Hydrogen Energy: Challenges and Solutions for a Cleaner Future

© Springer International Publishing AG, part of Springer Nature 2019

Bahman ZohuriHydrogen Energyhttps://doi.org/10.1007/978-3-319-93461-7_1

1. The Chemical Element Hydrogen

Bahman Zohuri¹  

(1)

Department of Electrical and Computer Engineering, Galaxy Advanced Engineering Inc., University of New Mexico, Albuquerque, NM, USA

Bahman Zohuri

This chapter provides a basic understanding in the form of a fact sheet for the element hydrogen—the oldest and cleanest element in the world—including its characteristics and physical properties, uses, sources, and other data. Hydrogen is the lightest and most abundant element in the universe; approximately 75% of the universe, but only a tiny fraction of the Earth, is comprised of hydrogen. A hydrogen atom consists of one proton and one electron and it is the first element on the periodic table. One of the most powerful gases we use is hydrogen—in our cars, buses, space launches from the Cape, and so on.

1.1 Introduction

Hydrogen is a chemical element with the symbol H and atomic number 1. With a standard atomic weight of 1.008, hydrogen is the lightest element on the periodic table. Its monatomic form (H) is the most abundant chemical substance in the universe, constituting roughly 75% of all baryonic mass. Non-remnant stars are mainly composed of hydrogen in the plasma state. The most common isotope of hydrogen, called protium (a name that is rarely used; symbol ¹H), has one proton and no neutrons (see Figs. 1.1 and 1.2).

Fig. 1.1

Hydrogen atom in the chemical periodic table

Fig. 1.2

The periodic table

By definition in physical cosmology science, recombination refers to the epoch (i.e., chronology of the universe, as shown in Fig. 1.3) in which charged electrons and protons first became bound to form electrically neutral hydrogen atoms [1]. Recombination occurred about 378,000 years after the Big Bang (at a redshift of z = 1100).

Fig. 1.3

Evolution of the (observable part) of the universe from the Big Bang (left) to the present

The word recombination is misleading, since the Big Bang theory doesn’t posit that protons and electrons had been combined before; however, the term exists for historical reasons as it was coined before the Big Bang hypothesis became the primary theory of the creation of the universe (see Fig. 1.4).

Fig. 1.4

The primary theory of the creation of the universe

Immediately after the Big Bang, the universe was a hot, dense plasma of photons, electrons, and quarks: the Quark epoch. At 10−6 s, the universe had expanded and cooled sufficiently to allow the formation of protons: the Hadron epoch. This plasma was effectively opaque to electromagnetic radiation due to Thomson scattering by free electrons, as the mean free path each photon could travel before encountering an electron was very short. This is the current state of the interior of the Sun. As the universe expanded, it also cooled. Eventually, this cooling of the universe occurred to the point that the formation of neutral hydrogen was energetically favored, and the fraction of free electrons and protons as compared with neutral hydrogen decreased to a few parts in 10,000 [1].

Recombination involves electrons binding to protons (hydrogen nuclei) to form neutral hydrogen atoms. Because direct recombination to the ground state (lowest energy) of hydrogen is very inefficient, these hydrogen atoms generally form with the electrons in a high-energy state, and the electrons quickly transition to their low-energy state by emitting photons. Two main pathways exist: either from the 2p state by emitting a Lyman-α photon—these photons will almost always be reabsorbed by another hydrogen atom in its ground state—or from the 2s state by emitting two photons, which is very slow [1].

This production of photons is known as decoupling, which leads to recombination sometimes being called photon decoupling, but recombination and photon decoupling are distinct events. Once photons decoupled from matter, they traveled freely through the universe without interacting with matter and constitute what is observed today as cosmic microwave background radiation (in that sense, the cosmic background radiation is infrared black-body radiation emitted when the universe was at a temperature of some 4000 K, redshifted by a factor of 1100 from the visible spectrum to the microwave spectrum) [1].

