Applications of Redox

Reactions
COMBUSTION AND E XPLOSIONS
As with any type of chemical reaction, combustion takes place when chemical bonds are
broken and new bonds are formed. It so happens that combustion is a particularly dramatic type of
oxidation-reduction reaction: whereas we cannot watch iron rust, combustion is a noticeable
event. Even more dramatic is combustion that takes place at a rate so rapid that it results in an
explosion.
Coal is almost pure carbon, and its combustion in air is a textbook example of oxidationreduction. Although there is far more nitrogen than oxygen in air (which is a mixture rather than a
compound), nitrogen is very unreactive at low temperatures. For this reason, it can be used to
clean empty fuel tanks, a situation in which the presence of pure oxygen is extremely dangerous. In
any case, when a substance burns, it is reacting with the oxygen in air.
As one might expect from what has already been said about oxidation-reduction, the
oxygen is reduced while the carbon is oxidized. In terms of oxidation numbers, the oxidation
number ofcarbon jumps from 0 to 4, while that of oxygen is reduced to 2. As they burn, these two
form carbon dioxide or CO 2 , in which the two 2 charges of the oxygen atoms cancel out the +4
charge of the carbon atom to yield a compound that is electrically neutral.

COMBUSTION IN HUMAN EXPERIENCE.

Combustion has been a significant part of human life ever since our prehistoric ancestors
learned how to harness the power of fire to cook food and light their caves. We tend to think of
premodern timesto use the memorable title of a book by American historian William
Manchester, about the middle Agesas A World Lit Only by Fire. In fact, our modern age is even
more combustion-driven than that of our forebears.
For centuries, burning animal fatin torches, lamps, and eventually in candlesprovided
light for humans. Wood fires supplied warmth, as well as a means to cook meals. These were the
main uses of combustion, aside from the occasional use of fire in warfare or for other purposes
(including that ghastly medieval form of execution, burning at the stake). One notable military
application, incidentally, was "Greek fire," created by the Byzantines in the seventh century A.D. A
mixture of petroleum, potassium nitrate, and possibly quicklime, Greek fire could burn on water,
and was used in naval battles to destroy enemy ships.

For the most part, however, the range of activities to which combustion could be applied
was fairly narrow until the development of the steam engine in the period from the late seventeenth
century to the early nineteenth century. The steam engine applied the combustion of coal to the
production of heat for boiling water, which in turn provided the power to run machinery. By the
beginning of the twentieth century, combustion had found a new application in the internal
combustion engine, used to power automobiles.

EXPLOSIONS AND EXPLOSIVES

An internal combustion engine does not simply burn fuel; rather, by the combined action of
the fuel injectors (in a modern vehicle), in concert with the pistons, cylinders, and spark plugs, it
actually produces small explosions in the molecules of gasoline. These produce the output of
power necessary to turn the crankshaft, and ultimately the wheels.
An explosion, in simple terms, is a sped-up form of combustion. The first explosives were
invented by the Chinese during the Middle Ages, and these included not only fireworks and
explosive rockets, but gunpowder. Ironically, however, China rejected the use of gunpowder in
warfare for many centuries, while Europeans took to it with enthusiasm. Needless to say,
Europeans' possession of firearms aided their conquest of the Americas, as well as much of Africa,
Asia, and the Pacific, during the period from about 1500 to 1900.
The late nineteenth and early twentieth centurys saw the development of new explosives,
such as TNT or trinitrotoluene, a hydrocarbon. Then in the mid-twentieth century came the most
fearsome explosive of all: the nuclear bomb. A nuclear explosion is not itself the result of an
oxidation-reduction reaction, but of something much more complexeither the splitting of atoms
(fission) or the forcing together of atomic nuclei (fusion).
Nuclear bombs release far more energy than any ordinary explosive, but the resulting blast
also causes plenty of ordinary combustion. When the United States dropped atomic bombs on the
Japanese cities of Hiroshima and Nagasaki in August 1945, those cities suffered not only the effects
of the immediate blast, but also massive fires resulting from the explosion itself.

