation

Food uses of sodium hydroxide include washing or chemical peeling of fruits and
vegetables, chocolate and cocoa processing, caramel coloring production, poultry
scalding, soft drink processing, and thickening ice cream. Olives are often soaked in
sodium hydroxide for softening; Pretzels and German lye rolls are glazed with a
sodium hydroxide solution before baking to make them crisp. Owing to the difficulty in
obtaining food grade sodium hydroxide in small quantities for home use, sodium
carbonate is often used in place of sodium hydroxide.

Specific foods processed with sodium hydroxide include: The Scandinavian delicacy
known as lutefisk (from lutfisk, "lye fish").Hominy is dried maize (corn) kernels
reconstituted by soaking in lye-water. These expand considerably in size and may be
further processed by frying to make corn nuts or by drying and grinding to make grits.
Nixtamal is similar, but uses calcium hydroxide instead of sodium hydroxide.

Sodium hydroxide is also the chemical that causes gelling of egg whites in the
production of Century eggs. German pretzels are poached in a boiling sodium
carbonate solution or cold sodium hydroxide solution before baking, which contributes
to their unique crust.
Lye-water is an essential ingredient in the crust of the traditional baked Chinese moon
cakes.Most yellow coloured Chinese noodles are made with lye-water but are
commonly mistaken for containing egg.Some methods of preparing olives involve
subjecting them to a lye-based brine. The Filipino dessert (kakanin) called kutsinta uses
a bit of lye water to help give the rice flour batter a jelly like consistency. A similar
process is also used in the kakanin known as pitsi-pitsi or pichi-pichi except that the
mixture uses grated cassava instead of rice flour.

3.1.1 Cleaning agent

• Sodium hydroxide is frequently used as an industrial cleaning agent
where it is often called "caustic".

• It is added to water, heated, and then used to clean process equipment,

storage tanks, etc. It can dissolve grease, oils, fats and protein based
deposits.

• It is also used for cleaning waste discharge pipes under sinks and drains
in domestic properties.

• Surfactants can be added to the sodium hydroxide solution in order to

stabilize dissolved substances and thus prevent redeposition.

• A sodium hydroxide soak solution is used as a powerful degreaser on

stainless steel and glass bakeware. It is also a common ingredient in
oven cleaners.

• A common use of sodium hydroxide is in the production of parts washer

detergents. Parts washer detergents based on sodium hydroxide are
some of the most aggressive parts washer cleaning chemicals.

• The sodium hydroxide based detergent include surfactants, rust

inhibitors and defoamers.
• A parts washer heats water and the detergent in a closed cabinet and
then sprays the heated sodium hydroxide and hot water at pressure
against dirty parts for degreasing applications.

• Sodium hydroxide used in this manner replaced many solvent based

systems in the early 1990s[citation needed] when trichloroethane was
outlawed by the Montreal Protocol.

• Water and sodium hydroxide detergent based parts washers are

considered to be an environmental improvement over the solvent based
cleaning methods.

• Hardware stores grade sodium hydroxide to be used as a type of drain

cleaners. Paint stripping with caustic soda

• Sodium hydroxide is used in the home as a type of drain opener to

unblock clogged drains, usually in the form of a dry crystal or as a thick
liquid gel.

• The alkali dissolves greases to produce water soluble products. It also

hydrolyzes the proteins such as those found in hair which may block
water pipes.

• These reactions are sped by the heat generated when sodium hydroxide
and the other chemical components of the cleaner dissolve in water.

• Such alkaline drain cleaners and their acidic versions are highly
corrosive and should be handled with great caution.

• Sodium hydroxide is used in some relaxers to straighten hair. However,

because of the high incidence and intensity of chemical burns,
manufacturers of chemical relaxers use other alkaline chemicals in
preparations available to average consumers
 • . Sodium hydroxide relaxers are still available, but they are used mostly
by professionals.

• A solution of sodium hydroxide in water was traditionally used as the

most common paint stripper on wooden objects.

• Its use has become less common, because it can damage the wood
surface, raising the grain and staining the colour.

Uses

• Sodium hydroxide has been used for detection of carbon monoxide

poisoning, with blood samples of such patients turning to a vermilion
color upon the addition of a few drops of sodium hydroxide.

• Today, carbon monoxide poisoning can be detected by CO oximetry.

Experimental

Sodium hydroxide test for flavonoids

Safety

• Chemical burns caused by sodium hydroxide solution photographed 44

hours after exposure.

• Like other corrosive acids and alkalis, drops of sodium hydroxide

solutions can decompose proteins and lipids in skin, eyes or other living
tissues via amide hydrolysis and ester hydrolysis, which consequently
causes chemical burns and may induce permanent blindness if it
contacts eyes.

• Solid alkali may also express its corrosive nature if there is water, so
protective equipment such as rubber gloves, safety clothing and eye
protection should always be used when handling the material or its
solutions.
 • Moreover, dissolution of sodium hydroxide is highly exothermic, and
the resulting heat may cause heat burns or ignite flammables. It also
produces heat when reacted with acids.

• The standard first aid measures for alkali spills on the skin is, as for
other corrosives, irrigation with large quantities of water. Washing is
continued for at least ten to fifteen minutes.

