Hydrogen

CONCEPT

First element on the periodic table, hydrogen is truly in a class by itself. It does not belong to any family of elements, and though it is a nonmetal, it appears on the left side of the periodic table with the metals. The other elements with it in Group 1 form the alkali metal family, but obviously, hydrogen does not belong with them. Indeed, if there is any element similar to hydrogen in simplicity and abundance, it is the only other one on the first row, or period, of the periodic table: helium. Together, these two elements make up 99.9% of all known matter in the entire universe, because hydrogen atoms in stars fuse to create helium. Yet whereas helium is a noble gas, and therefore chemically unreactive, hydrogen bonds with all sorts of other elements. In one such variety of bond, with carbon, hydrogen forms the backbone for a vast collection of organic molecules, known as hydrocarbons and their derivatives. Bonded with oxygen, hydrogen forms the single most important compound on Earth, and the most important complex substance other than air: water. Yet when it bonds with sulfur, it creates toxic hydrogen sulfide; and on its own, hydrogen is extremely flammable. The only element whose isotopes have names, hydrogen has long been considered as a potential source of power and transportation: once upon a time for airships, later as a component in nuclear reactions—and, perhaps in the future, as a source of abundant clean energy.

HOW IT WORKS

The Essentials

The atomic number of hydrogen is 1, meaning that it has a single proton in its nucleus. With its single electron, hydrogen is the simplest element of all. Because it is such a basic elemental building block, figures for the mass of other elements were once based on hydrogen, but the standard today is set by 12C or carbon-12, the most common isotope of carbon.
Hydrogen has two stable isotopes—forms of the element that differ in mass. The first of these, protium, is simply hydrogen in its most common form, with no neutrons in its nucleus. Protium (the name is only used to distinguish it from the other isotopes) accounts for 99.985% of all the hydrogen that appears in nature. The second stable isotope, deuterium, has one neutron, and makes up 0.015% of all hydrogen atoms. Tritium, hydrogen’s one radioactive isotope, will be discussed below.
The fact that hydrogen’s isotopes have separate names, whereas all other isotopes are designated merely by element name and mass number (for example,”carbon-12″) says something about the prominence of hydrogen as an element. Not only is its atomic number 1, but in many ways, it is like the number 1 itself—the essential piece from which all others are ultimately constructed. Indeed, nuclear fusion of hydrogen in the stars is the ultimate source for the 90-odd elements that occur in nature.
The mass of this number-one element is not, however, 1: it is 1.008 amu, reflecting the small quantities of deuterium, or “heavy hydrogen,” present in a typical sample. A gas at ordinary temperatures, hydrogen turns to a liquid at -423.2°F (-252.9°C), and to a solid at -434.°F (-259.3°C). These figures are its boiling point and melting point respectively; only the figures for helium are lower. As noted earlier, these two elements make up all but 0.01% of the known
Among the uses of tritium is in fuel for hydrogen bombs. Shown here is the Hanford plant in the state of Washington, where such fuel is produced.
Among the uses of tritium is in fuel for hydrogen bombs. Shown here is the Hanford plant in the state of Washington, where such fuel is produced.
elemental mass of the universe, and are the principal materials from which stars are formed.
Normally hydrogen is diatomic, meaning that its molecules are formed by two atoms. At the interior of a star, however, where the temperature is many millions of degrees, H2 molecules are separated into atoms, and these atoms become ionized. In other words, the electron separates from the proton, resulting in an ion with a positive charge, along with a free electron. The positive ions experience fusion—that is, their nuclei bond, releasing enormous amounts of energy as they form new elements.
Because the principal isotopic form of helium has two protons in the nucleus, it is natural that helium is the element usually formed; yet it is nonetheless true—amazing as it may seem— that all the elements found on Earth were once formed in stars. On Earth, however, hydrogen ranks ninth in its percentage of the planet’s known elemental mass: just 0.87%. In the human body, on the other hand, it is third, after oxygen and carbon, making up 10% of human elemental body mass.