At standard temperature and pressure, hydrogen is a colorless, odorless, tasteless, non-toxic, non-metallic, highly combustible diatomic gas with the molecular formula H2. Since hydrogen readily forms covalent compounds with most non-metallic elements, most of the hydrogen on Earth exists in molecular forms such as water or organic compounds. Hydrogen plays a particularly important role in acid–base reactions because most of these involve the exchange of protons between soluble molecules. In ionic compounds, hydrogen can take the form of a negative charge (i.e., anion) when it is known as a hydride, or as a positively charged (i.e., cation) species denoted by the symbol H+. The hydrogen cation is written as though composed of a bare proton, but, in reality, hydrogen cations in ionic compounds are always more complex. As the only neutral atom for which the Schrödinger equation can be solved analytically, study of the energetics and bonding of the hydrogen atom has played a key role in the development of quantum mechanics.

The physical cosmology, as illustrated in Fig. 1.4, is shown in Table 1.1.

Table 1.1

Physical cosmology

Table 1.2 describes the essential facts and chemical properties of hydrogen.

Table 1.2

Essential hydrogen facts

The element of hydrogen was discovered by Henry Cavendish in 1766, hydrogen having been produced for many years before it was recognized as a distinct element. The origin of the word hydrogen is from the Greek words hydro, meaning water, and gens, meaning forming. The element was given the name hydrogen by Antoine Lavoisier in 1783.

The physical properties of hydrogen are presented in Table 1.3 (for a vial containing ultrapure hydrogen gas). Hydrogen is a colorless gas that glows violet when it is ionized, as shown in Fig. 1.5.

Table 1.3

Physical and additional properties of hydrogen [2]

CAS Chemical Abstracts Service, STP standard temperature and pressure

Fig. 1.5

Ionized hydrogen

1.2 The History of Hydrogen

Hydrogen is one of the most powerful gases we use—in our cars, buses, space launches from the Cape, and so on. Hydrogen has been found to be the best, oldest, and cleanest element, and is the first substance of the chemical periodic table (see Fig. 1.2).

Today, we are studying fuels for the future. But in science we must study the past in order to make today’s world of hydrogen fuel and hydrogen fuel cells plausible [3].

Therefore, let us look at the history of this substance that is known as hydrogen.

1776

Hydrogen was first identified as a distinct element by British scientist Henry Cavendish after he produced hydrogen gas as a result of the reaction between zinc metal and hydrochloric acid. In a demonstration to the Royal Society of London, Cavendish applied a spark to hydrogen gas, yielding water. This discovery led to his later finding that water (H2O) is made of hydrogen and oxygen.

1788

Building on the discoveries of Cavendish, French chemist Antoine Lavoisier gave hydrogen its name, which was derived from the Greek words hydro and genes, meaning water and born of.

1800

English scientists William Nicholson and Sir Anthony Carlisle discovered that applying an electric current to water produced hydrogen and oxygen gases. This process was later termed electrolysis.

1838

The fuel cell effect, combining hydrogen and oxygen gases to produce water and an electric current, was discovered by Swiss chemist Christian Friedrich Schoenbein.

1845

Sir William Grove, an English scientist and judge, demonstrated Schoenbein’s discovery on a practical scale by creating a gas battery. He earned the title Father of the Fuel Cell for his achievement.

1874

Jules Verne, an English author, prophetically examined the potential use of hydrogen as a fuel in his popular work of fiction entitled The Mysterious Island.

1889

Ludwig Mond and Charles Langer attempted to build the first fuel cell device using air and industrial coal gas. They named the device a fuel cell.

1920s

A German engineer, Rudolf Erren, converted the internal combustion engines of trucks, buses, and submarines to use hydrogen or hydrogen mixtures. British scientist and Marxist writer J.B.S. Haldane introduced the concept of renewable hydrogen in his book Daedalus or Science and the Future by proposing that there will be great power stations where during windy weather the surplus power will be used for the electrolytic decomposition of water into oxygen and hydrogen.

1937

After ten successful trans-Atlantic flights from Germany to the United States, the Hindenburg, a dirigible inflated with hydrogen gas, crashed upon landing in Lakewood, New Jersey, USA. The mystery of the crash was solved in 1997 when a study concluded that the explosion was not due to the hydrogen gas, but rather to a weather-related static electric discharge which ignited the airship’s silver-colored canvas exterior covering, which had been treated with the key ingredients of solid rocket fuel.