Sodium hydroxide is corrosive to several metals, like aluminium which reacts with the
alkali to produce flammable hydrogen gas on contact:

2 Al + 2 NaOH + 2 H2O → 3 H2 + 2 NaAlO2

2 Al + 6 NaOH + x H2O → 3 H2 + 2 Na3AlO3 + x H2O

2 Al + 2 NaOH + 6 H2O → 3 H2 + 2 NaAl(OH)4

Sodium hydroxide is also mildly corrosive to glass, which can cause damage to glazing
or freezing of ground glass joints. Careful storage is needed.

3.1.2 Sodium chlorate

• Sodium chlorate is an inorganic compound with the chemical formula
NaClO3. It is a white crystalline powder that is readily soluble in water.

• It is hygroscopic.

• It decomposes above 300 °C to release oxygen[4] and leave sodium

chloride. Several hundred million tons are produced annually, mainly
for applications in bleaching paper.

Synthesis

• Industrially, sodium chlorate is produced by the electrolysis of a hot

sodium chloride solution:

NaCl + 3 H2O → NaClO3 + 3 H2

 • This reaction progresses in heat (at least 70 degrees Celsius), and
controlled pH. In lower temperature or with high pH another reaction
progresses:

2 NaCl + H2O → NaClO + NaCl + H2

• The Chloralkali process is an industrial process for the electrolytic

production of sodium chlorate.It can also be synthesized by passing
chlorine gas through a solution of sodium hydroxide. It is then purified
by crystallization.

Uses

• The main commercial use for sodium chlorate is for making chlorine
dioxide (ClO2).

• The largest application of ClO2, which accounts for about 95% of the use
of chlorate, is in bleaching of pulp.

• All perchlorate compounds are produced industrially by the oxidation

of solutions of sodium chlorate by electrolysis.

• Sodium chlorate is used as a non-selective herbicide. It is considered

phytotoxic to all green plant parts.

• It can also kill through root absorption. In 2009, wholesale of sodium

chlorate weedkiller was banned in all EU countries, but consumers were
allowed to use and store the product until May 2010.

• Sodium chlorate may be used to control a variety of plants including

morning glory, canada thistle, johnson grass, bamboo, Ragwort, and St
John's wort.
 • The herbicide is mainly used on non-crop land for spot treatment and
for total vegetation control on areas including roadsides, fenceways, and
ditches. Sodium chlorate is also used as a defoliant and desiccant for:

Chemical oxygen generation

• Chemical oxygen generators, such as those in commercial aircraft,

provide emergency oxygen to passengers to protect them from drops in
cabin pressure.

• Oxygen is generated by high-temperature decomposition of sodium

chlorate.

• Heat is generated by oxidation of a small amount of iron powder mixed

with the sodium chlorate, and the reaction consumes less oxygen than is
produced.

• Barium peroxide (BaO2) is used to absorb the chlorine which is a minor

product in the decomposition.

• An ignitor charge is activated by pulling on the emergency mask.

Similarly, the Solidox welding system used pellets of sodium chlorate
mixed with combustible fibers to generate oxygen.

Toxicity in humans

• Due to its oxidative nature, sodium chlorate can be very toxic if ingested.

• The oxidative effect on hemoglobin leads to methaemoglobinformation,

which is followed by denaturation of the globin protein and a cross-
linking of erythrocyte membrane proteins with resultant damage to the
membrane enzymes.
 • This leads to increased permeability of the membrane, and severe
hemolysis. The denaturation of hemoglobin overwhelms the capacity of
the G6PD metabolic pathway.

• In addition, this enzyme is directly denatured by chlorate reducing its

activity.

Therapy with ascorbic acid and methylene blue are frequently used in the treatment of
methemoglobinemia.

• However, since methylene blue requires the presence of NADPH that

requires normal functioning of G6PD system, it is less effective than in
other conditions characterized by hemoglobin oxidation.

Formulations

• Sodium chlorate comes in dust, spray and granule formulations.

• There is a risk of fire and explosion in dry mixtures with other

substances, especially organic materials, and other herbicides, sulfur,
phosphorus, powdered metals, and strong acids.

• In particular, when mixed with sugar, it has explosive properties. If

accidentally mixed with one of these substances it should not be stored
in human dwellings.

3.2 Battery (electricity)

 Various cells and batteries (top-left to bottom-right): two AA, one D, one
handheld ham radio battery, two 9-volt(PP3), two AAA, one C, one camcorder
battery, one cordless phone battery.

 An electric battery is a device consisting of one or more electrochemical cells that

convert stored chemical energy into electrical energy.
  Each cell contains a positive terminal, or cathode, and a negative terminal, or
anode.

 Electrolytes allow ions to move between the electrodes and terminals, which
allows current to flow out of the battery to perform work.

 Primary (single-use or "disposable") batteries are used once and discarded; the
electrode materials are irreversibly changed during discharge.

 Common examples are the alkaline battery used for flashlights and a multitude
of portable devices.

 Secondary (rechargeable batteries) can be discharged and recharged multiple

times; the original composition of the electrodes can be restored by reverse
current.

 Examples include the lead-acid batteries used in vehicles and lithium ion
batteries used for portable electronics.