Hydrogen and Bonding

Having just one electron, hydrogen can bond to other atoms in one of two ways. The first option is to combine its electron with one from the atom of a nonmetallic element to make a covalent bond, in which the two electrons are shared. Hydrogen is unusual in this regard, because most atoms conform to the octet rule, ending up with eight valence electrons. The bonding behavior of hydrogen follows the duet rule, resulting in just two electrons for bonding.
Examples of this first type of bond include water (H2O), hydrogen sulfide (H2S), and ammonia (NH3), as well as the many organic compounds formed on a hydrogen-carbon backbone. But hydrogen can form a second type of bond, in which it gains an extra electron to become the negative ion H-, or hydride. It is then able to combine with a metallic positive ion to form an ionic bond. Ionic hydrides are convenient sources of hydrogen gas: for instance, calcium hydride, or CaH2, is sold commercially, and provides a very convenient means of hydrogen generation. The hydrogen gas produced by the reaction of calcium hydride with water can be used to inflate life rafts.
The presence of hydrogen in certain types of molecules can also be a factor in intermolecular bonding. Intermolecular bonding is the attraction between molecules, as opposed to the bond-
The use of hydrogen in airships effectively ended with the crash of the Hindenburg in 1937.
The use of hydrogen in airships effectively ended with the crash of the Hindenburg in 1937.
ing within molecules, which is usually what chemists mean when they talk about “bonding.”

Hydrogen’s Early History

Because it bonds so readily with other elements, hydrogen almost never appears in pure elemental form on Earth. Yet by the late fifteenth century, chemists recognized that by adding a metal to an acid, hydrogen was produced. Only in 1766, however, did English chemist and physicist Henry Cavendish (1731-1810) recognize hydrogen as a substance distinct from all other “airs,” as gases then were called.
Seventeen years later, in 1783, French chemist Antoine Lavoisier (1743-1794) named the substance after two Greek words: hydro (water) and genes (born or formed). It was another two decades before English chemist John Dalton (1766-1844) formed his atomic theory of matter, and despite the great strides he made for science, Dalton remained convinced that hydrogen and oxygen in water formed “water atoms.” Around the same time, however, Italian physicist Amedeo Avogadro (1776-1856) clarified the distinction between atoms and molecules, though this theory would not be generally accepted until the 1850s.
Contemporary to Dalton and Avogadro was Swedish chemist Jons Berzelius (1779-1848), who developed a system of comparing the mass of various atoms in relation to hydrogen. This method remained in use for more than a century, until the discovery of neutrons, protons, and isotopes pointed the way toward a means of making more accurate determinations of atomic mass. In 1931, American chemist and physicist Harold Urey (1893-1981) made the first separation of an isotope: deuterium, from ordinary water.

REAL-LIFE APPLICATIONS

Deuterium and Tritium

Designated as 2H, deuterium is a stable isotope, whereas tritium—3H—is unstable, or radioactive. Not only do these two have names; they even have chemical symbols (D and T, respectively), as though they were elements on the periodic table. Just as hydrogen represents the most basic proton-electron combination against which other atoms are compared, these two are respectively the most basic isotope containing a single neutron, and the most basic radioisotope, or radioactive isotope.
Deuterium is sometimes called “heavy hydrogen,” and its nucleus is called a deuteron. In separating deuterium—an achievement for which he won the 1934 Nobel Prize—Urey collected a relatively large sample of liquid hydrogen: 4.2 qt (4 l). He then allowed the liquid to evaporate very slowly, predicting that the more abundant protium would evaporate more quickly than the heavier isotope. When all but 0.034 oz (1 ml) of the sample had evaporated, he submitted the remainder to a form of analysis called spectroscopy, adding a burst of energy to the atoms and then analyzing the light spectrum they emitted for evidence of differing varieties of atoms.
With an atomic mass of 2.014102 amu, deuterium is almost exactly twice as heavy as protium, which has an atomic mass of 1.007825. Its melting points and boiling points, respectively -426°F (-254°C) and -417°F (-249°C), are higher than for protium. Often, deuterium is applied as a tracer, an atom or group of atoms whose participation in a chemical, physical, or biological reaction can be easily observed.