FUELING THE SPACE SHUTTLE

Oxidation-reduction reactions also fuel the most advanced form of transportationknown
today, the space shuttle. The actual orbiter vehicle is relatively small compared to its external
power apparatus, which consists of two solid rocket boosters on either side, along with an external
fuel tank.

Inside the solid rocket boosters are ammonium perchlorate (NH 4 ClO 4 ) and powdered
aluminum, which undergo an oxidation-reduction reaction that gives the shuttle enormous
amounts of extra thrust. As for the larger single external fuel tank, this contains the gases that
power the rocket: hydrogen and oxygen.
Because these two are extremely explosive, they must be kept in separate compartments.
When they react, they form water, of course, but in doing so, they also release vast quantities of
energy. The chemical equation for this is: 2H 2 + O 2 2H 2 O + energy.
On January 28, 1986, something went terribly wrong with this arrangement on the space
shuttle Challenger. Cold weather had fatigued the O-rings that sealed the hydrogen and oxygen
compartments, and the gases fed straight into the flames behind the shuttle itself. This produced a
powerful and uncontrolled oxidation-reduction reaction, an explosion that took the lives of all
seven astronauts aboard the shuttle.

THE ENVIRONMENT AND H UMAN HEALTH

Combustion, though it can do much good, can also do much harm. This goes beyond the
obvious: by burning fossil fuels or hydrocarbons, excess carbon (in the form of carbon dioxide and
carbon monoxide) is released to the atmosphere, with a damaging effect on the environment.
In fact, oxidation-reduction reactions are intimately connected with the functioning of the
natural environment. For example, photosynthesis, the conversion of light to chemical energy by
plants, is a form of oxidation-reduction reaction that produces two essentials of human life: oxygen
and carbohydrates. Likewise cellular respiration, which along with photosynthesis is discussed in
the Carbon essay, is an oxidation-reduction reaction in which living things break down molecules
of food to produce energy, carbon dioxide, and water.

Enzymes in the human body regulate oxidation-reduction reactions. These complex

proteins, of which several hundred are known, act as catalysts, speeding up chemical processes in
the body. Oxidation-reduction reactions also take place in the metabolism of food for energy, with
substances in the food broken down into components the body can use.

OXIDATION: SPOILING AND AGING.

At the same time, oxidation-reduction reactions are responsible for the spoiling of food, the
culprit here being the oxidation portion of the reaction. To prevent spoilage, manufacturers of food
items often add preservatives, which act as reducing agents.

Oxidation may also be linked with the effects of aging in humans, as well as with other
conditions such as cancer, hardening of the arteries, and rheumatoid arthritis. It appears that
oxygen molecules and other oxidizing agents, always hungry for electrons, extract these from the
membranes in human cells. Over time, this can cause a gradual breakdown in the body's immune
system.
To forestall the effects of oxidation, some doctors and scientists recommend antioxidants
natural reducing agents such as vitamin C and vitamin E. The vitamin C in lemon juice can be used
to prevent oxidizing on the cut surface of an apple, to keep it from turning brown. Perhaps, some
experts maintain, natural reducing agents can also slow the pace of oxidation in the human body.