 Batteries come in many shapes and sizes, from miniature cells used to power
hearing aids and wristwatches to battery banks the size of rooms that provide
standby power for telephone exchanges and computer data centers.

 These wet cells used liquid electrolytes, which were prone to leakage and
spillage if not handled correctly.

 Many used glass jars to hold their components, which made them fragile. These
characteristics made wet cells unsuitable for portable appliances.

 Near the end of the nineteenth century, the invention of dry cell batteries, which
replaced the liquid electrolyte with a paste, made portable electrical devices
practical.

Principle of operation
  A voltaic cell for demonstration purposes. In this example the two half-cells are
linked by a salt bridgeseparator that permits the transfer of ions.

 Batteries convert chemical energy directly to electrical energy. A battery consists

of some number of voltaic cells.

 Each cell consists of two half-cells connected in series by a conductive electrolyte

containing anions and cations. One half-cell includes electrolyte and the negative
electrode, the electrode to which anions (negatively charged ions) migrate; the
other half-cell includes electrolyte and the positive electrode to which cations
(positively charged ions) migrate.

 Redox reactions power the battery. Cations are reduced (electrons are added) at
the cathode during charging, while anions are oxidized (electrons are removed)
at the anode during discharge.

 The electrodes do not touch each other, but are electrically connected by the
electrolyte.

 Some cells use different electrolytes for each half-cell. A separator allows ions to
flow between half-cells, but prevents mixing of the electrolytes.

 Each half-cell has an electromotive force (or emf), determined by its ability to
drive electric current from the interior to the exterior of the cell.

 The net emf of the cell is the difference between the emfs of its half-cells.

 Thus, if the electrodes have emfs and , then the net emf is ; in other words, the
net emf is the difference between the reduction potentials of the half-reactions.

Categories and types of batteries

 From top to bottom: a large 4.5-volt (3R12) battery, a D Cell, a C cell, an AA cell,
an AAA cell, an AAAA cell, anA23 battery, a 9-volt PP3 battery, and a pair of
button cells (CR2032 and LR44).
Batteries are classified into primary and secondary forms.

 Primary batteries irreversibly transform chemical energy to electrical energy.

When the supply of reactants is exhausted, energy cannot be readily restored to
the battery.

 Secondary batteries can be recharged; that is, they can have their chemical
reactions reversed by supplying electrical energy to the cell, approximately
restoring their original composition.

 Some types of primary batteries used, for example, for telegraph circuits, were
restored to operation by replacing the electrodes. Secondary batteries are not
indefinitely rechargeable due to dissipation of the active materials, loss of
electrolyte and internal corrosion.

3.2.1 Primary batteries

Primary cell

 Primary batteries, or primary cells, can produce current immediately on

assembly.

 These are most commonly used in portable devices that have low current drain,
are used only intermittently, or are used well away from an alternative power
source, such as in alarm and communication circuits where other electric power
is only intermittently available.

 Disposable primary cells cannot be reliably recharged, since the chemical

reactions are not easily reversible and active materials may not return to their
original forms.

 Battery manufacturers recommend against attempting to recharge primary cells.

  In general, these have higher energy densities than rechargeable batteries, but
disposable batteries do not fare well under high-drain applications with loads
under 75 ohms (75 Ω).

 Common types of disposable batteries include zinc–carbon batteries and alkaline

batteries.

Secondary batteries

Rechargeable battery

 Secondary batteries, also known as secondary cells, or rechargeable batteries,

must be charged before first use; they are usually assembled with active
materials in the discharged state.

 Rechargeable batteries are (re)charged by applying electric current, which

reverses the chemical reactions that occur during discharge/use. Devices to
supply the appropriate current are called chargers.

Battery cell types

 Many types of electrochemical cells have been produced, with varying chemical
processes and designs, including galvanic cells, electrolytic cells, fuel cells, flow
cells and voltaic piles.

Wet cell

 A wet cell battery has a liquid electrolyte. Other names are flooded cell, since the
liquid covers all internal parts, or vented cell, since gases produced during
operation can escape to the air.

 Wet cells were a precursor to dry cells and are commonly used as a learning tool
for electrochemistry.
  They can be built with common laboratory supplies, such asbeakers, for
demonstrations of how electrochemical cells work.

 A particular type of wet cell known as a concentration cell is important in

understanding corrosion. Wet cells may beprimary cells (non-rechargeable) or
secondary cells (rechargeable).

 Originally, all practical primary batteries such as the Daniell cell were built as
open-top glass jar wet cells. Other primary wet cells are the Leclanche cell, Grove
cell, Bunsen cell, Chromic acid cell, Clark cell, and Weston cell.

 The Leclanche cell chemistry was adapted to the first dry cells.

 Wet cells are still used in automobile batteries and in industry for standby power
for switchgear, telecommunication or large uninterruptible power supplies, but
in many places batteries with gel cells have been used instead.

 These applications commonly use lead–acid or nickel–cadmium cells.

Dry cell.

 A dry cell uses a paste electrolyte, with only enough moisture to allow current to
flow.

 Unlike a wet cell, a dry cell can operate in any orientation without spilling, as it
contains no free liquid, making it suitable for portable equipment.

 By comparison, the first wet cells were typically fragile glass containers with
lead rods hanging from the open top and needed careful handling to avoid
spillage.