Deuterium in war and peace

In nuclear power plants, deuterium is combined with oxygen to form “heavy water” (D2O), which likewise has higher boiling and melting points than ordinary water. Heavy water is often used in nuclear fission reactors to slow down the fission process, or the splitting of atoms. Deuterium is also present in nuclear fusion, both on the Sun and in laboratories.
During the period shortly after World War II, physicists developed a means of duplicating the thermonuclear fusion process. The result was the hydrogen bomb—more properly called a fusion bomb—whose detonating device was a compound of lithium and deuterium called lithium deuteride. Vastly more powerful than the “atomic” (that is, fission) bombs dropped by the United States over Japan (Nagaski and Hiroshima) in 1945, the hydrogen bomb greatly increased the threat of worldwide nuclear annihilation in the postwar years.
Yet the power that could destroy the world also has the potential to provide safe, abundant fusion energy from power plants—a dream as yet unrealized. Physicists studying nuclear fusion are attempting several approaches, including a process involving the fusion of two deuterons. This fusion would result in a triton, the nucleus of tritium, along with a single proton. Theoretically, the triton and deuteron would then be fused to create a helium nucleus, resulting in the production of vast amounts of energy.
tritium. Whereas deuterium has a single neutron, tritium—as its mass number of 3 indicates—has two. And just as deuterium has approximately twice the mass of protium, tritium has about three times the mass, or 3.016 amu. Its melting and boiling points are higher still than those of deuterium: thus tritium heavy water (T2O) melts at 40°F (4.5°C), as compared with 32°F (0°C) for H2O.
Tritium has a half-life (the length of time it takes for half the radioisotopes in a sample to become stable) of 12.26 years. As it decays, its nucleus emits a low-energy beta particle, which is either an electron or a subatomic particle called a positron, resulting in the creation of the helium-3 isotope. Due to the low energy levels involved, the radioactive decay of tritium poses little danger to humans. In fact, there is always a small quantity of tritium in the atmosphere, and this quantity is constantly being replenished by cosmic rays.
Like deuterium, tritium is applied in nuclear fusion, but due to its scarcity, it is usually combined with deuterium. Sometimes it is released in small quantities into the groundwater as a means of monitoring subterranean water flow. It is also used as a tracer in biochemical processes, and as an ingredient in luminous paints.

Hydrogen and Oxygen

Water

Water, of course, is the most well-known compound involving hydrogen. Nonetheless, it is worthwhile to consider the interaction between hydrogen and oxygen, the two ingredients in water, which provides an interesting illustration of chemistry in action.
Chemically bonded as water, hydrogen and oxygen can put out any type of fire except an oil or electrical fire; as separate substances, however, hydrogen and oxygen are highly flammable. In an oxyhydrogen torch, the potentially explosive reaction between the two gases is controlled by a gradual feeding process, which produces combustion instead of the more violent explosion that sometimes occurs when hydrogen and oxygen come into contact.

Hydrogen Peroxide

Aside from water, another commonly used hydrogen-oxygen compound is hydrogen peroxide, or H2O2. A colorless liquid, hydrogen peroxide is chemically unstable (not “unstable” in the way that a radioisotope is), and decomposes slowly to form water and oxygen gas. In high concentrations, it can be used as rocket fuel.
By contrast, the hydrogen peroxide used in homes as a disinfectant and bleaching agent is only a 3% solution. The formation of oxygen gas molecules causes hydrogen peroxide to bubble, and this bubbling is quite rapid when the peroxide is placed on cuts, because the enzymes in blood act as a catalyst to speed up the reaction.

Hydrogen Chloride

Another significant compound involving hydrogen is hydrogen chloride, or HCl—in other words, one hydrogen atom bonded to chlorine, a member of the halogens family. Dissolved in water, it produces hydrochloric acid, used in laboratories for analyses involving other acids. Normally, hydrogen chloride is produced by the reaction of salt with sulfuric acid, though it can also be created by direct bonding of hydrogen and chlorine at temperatures above 428°F (250°C).
Hydrogen chloride and hydrochloric acid have numerous applications in metallurgy, as well as in the manufacture of pharmaceuticals, dyes, and synthetic rubber. They are used, for instance, in making pharmaceutical hydrochlorides, water-soluble drugs that dissolve when ingested. Other applications include the production of fertilizers, synthetic silk, paint pigments, soap, and numerous other products.
Not all hydrochloric acid is produced by industry, or by chemists in laboratories. Active volcanoes, as well as waters from volcanic mountain sources, contain traces of the acid. So, too, does the human body, which generates it during digestion. However, too much hydrochloric acid in the digestive system can cause the formation of gastric ulcers.