1958

The United States formed the National Aeronautics and Space Administration (NASA). NASA’s space program currently uses the most liquid hydrogen worldwide, primarily for rocket propulsion and as a fuel for fuel cells.

1959

Francis T. Bacon of Cambridge University in England built the first practical hydrogen–air fuel cell. The 5-kilowatt (kW) system powered a welding machine. He named his fuel cell design the Bacon Cell. Later that year, Harry Karl Ihrig, an engineer for the Allis–Chalmers Manufacturing Company, demonstrated the first fuel cell vehicle: a 20-horsepower tractor. Hydrogen fuel cells, based on Bacon’s design, have been used to generate onboard electricity, heat, and water for astronauts aboard the famous Apollo spacecraft and all subsequent space shuttle missions.

1970

Electrochemist John O’Mara Bockris coined the term hydrogen economy during a discussion at the General Motors (GM) Technical Center in Warren, Michigan, USA. He later published Energy: The Solar-Hydrogen Alternative, describing his envisioned hydrogen economy where cities in the United States could be supplied with energy derived from the Sun.

1972

The 1972 Gremlin, modified by the University of California at Los Angeles, was entered the 1972 Urban Vehicle Design Competition and won first prize for the lowest tailpipe emissions. Students converted the Gremlin’s internal combustion engine to run on hydrogen supplied from an onboard tank.

1973

The OPEC (Organization of the Petroleum Exporting Countries) oil embargo and the resulting supply shock suggested that the era of cheap petroleum had ended, and that the world needed alternative fuels. The development of hydrogen fuel cells for conventional commercial applications began.

1974

The National Science Foundation transferred the Federal Hydrogen R&D Program to the United States Department of Energy. Professor T. Nejat Veziroglu of the University of Miami, Florida, organized The Hydrogen Economy Miami Energy (THEME) conference, the first international conference held to discuss hydrogen energy. Following the conference, the scientists and engineers who had attended it formed the International Association for Hydrogen Energy (IAHE).

1974

The International Energy Agency (IEA) was established in response to global oil market disruptions. IEA activities included the research and development of hydrogen energy technologies.

1988

The Soviet Union Tupolev Design Bureau successfully converted a 164-passenger TU-154 commercial jet to operate one of the jet’s three engines on liquid hydrogen. The maiden flight lasted 21 min.

1989

The National Hydrogen Association (NHA) formed in the United States with ten members. Today, the NHA has nearly 100 members, including representatives from the automobile and aerospace industries, federal, state, and local governments, and energy providers. The International Organization for Standardization’s Technical Committee for Hydrogen Technologies was also created.

1990

The world’s first solar-powered hydrogen production plant at Solar-Wasserstoff-Bayern, a research and testing facility in southern Germany, became operational. The United States Congress passed the Spark M. Matsunaga Hydrogen, Research, Development and Demonstration Act (PL 101–566), which prescribed the formulation of a 5-year management and implementation plan for hydrogen research and development in the United States.

The Hydrogen Technical Advisory Panel (HTAP) was mandated by the Matsunaga Act to ensure consultation on and coordination of hydrogen research. Work on a methanol-fueled 10-kW proton exchange membrane (PEM) fuel cell began through a partnership including GM, Los Alamos National Laboratory, the Dow Chemical Company, and Canadian fuel cell developer, Ballard Power Systems.

1994

Daimler-Benz demonstrated its first New Electric CAR (NECAR-I) fuel cell vehicle at a press conference in Ulm, Germany.

1997

Retired NASA engineer Addison Bain challenged the belief that hydrogen caused the Hindenburg accident. The hydrogen, Bain demonstrated, did not cause the catastrophic fire but rather the combination of static electricity and highly flammable material on the skin of the airship. German car manufacturer Daimler-Benz and Ballard Power Systems announced a US$300 million research collaboration on hydrogen fuel cells for transportation.

1998

Iceland unveiled a plan to create the first hydrogen economy by 2030 with Daimler-Benz and Ballard Power Systems.