 Lead–acid batteries did not achieve the safety and portability of the dry cell until
the development of the gel battery.
  A common dry cell is the zinc–carbon battery, sometimes called the dry
Leclanché cell, with a nominal voltage of 1.5 volts, the same as the alkaline
battery (since both use the same zinc–manganese dioxide combination).

 A standard dry cell comprises a zinc anode, usually in the form of a cylindrical
pot, with a carbon cathode in the form of a central rod. The electrolyte is
ammonium chloride in the form of a paste next to the zinc anode.

 The remaining space between the electrolyte and carbon cathode is taken up by
a second paste consisting of ammonium chloride and manganese dioxide, the
latter acting as a depolariser.

 In some designs, the ammonium chloride is replaced by zinc chloride.

Molten salt

 Molten salt batteries are primary or secondary batteries that use a molten salt as
electrolyte. They operate at high temperatures and must be well insulated to
retain heat.

 A reserve battery can be stored unassembled (unactivated and supplying no

power) for a long period (perhaps years).

 When the battery is needed, then it is assembled (e.g., by adding electrolyte);

once assembled, the battery is charged and ready to work.

 For example, a battery for an electronic artillery fuze might be activated by the
impact of firing a gun: The acceleration breaks a capsule of electrolyte that
activates the battery and powers the fuze's circuits.

 Reserve batteries are usually designed for a short service life (seconds or
minutes) after long storage (years). A

 water-activated battery for oceanographic instruments or military applications

becomes activated on immersion in water.
Battery cell performance

A battery's characteristics may vary over load cycle, over charge cycle, and over
lifetime due to many factors including internal chemistry, current drain, and
temperature.

Capacity and discharge

A device to check battery voltage

 A battery's capacity is the amount of electric charge it can deliver at the rated
voltage.

 The more electrode material contained in the cell the greater its capacity. A small
cell has less capacity than a larger cell with the same chemistry, although they
develop the same open-circuit voltage.

 Capacity is measured in units such as amp-hour (A•h).

 The rated capacity of a battery is usually expressed as the product of 20 hours

multiplied by the current that a new battery can consistently supply for 20 hours
at 68 °F (20 °C), while remaining above a specified terminal voltage per cell.

 For example, a battery rated at 100 A•h can deliver 5 A over a 20-hour period at
room temperature.

 The higher the discharge rate, the lower the capacity. The relationship between
current, discharge time and capacity for a lead acid battery is approximated
(over a typical range of current values) by Peukert's law:

where

 is the capacity when discharged at a rate of 1 amp.

  is the current drawn from battery (A).

 is the amount of time (in hours) that a battery can sustain.

 is a constant around 1.3.

 Batteries that are stored for a long period or that are discharged at a small
fraction of the capacity lose capacity due to the presence of generally
irreversible side reactions that consume charge carriers without producing
current.

 This phenomenon is known as internal self-discharge. Further, when batteries

are recharged, additional side reactions can occur, reducing capacity for
subsequent discharges. After enough recharges, in essence all capacity is lost and
the battery stops producing power.

 Internal energy losses and limitations on the rate that ions pass through the
electrolyte cause battery efficiency to vary. Above a minimum threshold,
discharging at a low rate delivers more of the battery's capacity than at a higher
rate.

C rate

 The C-rate is the multiple of the current over the current that a battery can
sustain for one hour.

 A rate of 1 C means that an entire 1.6Ah battery would be discharged in one

hour at a discharge current of 1.6 A. A 2C rate would mean a discharge
current of 3.2 A, over one half-hour.

Self-discharge

 Disposable batteries typically lose 8 to 20 percent of their original charge per year
when stored at room temperature (20°–30 °C).
  This is known as the "self-discharge" rate, and is due to non-current-producing
"side" chemical reactions that occur within the cell even when no load is applied.

 The rate of side reactions is reduced for batteries are stored at lower
temperatures, although some can be damaged by freezing.

 Old rechargeable batteries self-discharge more rapidly than disposable alkaline

batteries, especially nickel-based batteries; a freshly charged nickel cadmium
(NiCd) battery loses 10% of its charge in the first 24 hours, and thereafter
discharges at a rate of about 10% a month.

 However, newer low self-discharge nickel metal hydride (NiMH) batteries and
modern lithium designs display a lower self-discharge rate (but still higher than
for primary batteries).

Rechargeable batteries.

 Most nickel-based batteries are partially discharged when purchased, and must
be charged before first use.

 Newer NiMH batteries are ready to be used when purchased, and have only
15% discharge in a year.

 Some deterioration occurs on each charge–discharge cycle. Degradation usually

occurs because electrolyte migrates away from the electrodes or because active
material detaches from the electrodes.

 Low-capacity NiMH batteries (1700–2000 mA•h) can be charged some 1,000

times, whereas high-capacity NiMH batteries (above 2500 mA•h) last about 500
cycles.

 NiCd batteries tend to be rated for 1,000 cycles before their internal resistance
permanently increases beyond usable values.

Overcharging
 If a charger cannot detect when the battery is fully charged then overcharging is
likely, damaging it.

Memory effect

 NiCd cells, if used in a particular repetitive manner, may show a decrease in

capacity called "memory effect".