Hydrogen Sulfide

It may not be a pleasant subject, but hydrogen— in the form of hydrogen sulfide—is also present in intestinal gas. The fact that hydrogen sulfide is an extremely malodorous substance once again illustrates the strange things that happen when elements bond: neither hydrogen nor sulfur has any smell on its own, yet together they form an extremely noxious—and toxic—substance.
Pockets of hydrogen sulfide occur in nature. If a person were to breathe the vapors for very long, it could be fatal, but usually, the foul odor keeps people away. The May 2001 National Geographic included two stories relating to such natural hydrogen-sulfide deposits, on opposite sides of the Earth, and in both cases the presence of these toxic fumes created interesting results.
In southern Mexico is a system of caves known as Villa Luz, through which run some 20 underground springs, many of them carrying large quantities of hydrogen sulfide. The National Geographic Society’s team had to enter the caves wearing gas masks, yet the area teems with strange varieties of life. Among these are fish that are red from high concentrations of hemoglobin, or red blood cells. The creatures need this extra dose of hemoglobin, necessary to move oxygen through the body, in order to survive on the scant oxygen supplies. The waters of the cave are further populated by microorganisms that oxidize the hydrogen sulfide and turn it into sulfuric acid, which dissolves the rock walls and continually enlarges the cave.
Thousands of miles away, in the Black Sea, explorers supported by a grant from the National Geographic Society examined evidence suggesting that there indeed had been a great ancient flood in the area, much like the one depicted in the Bible. In their efforts, they had an unlikely ally: hydrogen sulfide, which had formed at the bottom of the sea, and was covered by dense layers of salt water. Because the Black Sea lacks the temperature differences that cause water to circulate from the bottom upward, the hydrogen sulfide stayed at the bottom.
Under normal circumstances, the wreck of a 1,500-year-old wooden ship would not have been preserved; but because oxygen could not reach the bottom of the Black Sea—and thus wood-boring worms could not live in the toxic envi-ronment—the ship was left undisturbed. Thanks to the presence of hydrogen sulfide, explorers were able to study the ship, the first fully intact ancient shipwreck to be discovered.

Hydrocarbons

Together with carbon, hydrogen forms a huge array of organic materials known as hydrocarbons—chemical compounds whose molecules are made up of nothing but carbon and hydrogen atoms. Theoretically, there is no limit to the number of possible hydrocarbons. Not only does carbon form itself into seemingly limitless molecular shapes, but hydrogen is a particularly good partner. Because it has the smallest atom of any element on the periodic table, it can bond to one of carbon’s valence electrons without getting in the way of the others.
Hydrocarbons may either be saturated or unsaturated. A saturated hydrocarbon is one in which the carbon atom is already bonded to four other atoms, and thus cannot bond to any others. In an unsaturated hydrocarbon, however, not all the valence electrons of the carbon atom are bonded to other atoms.
Hydrogenation is a term describing any chemical reaction in which hydrogen atoms are added to carbon multiple bonds. There are many applications of hydrogenation, but one that is particularly relevant to daily life involves its use in turning unsaturated hydrocarbons into saturated ones. When treated with hydrogen gas, unsaturated fats (fats are complex substances that involve hydrocarbons bonded to other molecules) become saturated fats, which are softer and more stable, and stand up better to the heat of frying. Many foods contain hydrogenated vegetable oil; however, saturated fats have been linked with a rise in blood cholesterol levels— and with an increased risk of heart disease.

Petrochemicals and functional groups

One important variety of hydrocarbons is described under the collective heading of petrochemicals—that is, derivatives of petroleum. These include natural gas; petroleum ether, a solvent; naphtha, a solvent (for example, paint thinner); gasoline; kerosene; fuel for heating and diesel fuel; lubricating oils; petroleum jelly; paraffin wax; and pitch, or tar. A host of other organic chemicals, including various drugs, plastics, paints, adhesives, fibers, detergents, synthetic rubber, and agricultural chemicals, owe their existence to petrochemicals.
Then there are the many hydrocarbon derivatives formed by the bonding of hydrocarbons to various functional groups—broad arrays of molecule types involving other elements. Among these are alcohols—both ethanol (the alcohol in beer and other drinks) and methanol, used in adhesives, fibers, and plastics, and as a fuel. Other functional groups include aldehydes, ketones, carboxylic acids, and esters. Products of these functional groups range from aspirin to butyric acid, which is in part responsible for the smell both of rancid butter and human sweat. Hydrocarbons also form the basis for polymer plastics such as Nylon and Teflon.