1999

The Royal Dutch/Shell Company committed to a hydrogen future by forming a hydrogen division. Europe’s first hydrogen fueling stations were opened in the German cities of Hamburg and Munich.

A consortium of Icelandic institutions, headed by the financial group New Business Venture Fund, partnered with Royal Dutch/Shell Group, Daimler Chrysler (a merger of Daimler-Benz and Chrysler), and Norsk Hydro to form the Icelandic Hydrogen and Fuel Cell Company, Ltd. to further the hydrogen economy in Iceland.

2000

Ballard Power Systems presented the world’s first production-ready PEM fuel cell for automotive applications at the Detroit Auto Show.

2003

President George W. Bush announced in his 2003 State of the Union Address a US$1.2 billion hydrogen fuel initiative to develop the technology for commercially viable hydrogen-powered fuel cells, such that the first car driven by a child born today could be powered by fuel cells.

2004

United States Energy Secretary Spencer Abraham announced that over US$350 million would be devoted to hydrogen research and vehicle demonstration projects. This appropriation represented nearly one-third of President Bush’s US$1.2 billion commitment to research in hydrogen and fuel cell technologies. The funding encompasses over 30 lead organizations and more than 100 partners selected through a competitive review process.

2004

The world’s first fuel cell-powered submarine underwent deep-water trials (German navy).

2005

Twenty-three states in the United States have hydrogen initiatives in place.

Today–2050: Future Vision

In the future, water will replace fossil fuels as the primary resource for hydrogen. Hydrogen will be distributed via national networks of hydrogen transport pipelines and fueling stations. Hydrogen energy and fuel cell power will be clean, abundant, reliable, affordable, and an integral part of all sectors of the economy in all regions of the United States.

1.3 Summary

Thus, in summary, in the early 1500s the alchemist Paracelsus noted that the bubbles given off when iron filings were added to sulfuric acid were flammable. In 1671, Robert Boyle made the same observation. Neither followed up their discovery of hydrogen, and so Henry Cavendish gets the credit. In 1766 he collected these bubbles and showed that they were different from other gases. He later showed that when hydrogen burns it forms water, thereby ending the belief that water was an element. The gas was given its name hydrogen, meaning water-former, by Antoine Lavoisier.

In 1931, Harold Urey and his colleagues at Columbia University in the United States detected a second, rarer, form of hydrogen. This has twice the mass of normal hydrogen, and they named it deuterium.

1.4 Hydrogen Sources

In nature, hydrogen can be found in volcanic gases and some natural gases as a free element, as illustrated in Fig. 1.6, which shows the volcanic eruption of Stromboli Volcano (a small island in the Tyrrhenian Sea, off the cost of Sicily in Italy), the most recent major eruption of which took place as recently as April 13, 2009.

Fig. 1.6

Volcanic eruption of Stromboli Volcano, Italy

Hydrogen is created by decomposition of hydrocarbons via heat, the action of sodium hydroxide or potassium hydroxide on aluminum electrolysis of water, steam on heated carbon, or displacement from acids by metals.

As mentioned earlier in this chapter, hydrogen is the most abundant element in the universe (Fig. 1.7). The heavier elements were formed from hydrogen or other elements that were made from hydrogen. Although approximately 75% of the universe’s elemental mass is hydrogen, the element is relatively rare on Earth.

Fig. 1.7

Ionized hydrogen within the Triangulum Galaxy

Figure 1.7, an image taken by the Hubble Space Telescope, shows a region of ionized hydrogen in the Triangulum Galaxy.

1.5 Hydrogen Isotopes

The three most stable isotypes of hydrogen occur naturally, and each have their own names (Fig. 1.8):

Fig. 1.8

The three most stable isotopes of hydrogen: protium (A = 1), deuterium (A = 2), and tritium (A = 3). A atomic number

1.

Protium (0 Neutron, Atomic Number A = 1);

2.

Deuterium (1 Neutron, Atomic Number A = 2); and

3.

Tritium (2 Neutrons, Atomic Number A = 3).