 The effect can be avoided with simple practices. NiMH cells, although similar in
chemistry, suffer less from memory effect.

 An analog camcorder battery [lithium ion].

Storage

 Battery life can be extended by storing the batteries at a low temperature, as in a

refrigerator or freezer, which slows the side reactions.

 Such storage can extend the life of alkaline batteries by about 5%; rechargeable
batteries can hold their charge much longer, depending upon type.

 To reach their maximum voltage, batteries must be returned to room

temperature; discharging an alkaline battery at 250 mA at 0 °C is only half as
efficient as at 20 °C. Alkaline battery manufacturers such as Duracell do not
recommend refrigerating batteries.

Battery sizes

 Primary batteries readily available to consumers range from tiny button cells
used for electric watches, to the No. 6 cell used for signal circuits or other long
duration applications.

 Secondary cells are made in very large sizes; very large batteries can power a
submarine or stabilize an electrical grid and help level out peak loads.
  A battery explosion is caused by misuse or malfunction, such as attempting to
recharge a primary (non-rechargeable) battery, or a short circuit. Car batteries are
most likely to explode when a short-circuit generates very large currents.

 Car batteries produce hydrogen, which is very explosive, when they are
overcharged (because of electrolysis of the water in the electrolyte).

 The amount of overcharging is usually very small and generates little hydrogen,
which dissipates quickly.

 However, when "jumping" a car battery, the high current can cause the rapid
release of large volumes of hydrogen, which can be ignited explosively by a
nearby spark, for example, when disconnecting a jumper cable.

 When a battery is recharged at an excessive rate, an explosive gas mixture of

hydrogen and oxygen may be produced faster than it can escape from within the
battery, leading to pressure build-up and eventual bursting of the battery case.

 In extreme cases, battery acid may spray violently from the casing and cause
injury.

 Overcharging—that is, attempting to charge a battery beyond its electrical

capacity—can also lead to a battery explosion, in addition to leakage or
irreversible damage.

 It may also cause damage to the charger or device in which the overcharged
battery is later used.

 In addition, disposing of a battery via incineration may cause an explosion as

steam builds up within the sealed case.

Leakage
Leaked alkaline battery.

 Many battery chemicals are corrosive, poisonous or both. If leakage occurs, either
spontaneously or through accident, the chemicals released may be dangerous.

 For example, disposable batteries often use a zinc "can" both as a reactant and as
the container to hold the other reagents.

 If this kind of battery is over-discharged, the reagents can emerge through the
cardboard and plastic that form the remainder of the container.

 The active chemical leakage can then damage the equipment that the batteries
power.

 For this reason, many electronic device manufacturers recommend removing the
batteries from devices that will not be used for extended periods of time.

Toxic materials

 Many types of batteries employ toxic materials such as lead, mercury, and
cadmium as an electrode or electrolyte.

 When each battery reaches end of life it must be disposed of to prevent

environmental damage. Battery are one form of electronic waste (e-waste).

 E-waste recycling services recover toxic substances, which can then be used for
new batteries.

Primary cell

 A primary cell is a battery that is designed to be used once and discarded, and
not recharged with electricity and reused like a secondary cell (rechargeable
battery).

 In general, the electrochemical reaction occurring in the cell is not reversible,

rendering the cell unrechargeable.
  As a primary cell is used, chemical reactions in the battery use up the chemicals
that generate the power; when they are gone, the battery stops producing
electricity and is useless.

 In contrast, in a secondary cell, the reaction can be reversed by running a current

into the cell with a battery charger to recharge it, regenerating the chemical
reactants. Primary cells are made in a range of standard sizes to power small
household appliances.

 In the twenty-first century, primary cells began losing market share to secondary
cells, as relative costs for the latter declined.

 Flashlight power demands were reduced by the switch from incandescent bulbs
to light-emitting diodes.

Usage and applications

 Rechargeable batteries are used for automobile starters, portable consumer

devices, light vehicles (such as motorized wheelchairs, golf carts, electric
bicycles, and electric forklifts), tools, and uninterruptible power supplies.

 Emerging applications in hybrid electric vehicles and electric vehicles are driving
the technology to reduce cost and weight and increase lifetime.

 Traditional rechargeable batteries have to be charged before their first use; newer
low self-discharge NiMH batteries hold their charge for many months, and are
typically charged at the factory to about 70% of their rated capacity before
shipping.

Charging and discharging

A solar-powered charger for rechargeable AA batteries

Battery charger

 During charging, the positive active material is oxidized, producing electrons,

and the negative material is reduced, consuming electrons.

 These electrons constitute the current flow in the external circuit.

 The electrolyte may serve as a simple buffer for internal ion flow between the
electrodes, as in lithium-ion and nickel-cadmium cells, or it may be an active
participant in the electrochemical reaction, as in lead–acid cells.

 The energy used to charge rechargeable batteries usually comes from a battery
charger using AC mains electricity, although some are equipped to use a
vehicle's 12-volt DC power outlet.

 Regardless, to store energy in a secondary cell, it has to be connected to a DC

voltage source.

 The negative terminal of the cell has to be connected to the negative terminal of
the voltage source and the positive terminal of the voltage source with the
positive terminal of the battery.

