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Inorganic Carbon
Elemental Forms of
Carbon: Graphite,
Diamond, Coke, and
Carbon Black
Carbides: Covalent,
Ionic, and
Interstitial
The Chemistry of
Carbonates: CO32- and
HCO3-
Fullerenes
Inorganic Carbon
For more than 200 years, chemists have divided compounds into two categories.
Those that were isolated from plants or animals were called organic, while those
extracted from ores and minerals were inorganic. Organic chemistry is often defined
as the chemistry of carbon. But this definition would include calcium carbonate
(CaCO3) and graphite, which more closely resemble inorganic compounds. We will
therefore define organic chemistry as the study of compounds, such as formic acid
(HCO2H), methane (CH4), and vitamin C (C6H8O6), that contain both carbon and
hydrogen.
The chemistry of carbon is dominated by three factors.
1. Carbon forms unusually strong C-C single bonds, C=C double bonds, and carboncarbon triple bonds.
2. The electronegativity of carbon (EN = 2.55) is too small to allow carbon to form C4ions with most metals and too large for carbon to form C4+ ions when it reacts with
nonmetals. Carbon therefore forms covalent bonds with many other elements.
3. Carbon forms strong double and triple bonds with a number of other nonmetals,
including N, O, P, and S.
In some ways, the properties of graphite are like those of diamond. Both compounds
boil at 4827oC, for example. But graphite is also very different from diamond.
Diamond (3.514 g/cm3) is much denser than graphite (2.26 g/cm3). Whereas diamond
is the hardest substance known, graphite is one of the softest. Diamond is an excellent
insulator, with little or no tendency to carry an electric current. Graphite is such a
good conductor of electricity that graphite electrodes are used in electrical cells.
The physical properties of graphite can be understood from the structure of the solid
shown in the figure below.
SiC(s + 2 CO(g)
)
Covalent carbides have properties similar to those of diamond. Both SiC and diamond
are inert to chemical reactions, except at very high temperatures; both have very high
melting points; and both are among the hardest substances known. SiC was first
synthesized by Edward Acheson in 1891. Shortly thereafter, Acheson founded the
Carborundum Company to market this material. Then, as now, materials in this class
are most commonly used as abrasives.
Compounds that contain carbon and one of the more active metals are called ionic
carbides.
CaO(s) + 3 C(s)
CH + 4 OH4
The ionic carbides that formally contain the C22- ion react with water to form
acetylene, which is ignited by the heat of reaction.
C22- + 2 H2O
C 2H + 2 OH2
At one time, miners' lamps were fueled by the combustion of acetylene prepared from
the reaction of calcium carbide with water.
Interstitial carbides, such as tungsten carbide (WC), form when carbon combines
with a metal that has an intermediate electronegativity and a relatively large atomic
radius. In these compounds, the carbon atoms pack in the holes (interstices) between
planes of metal atoms. The interstitial carbides, which include TiC, ZrC, and MoC
retain the properties of metals. They act as alloys, rather than as either salts or
covalent compounds.
2 CO(g)
Ho = -110.52 kJ/mol
CO
C(s)
+ O2(g)
CO2(g)
Ho = -393.51 kJ/mol
CO2
CO(g) + H2(g)
Because this mixture of gases is formed by the reaction of charcoal or coke with water
it is often referred to as water gas. It is also known as town gas because it was once
made by towns and cities for use as a fuel. Water gas, or town gas, was a common fuel
for both home and industrial use before natural gas became readily available. The H2
burns to form water, and the CO is oxidized to CO2. Eventually, as our supply of
natural gas is depleted, it will become economical to replace natural gas with other
fuels, such as water gas, that can be produced from our abundant supply of coal.
CO and CO2 are both colorless gases. CO boils at -191.5oC, and CO2 sublimes at
-78.5oC. Although CO has no odor or taste, CO2 has a faint, pungent odor and a
distinctly acidic taste. Both are dangerous substances but at very different levels of
exposure. Air contaminated with as little as 0.002 grams of CO per liter can be fatal
because CO binds tightly to the hemoglobin and myoglobin that carry oxygen through
the blood. CO2 is not lethal until the concentration in the air approaches 15%. At that
point, it has replaced so much oxygen that a person who attempts to breathe this
atmosphere suffocates. The danger of CO2 poisoning is magnified by the fact that CO2
is roughly 1.5 times more dense than the air in our atmosphere. Thus, CO2 can
accumulate at the bottom of tanks or wells.
At one time, the amount of CO2 released to the atmosphere was not a matter for
concern because natural processes that removed CO2 from the atmosphere could
compensate for the CO2 that entered the atmosphere. The vast majority of the CO2
liberated by volcanic action, for example, was captured by calcium oxide or
magnesium oxide to form calcium carbonate or magnesium carbonate.
CaO(s) + CO2(g)
MgO(s) + CO2(g)
CaCO3(s)
MgCO3(s)
CO2(g)
CO2(aq)
H2CO3(aq)
As a result of these reactions, the sea contains about 60 times more CO2 than the
atmosphere.
Can the sea absorb more CO2 from the atmosphere, or is it near its level of saturation?
