Hydrogen

This article is about the chemical element. For other uses, see Hydrogen (disambiguation).

Hydrogen, ₁H

Purple glow in its plasma state
Hydrogen
Appearance	Colorless gas
Standard atomic weight Ar°(H)
	[1.00784, 1.00811] [1] 1.0080±0.0002 (abridged) [2]
Hydrogen in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson – ↑ H ↓ Li (none) ← hydrogen → helium
Atomic number (Z)	1
Group	group 1: hydrogen and alkali metals
Period	period 1
Block	s-block
Electron configuration	1s1
Electrons per shell	1
Physical properties
Phase at  STP	gas
Melting point	(H2) 13.99  K ​(−259.16 °C,​−434.49 °F)
Boiling point	(H2) 20.271 K​(−252.879 °C,​−423.182 °F)
Density (at STP)	0.08988 g/L
when liquid (at  m.p.)	0.07 g/cm3(solid: 0.0763 g/cm3) [3]
when liquid (at  b.p.)	0.07099 g/cm3
Triple point	13.8033 K,​7.041 kPa
Critical point	32.938 K, 1.2858 MPa
Heat of fusion	(H2) 0.117  kJ/mol
Heat of vaporization	(H2) 0.904 kJ/mol
Molar heat capacity	(H2) 28.836 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 15 20
Atomic properties
Oxidation states	common: −1, +1
Electronegativity	Pauling scale: 2.20
Ionization energies	1st: 1312.0 kJ/mol
Covalent radius	31±5  pm
Van der Waals radius	120 pm
Other properties
Natural occurrence	primordial
Crystal structure	​ hexagonal (hP4)
Lattice constants	a = 378.97 pm c = 618.31 pm (at triple point) [4]
Thermal conductivity	0.1805 W/(m⋅K)
Magnetic ordering	diamagnetic [5]
Molar magnetic susceptibility	−3.98×10−6 cm3/mol(298 K) [6]
Speed of sound	1310 m/s (gas, 27 °C)
CAS Number	12385-13-6 1333-74-0 (H2)
History
Discovery and first isolation	Robert Boyle (1671)
Named by	Antoine Lavoisier [7] [8] (1783)
Recognized as an element by	Henry Cavendish [9] [10] (1766)
Isotopes of hydrogen v e
Main isotopes Decay abun­dance half-life (t1/2) mode pro­duct 1H 99.9855% stable 2H 0.0145% stable 3H trace 12.32 y β− 3He
Category: Hydrogen view talk edit | references

Hydrogen is a chemical element; it has symbol H and atomic number 1. It is the lightest element and, at standard conditions, is a gas of diatomic molecules with the formula H₂, sometimes called dihydrogen, ^[11] hydrogen gas, molecular hydrogen, or simply hydrogen. It is colorless, odorless, ^[12] non-toxic, and highly combustible. Constituting about 75% of all normal matter, hydrogen is the most abundant chemical element in the universe. ^[13] Stars, including the Sun, mainly consist of hydrogen in a plasma state, while on Earth, hydrogen is found in water, organic compounds, as dihydrogen, and in other molecular forms. The most common isotope of hydrogen (protium, ¹H) consists of one proton, one electron, and no neutrons.

In the early universe, the formation of hydrogen's protons occurred in the first second after the Big Bang; neutral hydrogen atoms only formed about 370,000 years later during the recombination epoch as the universe expanded and plasma had cooled enough for electrons to remain bound to protons. ^[14] Hydrogen gas was first produced artificially in the early 16th century by the reaction of acids with metals. Henry Cavendish, in 1766–81, identified hydrogen gas as a distinct substance ^[15] and discovered its property of producing water when burned; hence its name means "water-former" in Greek. Understanding the colors of light absorbed and emitted by hydrogen was a crucial part of developing quantum mechanics.