 Further, the voltage output of the source must be higher than that of the battery,
but not much higher: the greater the difference between the power source and
the battery's voltage capacity, the faster the charging process, but also the greater
the risk of overcharging and damaging the battery.

Charging of a secondary cell battery

 Battery charging and discharging rates are often discussed by referencing a "C"
rate of current.
  The C rate is that which would theoretically fully charge or discharge the battery
in one hour.

 For example, trickle charging might be performed at C/20 (or a "20 hour" rate),
while typical charging and discharging may occur at C/2 (two hours for full
capacity).

 The available capacity of electrochemical cells varies depending on the discharge

rate. Some energy is lost in the internal resistance of cell components (plates,
electrolyte, interconnections), and the rate of discharge is limited by the speed at
which chemicals in the cell can move about.

 For lead-acid cells, the relationship between time and discharge rate is described
by Peukert's law; a lead-acid cell that can no longer sustain a usable terminal
voltage at a high current may still have usable capacity, if discharged at a much
lower rate.

 Data sheets for rechargeable cells often list the discharge capacity on 8-hour or
20-hour or other stated time; cells for uninterruptible power supply systems may
be rated at 15 minute discharge.

Damage from cell reversal

 Subjecting a discharged cell to a current in the direction which tends to discharge

it further, rather than charge it, is called reverse charging.

 Generally, pushing current through a discharged cell in this way causes

undesirable and irreversible chemical reactions to occur, resulting in permanent
damage to the cell.

 Reverse charging can occur under a number of circumstances, the two most
common being:

.Depth of discharge
  Depth of discharge (DOD) is normally stated as a percentage of the nominal
ampere-hour capacity; 0% DOD means no discharge.

 Seeing as the usable capacity of a battery system depends on the rate of

discharge and the allowable voltage at the end of discharge, the depth of
discharge must be qualified to show the way it is to be measured. Due to
variations during manufacture and aging, the DOD for complete discharge can
change over time or number of charge cycles.

 Generally a rechargeable battery system will tolerate more charge/discharge

cycles if the DOD is lower on each cycle.

Active components

 The active components in a secondary cell are the chemicals that make up the
positive and negative active materials, and the electrolyte.

 The positive and negative are made up of different materials, with the positive
exhibiting a reduction potential and the negative having an oxidation potential.
The sum of these potentials is the standard cell potential or voltage.

 In primary cells the positive and negative electrodes are known as the cathode
and anode, respectively.

 Although this convention is sometimes carried through to rechargeable systems

— especially with lithium-ion cells, because of their origins in primary lithium
cells — this practice can lead to confusion.

 In rechargeable cells the positive electrode is the cathode on discharge and the
anode on charge, and vice versa for the negative electrode.

Types

 Nominal cell voltage in V.

  Graph of mass and volume energy densities of several secondary cells

 Energy density = energy/weight or energy/size, given in three different units

 Specific power = power/weight in W/kg

 Energy/consumer price in W•h/US$ (approximately)

 Self-discharge rate in %/month

 Cycle durability in number of cycles

 Time durability in years

Experimental types

 The lithium sulfur battery was developed by Sion Power in 1994. The company
claims superior energy density to other lithium technologies.

 The thin film battery (TFB) is a refinement of lithium ion technology by

Excellatron.

 The developers claim a large increase in recharge cycles to around 40,000 and
higher charge and discharge rates, at least 5 C charge rate.

 Sustained 60 C discharge and 1000C peak discharge rate and a significant

increase in specific energy, and energy density.Infinite Power Solutions makes
TFB for microelectronic applications. A smart battery has voltage monitoring
circuit built inside. Carbon foam-based lead acid battery:

 Firefly Energy developed a carbon foam-based lead acid battery with a reported
energy density of 30-40% more than their original 38 Wh/kg, with long life and
very high power density.

Theory

 The solar cell works in several steps:

  Photons in sunlight hit the solar panel and are absorbed by semiconducting
materials, such as silicon.

 Electrons are excited from their current molecular/atomic orbital. Once excited
an electron can either dissipate the energy as heat and return to its orbital or
travel through the cell until it reaches an electrode. Current flows through the
material to cancel the potential and this electricity is captured.

 An array of solar cells converts solar energy into a usable amount of direct
current (DC) electricity.

 An inverter can convert the power to alternating current (AC).

Efficiency

 The Shockley-Queisser limit for the theoretical maximum efficiency of a solar

cell.

 Semiconductors with band gap between 1 and 1.5eV, or near-infrared light, have
the greatest potential to form an efficient single-junction cell. (The efficiency
"limit" shown here can be exceeded bymultijunction solar cells.)

 Solar cell efficiency may be broken down into reflectance efficiency,

thermodynamic efficiency, charge carrier separation efficiency and conductive
efficiency. The overall efficiency is the product of these individual metrics.

 A solar cell has a voltage dependent efficiency curve, temperature coefficients

and allowable shadow angles.

 Due to the difficulty in measuring these parameters directly, other parameters

are substituted: thermodynamic efficiency, quantum efficiency, integrated
quantum efficiency, VOC ratio, and fill factor.
  Reflectance losses are a portion of quantum efficiency under "external quantum
efficiency". Recombination losses make up another portion of quantum
efficiency, VOC ratio, and fill factor.