Is the rate at which the sea absorbs CO2 greater than the rate at which we are adding it
to the atmosphere? The observed increase in the concentration of CO2 in recent years
suggests pessimistic answers to these two questions. A gradual warming of the earth's
atmosphere could result from continued increases in CO2 levels, with adverse effects
on the climate and therefore the agriculture of at least the northern hemisphere.
The Chemistry of Carbonates: CO32- and HCO3Egg shells are almost pure calcium carbonate. CaCO3 can also be found in the shells
of many marine organisms and in both limestone and marble. The fact that none of
these substances dissolve in water suggests that CaCO3 is normally insoluble in water.
Calcium carbonate will dissolve in water saturated with CO2, however, because
carbonated water (or carbonic acid) reacts with calcium carbonate to form calcium
bicarbonate, which is soluble in water.
CaCO3(s) + H2CO3(aq)
Ca2+(aq) + 2 HCO3-(aq)
When water rich in carbon dioxide flows through limestone formations, part of the
limestone dissolves. If the CO2 escapes from this water, or if some of the water
evaporates, solid CaCO3 is redeposited. When this happens as water runs across the
roof of a cavern, stalactites, which hang from the roof of the cave, are formed. If the
water drops before the carbonate reprecipitates, stalagmites, which grow from the
floor of the cave, are formed.
The chemistry of carbon dioxide dissolved in water is the basis of the soft drink
industry. The first artificially carbonated beverages were introduced in Europe at the
end of the nineteenth century. Carbonated soft drinks today consist of carbonated
water, a sweetening agent (such as sugar, saccharin, or aspartame), an acid to impart a
sour or tart taste, flavoring agents, coloring agents, and preservatives. As much as 3.5
liters of gaseous CO2 dissolve in a liter of soft drink. The CO2 contributes the
characteristic bite associated with carbonated beverages.
Carbonate chemistry plays an important role in other parts of the food industry as
well. Baking soda, or bicarbonate of soda, is sodium bicarbonate, NaHCO3, a weak
base, which is added to recipes to neutralize the acidity of other ingredients. Baking
powder is a mixture of baking soda and a weak acid, such as tartaric acid or calcium
hydrogen phosphate (CaHPO4). When mixed with water, the acid reacts with the
HCO3- ion to form CO2 gas, which causes the dough or batter to rise.
HCO3-(aq) + H+(aq)
H2CO3(aq)
H2O(l) + CO2(g)
Before commercial baking powders were available, cooks obtained the same effect by
mixing roughly a teaspoon of baking soda with a cup of sour milk or buttermilk. The
acids that give sour milk and buttermilk their characteristic taste also react with the
bicarbonate ion to give CO2.
Fullerenes
In 1985 Richard Smalley and co-workers at Rice University made a uniquely stable
form of carbon by vaporizing graphite with a laser. The apparatus in which this
experiment was performed was designed to create small molecules that were clusters
of atoms. In this cluster generator, a pulse of helium gas was swept over the surface of
the graphite as it was excited with the laser. The mixture of helium and carbon atoms
that vaporized from the graphite surface cooled as the gas expanded, and molecules
with the formula C60 were formed that have a structure that has the symmetry of a
soccer-ball. Because this structure resembles the geodesic dome invented by R.
Buckminster Fuller, C60 was named buckminsterfullerene, or "buckyball" for short.
Although it was formally a new form of pure carbon, C60 seemed to be nothing more
than a laboratory curiosity until 1990, when Wolfgang Kratschmer and Konsantinos
Kostiropoulos, at the Max Planck Institute in Heidelberg, reported that this material
could be made by heating a graphite rod in an atmosphere of helium until the graphite
evaporated. Once it was known that C60 could be synthesized in large quantities,
researchers looked for, and found it, in such common sources as the flame of a sooty
candle. It has even been found in the black soot that collects on the glass screen in
front of a fireplace.
Some of the excitement chemists experienced when C60 was synthesized can be
understood by contrasting this form of pure carbon with diamond and graphite. C60 is
unique because it exists as distinct molecules, not extended arrays of atoms. Equally
important, C60 can be obtained as a pure substance, whereas the surfaces of diamond
and graphite are inevitably contaminated by hydrogen atoms that bind to the carbon
atoms on the surface.
C60 is now known to be a member of a family of compounds known as the fullerenes.
Other compounds in this family include C32, C44, C50, C58, and C70. C60
may be the most important of the fullerenes because it is the most perfectly symmetric
molecule possible, spinning in the solid at a rate of more than 100 million times per
second. Because of their symmetry, C60 molecules pack as regularly as Ping-Pong
balls. The resulting solid has unusual properties. Initially, it is as soft as graphite, but
when compressed by 30%, it becomes harder than diamond. When this pressure is
released, the solid springs back to its original volume. C60 therefore has the
remarkable property that it bounces back when shot at a metal surface at high speeds.
C60 also has the remarkable ability to form compounds in which it is an insulator, a
conductor, a semiconductor, or a superconductor. By itself, C60 is a semiconductor.
When mixed with just enough potassium to give a compound with the empirical
formula K3C60, it conducts electricity like a metal. When excess potassium is added,
this solid becomes an insulator. When K3C60 is cooled to 18 K, the result is a
superconductor. The potential of fullerene chemistry for both practical materials and
laboratory curiosities is large enough to explain why this molecule can be described as
"exocharmic"
it exudes charm.