Hydrogen, typically nonmetallic except under extreme pressure, readily forms covalent bonds with most nonmetals, contributing to the formation of compounds like water and various organic substances. Its role is crucial in acid-base reactions, which mainly involve proton exchange among soluble molecules. In ionic compounds, hydrogen can take the form of either a negatively charged anion, where it is known as hydride, or as a positively charged cation, H⁺, called a proton. Although tightly bonded to water molecules, protons strongly affect the behavior of aqueous solutions, as reflected in the importance of pH. Hydride on the other hand, is rarely observed because it tends to deprotonate solvents, yielding H₂.

Industrial hydrogen production occurs through steam reforming of natural gas. The more familiar electrolysis of water is uncommon because it is energy-intensive, i.e. expensive. ^{[16] [17]} Its main industrial uses include fossil fuel processing, such as hydrocracking and hydrodesulfurization. Ammonia production also is a major consumer of hydrogen. Fuel cells for electricity generation from hydrogen is rapidly emerging. ^[18]

Properties

Combustion

Combustion of hydrogen with the oxygen in the air. When the bottom cap is removed, allowing air to enter at the bottom, the hydrogen in the container rises out of top and burns as it mixes with the air.

Space Shuttle Main Engine burning hydrogen with oxygen, produces a nearly invisible flame at full thrust.

Hydrogen gas is highly flammable:

2 H₂(g) + O₂(g) → 2 H₂O(l) (572 kJ/2 mol = 286 kJ/mol = 141.865 MJ/kg) ^{[note 1]}

Enthalpy of combustion: −286 kJ/mol. ^[19]

Hydrogen gas forms explosive mixtures with air in concentrations from 4–74% ^[20] and with chlorine at 5–95%. The hydrogen autoignition temperature, the temperature of spontaneous ignition in air, is 500 °C (932 °F). ^[21]

Flame

Pure hydrogen-oxygen flames emit ultraviolet light and with high oxygen mix are nearly invisible to the naked eye, as illustrated by the faint plume of the Space Shuttle Main Engine, compared to the highly visible plume of a Space Shuttle Solid Rocket Booster, which uses an ammonium perchlorate composite. The detection of a burning hydrogen leak, may require a flame detector; such leaks can be very dangerous. Hydrogen flames in other conditions are blue, resembling blue natural gas flames. ^[22] The destruction of the Hindenburg airship was a notorious example of hydrogen combustion and the cause is still debated. The visible flames in the photographs were the result of carbon compounds in the airship skin burning. ^[23]

Electron energy levels

Main article: Hydrogen atom

A depiction of a hydrogen atom with size of central proton shown, and the atomic diameter shown as about twice the Bohr model radius (image not to scale)

The ground state energy level of the electron in a hydrogen atom is −13.6  eV, ^[24] equivalent to an ultraviolet photon of roughly 91 nm wavelength. ^[25] The energy levels of hydrogen are referred to by consecutive quantum numbers, with ${\displaystyle n=1}$ being the ground state. The hydrogen spectral series corresponds to emission of light due to transitions from higher to lower energy levels. ^{[26] : 105}

The energy levels of hydrogen can be calculated fairly accurately using the Bohr model of the atom, in which the electron "orbits" the proton, like how Earth orbits the Sun. However, the electron and proton are held together by electrostatic attraction, while planets and celestial objects are held by gravity. Due to the discretization of angular momentum postulated in early quantum mechanics by Bohr, the electron in the Bohr model can only occupy certain allowed distances from the proton, and therefore only certain allowed energies. ^[27]

An accurate description of the hydrogen atom comes from a quantum analysis that uses the Schrödinger equation, Dirac equation or Feynman path integral formulation to calculate the probability density of the electron around the proton. ^[28] The most complex formulas include the small effects of special relativity and vacuum polarization. In the quantum mechanical treatment, the electron in a ground state hydrogen atom has no angular momentum—illustrating how the "planetary orbit" differs from electron motion.^{[ citation needed ]}