 Resistive losses are predominantly categorized under fill factor, but also make
up minor portions of quantum efficiency, VOC ratio.

 The fill factor is the ratio of the actual maximum obtainable power to the
product of the open circuit voltage and short circuit current.

 This is a key parameter in evaluating performance. In 2009, typical commercial

solar cells had a fill factor > 0.70. Grade B cells were usually between 0.4 to 0.7.
Cells with a high fill factor have a low equivalent series resistance and a high
equivalent shunt resistance, so less of the current produced by the cell is
dissipated in internal losses.

 Single p–n junction crystalline silicon devices are now approaching the
theoretical limiting power efficiency of 33.7%, noted as the Shockley–Queisser
limit in 1961. In the extreme, with an infinite number of layers, the
corresponding limit is 86% using concentrated sunlight.

Materials

 Basic structure of a conventional solar cell and its working mechanism.

 Solar cells are typically named after the semiconducting material they are made
of. These materials must have certain characteristics in order to absorb sunlight.

 Some cells are designed to handle sunlight that reaches the Earth's surface, while
others are optimized for use in space.

 Solar cells can be made of only one single layer of light-absorbing material
(single-junction) or use multiple physical configurations (multi-junctions) to take
advantage of various absorption and charge separation mechanisms.
  Solar cells can be classified into first, second and third generation cells. The first
generation cells—also called conventional, traditional or waver-based cells—are
made of crystalline silicon, the commercially predominant PV technology, that
includes materials such as polysilicon and monocrystalline silicon. Second
generation cells are thin film solar cells, that include amorphous silicon, CdTe
and CIGS cells and are commercially significant in utility-scale photovoltaic
power stations, building integrated photovoltaics or in small stand alone devices.

Perovskite solar cells

 Perovskite solar cells are solar cells that include a perovskite-structured material
as the active layer.

 Most commonly, this is a solution-processed hybrid organic-inorganic tin or lead

halide based material. Efficincies have increased from below 10% at their first
usage in 2009 to over 17% in 2014, making them a very rapidly advancing
technology and a hot topic in the solar cell field.]

 Perovskite solar cells are also forecast to be extremely cheap to scale up, making
them a very attractive option for commercialisation.

 Light-absorbing dyes

 Dye-sensitized solar cells (DSSCs) are made of low-cost materials and do not
need elaborate manufacturing equipment, so they can be made in a DIY fashion.
In bulk it should be significantly less expensive than older solid-state cell
designs.

 DSSC's can be engineered into flexible sheets and although its conversion
efficiency is less than the best thin film cells, its price/performance ratio may be
high enough to allow them to compete with fossil fuel electrical generation.

Quantum dots
  Quantum dot solar cells (QDSCs) are based on the Gratzel cell, or dye-sensitized
solar cell architecture, but employ low band gap semiconductor nanoparticles,
fabricated with crystallite sizes small enough to form quantum dots (such as
CdS, CdSe, Sb2S3, PbS, etc.), instead of organic or organometallic dyes as light
absorbers. QD's size quantization allows for the band gap to be tuned by simply
changing particle size.

 They also have high extinction coefficients and have shown the possibility of
multiple exciton generation. In a QDSC, a mesoporous layer of titanium dioxide
nanoparticles forms the backbone of the cell, much like in a DSSC.

 This TiO2 layer can then be made photoactive by coating with semiconductor
quantum dots using chemical bath deposition, electrophoretic deposition or
successive ionic layer adsorption and reaction.

 The electrical circuit is then completed through the use of a liquid or solid redox
couple. The efficiency of QDSCs has increasedto over 5% shown for both liquid-
junction and solid state cells. In an effort to decrease production costs, the
Prashant Kamat research group demonstrated a solar paint made with TiO

Organic/polymer solar cells

 Organic solar cells and polymer solar cells are built from thin films (typically 100
nm) of organic semiconductors including polymers, such as polyphenylene
vinylene and small-molecule compounds like copper phthalocyanine (a blue or
green organic pigment) and carbon fullerenes and fullerene derivatives such as
PCBM.

 They can be processed from liquid solution, offering the possibility of a simple
roll-to-roll printing process, potentially leading to inexpensive, large scale
production.
  In addition, these cells could be beneficial for some applications where
mechanical flexibility and disposability are important.

 Current cell efficiencies are, however, very low, and practical devices are
essentially non-existent.

Adaptive cells

 Adaptive cells change their absorption/reflection characteristics depending to

respond to environmental conditions.

 An adaptive material responds to the intensity and angle of incident light. At the
part of the cell where the light is most intense, the cell surface changes from
reflective to adaptive, allowing the light to penetrate the cell.

 The other parts of the cell remain reflective increasing the retention of the
absorbed light within the cell.

Early solar-powered calculator

 Solar cells share some of the same processing and manufacturing techniques as
other semiconductor devices.

 However, the stringent requirements for cleanliness and quality control of

semiconductor fabrication are more relaxed for solar cells, lowering costs.

 Polycrystalline silicon wafers are made by wire-sawing block-cast silicon ingots

into 180 to 350 micrometer wafers.