Hydrogen for Transportation and Power

We have already seen that hydrogen is a component of petroleum, and that hydrogen is used in creating nuclear power—both deadly and peaceful varieties. But hydrogen has been applied in many other ways in the transportation and power industries.
There are only three gases practical for lifting a balloon: hydrogen, helium, and hot air. Each is much less dense than ordinary air, and this gives them their buoyancy. Because hydrogen is the lightest known gas and is relatively cheap to produce, it initially seemed the ideal choice, particularly for airships, which made their debut near the end of the nineteenth century.
For a few decades in the early twentieth century, airships were widely used, first in warfare and later as the equivalent of luxury liners in the skies. One of the greatest such craft was Germany’s Hindenburg, which used hydrogen to provide buoyancy. Then, on May 6, 1937, the Hindenburg caught fire while mooring at Lakehurst, New Jersey, and 36 people were killed—a tragic and dramatic event that effectively ended the use of hydrogen in airships.
Adding to the pathos of the Hindenburg crash was the voice of radio announcer Herb Morrison, whose audio report has become a classic of radio history. Morrison had come to Lake-hurst to report on the landing of the famous airship, but ended up with the biggest—and most horrifying—story of his career. As the ship burst into flames, Morrison’s voice broke, and he uttered words that have become famous: “Oh, the humanity!”
Half a century later, a hydrogen-related disaster destroyed a craft much more sophisticated than the Hindenburg, and this time, the medium of television provided an entire nation with a view of the ensuing horror. The event was the explosion of the space shuttle Challenger on January 28, 1986, and the cause was the failure of a rubber seal in the shuttle’s fuel tanks. As a result,hydrogen gas flooded out of the craft and straight into the jet of flame behind the rocket. All seven astronauts aboard were killed.

KEY TERMS

Covalent bonding: A type of chemical bonding in which two atoms share valence electrons.
Diatomic: A term describing an element that exists as molecules composed of two atoms.
Duet rule: A term describing the distribution of valence electrons when hydrogen atoms—which end up with only two valence electrons—experience chemical bonding with other atoms. Most other elements follow the octet rule.
Electrolysis: The use of an electric current to cause a chemical reaction.
Fission: A nuclear reaction involving the splitting of atoms.
Fusion: A nuclear reaction that involves the joining of atomic nuclei.
Hydrocarbon: Any chemical compound whose molecules are made up of nothing but carbon and hydrogen atoms.
Hydrogenation: A chemical reaction in which hydrogen atoms are added to carbon multiple bonds, as in a hydrocarbon.
Ion: An atom or group of atoms that has lost or gained one or more electrons, and thus has a net electrical charge.
Ionic bonding: A form of chemical bonding that results from attractions between ions with opposite electric charges. The bonding of a metal to a non-metal such as hydrogen is ionic.
Isotopes: Atoms that have an equal number of protons, and hence are of the same element, but differ in their number of neutrons. This results in a difference of mass. An isotope may either be stable or radioactive.
Nucleus: The center of an atom, a region where protons and neutrons are located, and around which electrons spin. The plural of”nucleus” is nuclei.
Octet rule: A term describing the distribution of valence electrons that takes place in chemical bonding for most elements, which end up with eight valence electrons. Hydrogen is an exception, and follows the duet rule.
Organic: At one time, chemists used the term “organic” only in reference to living things. Now the word is applied to most compounds containing carbon, with the exception of calcium carbonate (limestone) and oxides such as carbon dioxide.
Radioisotope: An isotope subject to the decay associated with radioactivity. A radioisotope is thus an unstable isotope.
Saturated: A term describing a hydrocarbon in which each carbon is already bound to four other atoms.
Tracer: An atom or group of atoms whose participation in a chemical, physical, or biological reaction can be easily observed. Radioisotopes are often used as tracers.
Unsaturated: A term describing a hydrocarbon, in which the carbons involved in a multiple bond are free to bond with other atoms.
Valence electrons: Electrons that occupy the highest principal energy level in an atom. These are the electrons involved in chemical bonding.

The future of hydrogen power

Despite the misfortunes that have occurred as a result of hydrogen’s high flammability, the element nonetheless holds out the promise of cheap, safe power. Just as it made possible the fusion, or hydrogen, bomb—which fortunately has never been dropped in wartime, but is estimated to be many hundreds of times more lethal than the fission bombs dropped on Japan—hydrogen may be the key to the harnessing of nuclear fusion, which could make possible almost unlimited power.
A number of individuals and agencies advocate another form of hydrogen power, created by the controlled burning of hydrogen in air. Not only is hydrogen an incredibly clean fuel, producing no by-products other than water vapor, it is available in vast quantities from water. In order to separate it from the oxygen atoms, electrolysis would have to be applied—and this is one of the challenges that must be addressed before hydrogen fuel can become a reality.
Electrolysis requires enormous amounts of electricity, which would have to be produced before the benefits of hydrogen fuel could be realized. Furthermore, though the burning of hydrogen could be controlled, there are the dangers associated with transporting it across country in pipelines. Nonetheless, a number of advocacy groups—some of whose Web sites are listed below—continue to promote efforts toward realizing the dream of nonpolluting, virtually limitless, fuel.

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