Spin isomers

Main article: Spin isomers of hydrogen

Molecular H₂ exists as two nuclear isomers that differ in the spin states of their nuclei. ^[29] In the orthohydrogen form, the spins of the two nuclei are parallel, forming a spin triplet state having a total molecular spin ${\displaystyle S=1}$; in the parahydrogen form the spins are antiparallel and form a spin singlet state having spin ${\displaystyle S=0}$. The equilibrium ratio of ortho- to para-hydrogen depends on temperature. At room temperature or warmer, equilibrium hydrogen gas contains about 25% of the para form and 75% of the ortho form. ^[30] The ortho form is an excited state, having higher energy than the para form by 1.455 kJ/mol, ^[31] and it converts to the para form over the course of several minutes when cooled to low temperature. ^[32] The thermal properties of these isomers differ because each has distinct rotational quantum states. ^[33]

The ortho-to-para ratio in H₂ is an important consideration in the liquefaction and storage of liquid hydrogen: the conversion from ortho to para is exothermic and produces sufficient heat to evaporate most of the liquid if not converted first to parahydrogen during the cooling process. ^[34] Catalysts for the ortho-para interconversion, such as ferric oxide and activated carbon compounds, are used during hydrogen cooling to avoid this loss of liquid. ^[35]

Phases

Hydrogen gas is colorless and transparent, here contained in a glass ampoule.

Phase diagram of hydrogen. The temperature and pressure scales are logarithmic, so one unit corresponds to a 10× change. The left edge corresponds to 10 Pa, or about one atmosphere.

Liquid hydrogen can exist at temperatures below hydrogen's critical point of 33  K. ^[36] However, for it to be in a fully liquid state at atmospheric pressure, H₂ needs to be cooled to 20.28 K (−252.87 °C; −423.17 °F). Hydrogen was liquefied by James Dewar in 1898 by using regenerative cooling and his invention, the vacuum flask. Liquid hydrogen is a common rocket propellant, and it can also be used as the fuel for an internal combustion engine or fuel cell.^{[ citation needed ]}

Solid hydrogen can be made at standard pressure, by decreasing the temperature below hydrogen's melting point of 14.01 K (−259.14 °C; −434.45 °F). It was collected for the first time by James Dewar in 1899.^{[ citation needed ]} Multiple distinct solid phases exist, known as Phase I through Phase V, each exhibiting a characteristic molecular arrangement. ^[37] Liquid and solid phases can exist in combination at the triple point, a substance known as slush hydrogen. ^[38]

Metallic hydrogen, a phase obtained at extremely high pressures (in excess of 400 gigapascals (3,900,000 atm; 58,000,000 psi)), is an electrical conductor. It is believed to exist deep within giant planets like Jupiter. ^{[37] [39]}

When ionized, hydrogen becomes a plasma. This is the form in which hydrogen exists within stars.

Isotopes

Main article: Isotopes of hydrogen

The three naturally-occurring isotopes of hydrogen: hydrogen-1 (protium), hydrogen-2 (deuterium), and hydrogen-3 (tritium)

Hydrogen discharge (spectrum) tube

Deuterium discharge (spectrum) tube

Hydrogen has three naturally occurring isotopes, denoted ¹
H, ²
H and ³
H. Other, highly unstable nuclei (⁴
H to ⁷
H) have been synthesized in the laboratory but not observed in nature. ^{[40] [41]}

• ¹
  H is the most common hydrogen isotope, with an abundance of >99.98%. Because the nucleus of this isotope consists of only a single proton, it is given the descriptive but rarely used formal name protium. ^[42] It is the only stable isotope with no neutrons; see diproton for a discussion of why others do not exist.
• ²
  H, the other stable hydrogen isotope, is known as deuterium and contains one proton and one neutron in the nucleus. Nearly all deuterium in the universe is thought to have been produced at the time of the Big Bang, and has endured since then. Deuterium is not radioactive, and is not a significant toxicity hazard. Water enriched in molecules that include deuterium instead of normal hydrogen is called heavy water. Deuterium and its compounds are used as a non-radioactive label in chemical experiments and in solvents for ¹
  H-NMR spectroscopy. ^[43] Heavy water is used as a neutron moderator and coolant for nuclear reactors. Deuterium is also a potential fuel for commercial nuclear fusion. ^[44]
• ³
  H 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. ^[45] It is radioactive enough to be used in luminous paint to enhance the visibility of data displays, such as for painting the hands and dial-markers of watches. The watch glass prevents the small amount of radiation from escaping the case. ^[46] Small amounts of tritium are produced naturally by cosmic rays striking atmospheric gases; tritium has also been released in nuclear weapons tests. ^[47] It is used in nuclear fusion, ^[48] as a tracer in isotope geochemistry, ^[49] and in specialized self-powered lighting devices. ^[50] Tritium has also been used in chemical and biological labeling experiments as a radiolabel. ^[51]