In fact, hydrogen is the only element with names for its common isotopes. Protium is the most abundant hydrogen isotope (see Fig. 1.9). H4 to H7 are extremely unstable isotopes that have been made in the laboratory but are not seen in nature. Both protium and deuterium are not radioactive. Tritium, however, decays into helium-3 through beta decay.

Fig. 1.9

Protium: hydrogen isotope

Protium is the most common isotope of the element hydrogen. It has one proton and one electron but no neutrons.

Hydrogen is the only element whose isotopes have different names that are in common use today. The H2 (or hydrogen-2) isotope is usually called deuterium (D, contains one proton, one neutron, and one electron; Fig. 1.10a), while the H3 (or hydrogen-3) isotope is usually called tritium (T, contains one proton, two neutrons, and one electron; Fig. 1.10b). The symbols D and T (instead of H2 and H3) are sometimes used for deuterium and tritium, and it should be noted that the International Union of Pure and Applied Chemistry (IUPAC) states in the 2005 Red Book that the use of D and T is very common.

Fig. 1.10

Hydrogen isotopes of deuterium (a) and tritium (b)

As mentioned earlier, H2 (atomic mass 2.01410177811(12) u), the other stable hydrogen isotope, is known as deuterium and contains one proton and one neutron in its nucleus. The nucleus of deuterium is called a deuteron. Deuterium comprises 0.0026–0.0184% (by population, not by mass) of hydrogen samples on Earth, with the lower number tending to be found in samples of hydrogen gas and the higher enrichment (0.015% or 150 ppm) typical of ocean water. Deuterium on Earth has been enriched with respect to its initial concentration in the Big Bang and the outer solar system (about 27 ppm, by atom fraction) and its concentration in older parts of the Milky Way galaxy (about 23 ppm). Presumably, the differential concentration of deuterium in the inner solar system is due to the lower volatility of deuterium gas and compounds, enriching deuterium fractions in comets and planets exposed to significant heat from the Sun over billions of years of solar system evolution [4].

Deuterium is not radioactive and does not represent a significant toxicity hazard. Water enriched in molecules that include deuterium instead of protium is called heavy water. Deuterium and its compounds are used as a non-radioactive label in chemical experiments and in solvents for 1H-NMR (hydrogen-1 nuclear magnetic resonance) spectroscopy. Heavy water is used as a neutron moderator and coolant for nuclear reactors. Deuterium is also a potential fuel for commercial nuclear fusion [4].

H3 (atomic mass 3.01604928199(23) u) is known as tritium and contains one proton and two neutrons in its nucleus. It is radioactive, decaying into helium-3 through beta decay with a half-life of 12.32 years [4]. Trace amounts of tritium occur naturally because of the interaction of cosmic rays with atmospheric gases. Tritium has also been released during nuclear weapons tests. It is used in thermonuclear fusion weapons, as a tracer in isotope geochemistry, and in specialized self-powered lighting devices.

The most common method of producing tritium is by bombarding a natural isotope of lithium, lithium-6, with neutrons in a nuclear reactor.

Tritium was once used routinely in chemical and biological labeling experiments as a radiolabel, which has become less common in recent times. D–T nuclear fusion uses tritium as its main reactant, along with deuterium, liberating energy through the loss of mass when the two nuclei collide and fuse at high temperatures.

Figure 1.11 demonstrates ionized deuterium in an Inertial Electrostatic Confinement (IEC); the characteristic pink or reddish glow displayed by ionized deuterium can be seen.

Fig. 1.11

Ionized deuterium in an Inertial Electrostatic Confinement (IEC) reactor

Note that IEC is a branch of fusion reaction research that uses an electric field to heat plasma to fusion conditions. Electric fields can work on charged particles (either ions or electrons), heating them to fusion conditions. This is typically done in a sphere, with material moving radially inward, but can also be done in a cylindrical or beam geometry. The electric field can be generated using a wire grid or a non-neutral plasma cloud [5].

Some other facts about hydrogen can be summarized here:

Hydrogen is the lightest element; hydrogen gas is so light and diffusive that uncombined hydrogen can escape from the atmosphere.