 The wafers are usually lightly p-type-doped. A surface diffusion of n-type

dopants is performed on the front side of the wafer. This forms a p–n junction a
few hundred nanometers below the surface.
3.2.2 Fuel cell
 Demonstration model of a direct-methanol fuel cell. The actual fuel cell stack is
the layered cube shape in the center of the image.

 Scheme of a proton-conducting fuel cell

 A fuel cell is a device that converts the chemical energy from a fuel into
electricity through a chemical reaction with oxygen or another oxidizing agent.

 Hydrogen produced from the steam methane reforming of natural gas is the
most common fuel, but for greater efficiency hydrocarbons can be used directly
such as natural gas and alcohols like methanol.

 Fuel cells are different from batteries in that they require a continuous source of
fuel and oxygen/air to sustain the chemical reaction whereas in a battery the
chemicals present in the battery react with each other to generate an
electromotive force (emf).

 Fuel cells can produce electricity continuously for as long as these inputs are
supplied.

Types of fuel cells;

 Fuel cells come in many varieties; however, they all work in the same general
manner.

 They are made up of three adjacent segments: the anode, the electrolyte, and the
cathode.

 Two chemical reactions occur at the interfaces of the three different segments.
The net result of the two reactions is that fuel is consumed, water or carbon
dioxide is created, and an electric current is created, which can be used to power
electrical devices, normally referred to as the load.
  At the anode a catalyst oxidizes the fuel, usually hydrogen, turning the fuel into
a positively charged ion and a negatively charged electron.

 The electrolyte is a substance specifically designed so ions can pass through it,
but the electrons cannot.

 The freed electrons travel through a wire creating the electric current. The ions
travel through the electrolyte to the cathode.

 Once reaching the cathode, the ions are reunited with the electrons and the two
react with a third chemical, usually oxygen, to create water or carbon dioxide.

 The electrolyte substance.

 The electrolyte substance usually defines the type of fuel cell.

 The fuel that is used. The most common fuel is hydrogen.

 The anode catalyst breaks down the fuel into electrons and ions. The anode
catalyst is usually made up of very fine platinum powder.

 The cathode catalyst turns the ions into the waste chemicals like water or carbon
dioxide. The cathode catalyst is often made up of nickel but it can also be a nano
material-based catalyst.

 A typical fuel cell produces a voltage from 0.6 V to 0.7 V at full rated load.
Voltage decreases as current increases, due to several factors:

SOFC

 Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic
material called yttria-stabilized zirconia (YSZ), as the electrolyte.

 Because SOFCs are made entirely of solid materials, they are not limited to the
flat plane configuration of other types of fuel cells and are often designed as
rolled tubes.
 They require high operating temperatures(800–1000 °C) and can be run on a
variety of fuels including natural gas.

 SOFCs are unique since in those, negatively charged oxygen ions travel from the
cathode (positive side of the fuel cell) to the anode (negative side of the fuel cell)
instead of positively charged hydrogen ions travelling from the anode to the
cathode, as is the case in all other types of fuel cells.

 Oxygen gas is fed through the cathode, where it absorbs electrons to create
oxygen ions.

 The oxygen ions then travel through the electrolyte to react with hydrogen gas
at the anode.

 The reaction at the anode produces electricity and water as by-products. Carbon
dioxide may also be a by-product depending on the fuel, but the carbon
emissions from an SOFC system are less than those from a fossil fuel combustion
plant.

 The chemical reactions for the SOFC system can be expressed as follows:

Anode Reaction: 2H2 + 2O2− → 2H2O + 4e−

Cathode Reaction: O2 + 4e– → 2O2−

Overall Cell Reaction: 2H2 + O2 → 2H2O

 SOFC systems can run on fuels other than pure hydrogen gas. However, since
hydrogen is necessary for the reactions listed above, the fuel selected must
contain hydrogen atoms.

 For the fuel cell to operate, the fuel must be converted into pure hydrogen gas.
SOFCs are capable of internally reforming light hydrocarbons such as methane
(natural gas), propane and butane.
 These fuel cells are at an early stage of development. Challenges exist in SOFC
systems due to their high operating temperatures.

 One such challenge is the potential for carbon dust to build up on the anode,
which slows down the internal reforming process.

 Research to address this "carbon coking" issue at the University of Pennsylvania

has shown that the use of copper-based cermet (heat-resistant materials made of
ceramic and metal) can reduce coking and the loss of performance. Another
disadvantage of SOFC systems is slow start-up time, making SOFCs less useful
for mobile applications.

 Hydrogen-Oxygen Fuel Cell (Bacon Cell)

 The Hydrogen-Oxygen Fuel Cell was designed by Bacon in the year 1959. It was
used as a primary source of electrical energy in the Apollo space program.

 The cell consists of two porous carbon electrodes impregnated with a suitable
catalyst such as Pt, Ag, CoO, etc.

 The space between the two electrodes is filled with a concentrated solution of
KOH or NaOH which serves as an electrolyte. 2H 2 gas and O2 gas are bubbled
into the electrolyte through the porous carbon electrodes.

 Thus the overall reaction involves the combination of hydrogen gas and oxygen
gas to form water.

 The cell runs continuously until the reactant's supply is exhausted. This type of
cell operates efficiently in the temperature range 343 K to 413 K and provides a
potential of about 0.9 V.