FORMING A NEW SURFACE ON METAL

Clearly, oxidization can have a corrosive effect, and nowhere is this more obvious than in
the corrosion of metals by exposure to oxidizing agentsprimarily oxygen itself. Most metals react
with O 2 , and might corrode so quickly that they become useless, were it not for the formation of a
protective coatingan oxide.
Iron forms an oxide, commonly known as rust, but this in fact does little to protect it from
corrosion, because the oxide tends to flake off, exposing fresh surfaces to further oxidation. Every
year, businesses and governments devote millions of dollars to protecting iron and steel from
oxidation by means of painting and other measures, such as galvanizing with zinc. In fact,
oxidation-reduction reactions virtually define the world of iron. Found naturally only in ores, the
element is purified by heating the ore with coke (impure carbon) in the presence of oxygen, such
that the coke reduces the iron.
COINAGE METALS
Copper, as we have seen, responds to oxidation by corroding in a different way: not by
rusting, but by changing color. A similar effect occurs in silver, which tarnishes, forming a surface
of silver sulfide, or Ag 2 S. Copper and silver are two of the "coinage metals," so named because
they have often been used to mint coins. They have been used for this purpose not only because of
their beauty, but also due to their relative resistance to corrosion. This resistance has, in fact,
earned them the nickname "noble metals."
The third member of this mini-family is gold, which is virtually noncorrosive. Wonderful as
gold is in this respect, however, no one is likely to use it as a roofing material, or for any such largescale application involving its resistance to oxidation. Aside from the obvious expense, gold is soft,
and not very good for structural uses, even if it were much cheaper. Yet there is such a "wonder
metal": one that experiences virtually no corrosion, is cheap, and strong enough in alloys to be
used for structural purposes. Its name is aluminum.

ALUMINUM
There was a time, in fact, when aluminum was even more expensive than gold. When the
French emperor Napoleon III wanted to impress a dinner guest, he arranged for the person to be
served with aluminum utensils, while less distinguished personages had to settle for "ordinary"
gold and silver.
In 1855, aluminum sold for $100,000 a pound, whereas in 1990, the going rate was about
$0.74. Demand did not go downin fact, it increased exponentiallybut rather, supply increased,
thanks to the development of an inexpensive aluminum-reduction process. Two men, one
American and one French, discovered this process at the same time: interestingly, their years of
birth and death were the same.
Aluminum was once a precious metal because it proved extremely difficult to separate from
oxygen. The Hall-Heroult process overcame the problem by applying electrolysisthe use of an
electric current to produce a chemical changeas a way of reducing Al 3+ ions (which have a high
affinity for oxygen) to neutral aluminum atoms. In the United States today, 4.5% of the total
electricity output is used for the production of aluminum through electrolysis.

The foregoing statistic is staggering, considering just how much electricity Americans use,
and it indicates the importance of this once-precious metal. Actually, aluminum oxidizes just like
any other metaland does so quite quickly, as a matter of fact, by forming a coating of aluminum
oxide (Al 2 O 3 ). But unlike rust, the aluminum oxide is invisible, and acts as a protective coating.
Chromium, nickel, and tin react to oxygen in a similar way, but these are not as inexpensive as
aluminum.

ELECTROCHEMISTRY AND BATTERIES

Electrochemistry is the study of the relationship between chemical and electrical energy.
Among its applications is the creation of batteries, which use oxidation-reduction reactions to
produce an electric current.
A basic battery can be pictured schematically as two beakers of solution connected by a
wire. In one solution is the oxidizing agent; in the other, a reducing agent. The wire allows electrons
to pass back and forth between the two solutions, but to ensure that the flow goes both ways, the
two solutions are also connected by a "salt bridge." The salt bridge contains a gel or solution that
permits ions to pass back and forth, but a porous membrane prevents the solutions from actually
mixing.
In the lead storage battery of an automobile, lead itself is the reducing agent, while lead (IV)
oxide (PbO 2 ) acts as the oxidizing agent. A highly efficient type of battery, able to with stand wide

extremes in temperature, the lead storage battery has been in use since 1915. Along the way,
features have been altered, but the basic principles have remaineda testament to the soundness
of its original design.
The batteries people use for powering all kinds of portable appliances, from flashlights to
boom boxes, are called dry cell batteries. In contrast to the model described above, using
solutions, a dry cell (as its name implies) involves no liquid components. Instead, it utilizes various
elements in a range of combinations, including zinc, magnesium, mercury, silver, nickel, and
cadmium. The last two are applied in the nickel-cadmium battery, which is particularly useful
because it can be recharged over and over again by an external current. The current turns the
products of the chemical reactions in the battery back into reactants.