Hydrogen gas is a mixture of two molecular forms, ortho- and para-hydrogen, which differ by the spins of their electrons and nuclei. Normal hydrogen at room temperature consists of 25% para-hydrogen and 75% ortho-hydrogen. The ortho form cannot be prepared in the pure state. The two forms of hydrogen differ in energy, so their physical properties also differ.

Hydrogen gas is extremely flammable.

Hydrogen can take a negative charge (H−) or a positive charge (H+) in compounds.

Hydrogen compounds are called hydrides.

Ionized deuterium displays a characteristic reddish or pink glow.

1.6 Uses for Hydrogen

At first glance, hydrogen is the simplest element known to exist. A hydrogen atom has one proton and one electron. Hydrogen has the highest energy content of any common fuel by weight, but the lowest energy content by volume. It is the lightest element and a gas at normal temperature and pressure. Hydrogen is also the most abundant gas in the universe, and the source of all of the energy we receive from the Sun, and is also one of the most plentiful elements in the Earth’s crust. Hydrogen as a gas (H2), however, does not exist naturally on Earth; it is found only in compound form. Combined with oxygen, it forms water (H2O). Combined with carbon, it forms organic compounds such as methane (CH⁴), coal, and petroleum. It is found in all growing things—biomass.

Hydrogen is one of the most promising energy carriers for the future. It is a high efficiency, low polluting fuel that can be used for transportation, heating, and power generation in places where it is difficult to use electricity.

Hydrogen is a very important molecule with an enormous breadth and extent of application and use. It is currently being used in many industries, from chemical and refining to metallurgical, glass, and electronics. Hydrogen is primarily used as a reactant. But it is also being used as a fuel in space applications, as an O2 scavenger in heat treating of metals, and for its low viscosity and density. Current uses of hydrogen in various industries throughout the world can be seen as, due to the increased use of heavier crude oils containing higher amounts of sulfur and nitrogen and to meet stringent emission standards, the need for hydrogen is experiencing very rapid growth in the petroleum refining industry. Hence, this application is discussed in more detail in the following sections and chapters.

1.6.1 Zeppelins and Airships

Historically, hydrogen was used during World War I (WWI) as a lifting substance for Zeppelins, with Germany leading such technology to transport passengers between Germany and the United States around the 1930s as well as these Zeppelins being used as means of weaponry war machine. The most famous passenger transport Zeppelin was called the Hindenburg—it eventually burned and crashed on May 6, 1937 at Lakehurst, New Jersey, USA (Fig. 1.12).

Fig. 1.12

Hindenburg disaster at Lakehurst, New Jersey, USA

The idea of building these blimps originated with Count von Zeppelin, a retired German army officer, who created a flying weapon lighter than air, filled with hydrogen, and held together by a steel framework.

When WWI started in 1914, the German armed forces had several Zeppelins, each capable of travelling at about 85 mph and carrying up to 2 tons of bombs. With military deadlock on the Western Front, the Germans decided to use them against towns and cities in Britain. The first raid took place on the eastern coastal towns of Great Yarmouth and King’s Lynn on January19, 1915, during which they were photographed over London (Fig. 1.13). Residents reported hearing an eerie throbbing sound above them, followed shortly afterwards by the sound of explosions in the streets. This was the first time that the full horror of aerial warfare was unleashed. Although people in England claimed that aerial attacks using Zeppelins held no military advantage over other aircraft of the era, it was all about instilling terror—and that is what these aerial bombardments did.

Fig. 1.13

Zeppelin raid over London in 1915

The Zeppelins would come out of the dark - you could not see them, and it was totally random. You didn’t know if you were running towards danger or away from its.

The aim of the Zeppelins was clear—the Germans hoped to destroy morale at home and force the British Government into abandoning the war in the trenches, but the sort of chaos and panic that the Germans had wanted was not created.

However, in 20 min a Zeppelin had dropped 3000 pounds of bombs, including 91 incendiaries, which had started 40 fires, gutted buildings, and left seven people dead. Not a single shot was fired in retaliation.

While Britain celebrated victories elsewhere, the Germans stepped things up with the so-called Super Zeppelins, but Britain had found the Zeppelin’s Achilles heel—explosive bullets that could set alight the hydrogen that was floating them