Unique among the elements, distinct names are assigned to its isotopes in common use. During the early study of radioactivity, heavy radioisotopes were given their own names, but these are mostly no longer used. The symbols D and T (instead of ²
H and ³
H) are sometimes used for deuterium and tritium, but the symbol P was already used for phosphorus and thus was not available for protium. ^[52] In its nomenclatural guidelines, the International Union of Pure and Applied Chemistry (IUPAC) allows any of D, T, ²
H, and ³
H to be used, though ²
H and ³
H are preferred. ^[53]

The exotic atom muonium (symbol Mu), composed of an antimuon and an electron, can also be considered a light radioisotope of hydrogen. ^[54] Because muons decay with lifetime 2.2  µs , muonium is too unstable for observable chemistry. ^[55] Nevertheless, muonium compounds are important test cases for quantum simulation, due to the mass difference between the antimuon and the proton, ^[56] and IUPAC nomenclature incorporates such hypothetical compounds as muonium chloride (MuCl) and sodium muonide (NaMu), analogous to hydrogen chloride and sodium hydride respectively. ^[57]

Antihydrogen (
H
) is the antimatter counterpart to hydrogen. It consists of an antiproton with a positron. Antihydrogen is the only type of antimatter atom to have been produced as of 2015 ^[update] . ^{[58] [59]}

Thermal and physical properties

Table of thermal and physical properties of hydrogen (H₂) at atmospheric pressure: ^{[60] [61]}

Temperature (K)	Density (kg/m^3)	Specific heat (kJ/kg K)	Dynamic viscosity (kg/m s)	Kinematic viscosity (m^2/s)	Thermal conductivity (W/m K)	Thermal diffusivity (m^2/s)	Prandtl Number
100	0.24255	11.23	4.21E-06	1.74E-05	6.70E-02	2.46E-05	0.707
150	0.16371	12.602	5.60E-06	3.42E-05	0.0981	4.75E-05	0.718
200	0.1227	13.54	6.81E-06	5.55E-05	0.1282	7.72E-05	0.719
250	0.09819	14.059	7.92E-06	8.06E-05	0.1561	1.13E-04	0.713
300	0.08185	14.314	8.96E-06	1.10E-04	0.182	1.55E-04	0.706
350	0.07016	14.436	9.95E-06	1.42E-04	0.206	2.03E-04	0.697
400	0.06135	14.491	1.09E-05	1.77E-04	0.228	2.57E-04	0.69
450	0.05462	14.499	1.18E-05	2.16E-04	0.251	3.16E-04	0.682
500	0.04918	14.507	1.26E-05	2.57E-04	0.272	3.82E-04	0.675
550	0.04469	14.532	1.35E-05	3.02E-04	0.292	4.52E-04	0.668
600	0.04085	14.537	1.43E-05	3.50E-04	0.315	5.31E-04	0.664
700	0.03492	14.574	1.59E-05	4.55E-04	0.351	6.90E-04	0.659
800	0.0306	14.675	1.74E-05	5.69E-04	0.384	8.56E-04	0.664
900	0.02723	14.821	1.88E-05	6.90E-04	0.412	1.02E-03	0.676
1000	0.02424	14.99	2.01E-05	8.30E-04	0.448	1.23E-03	0.673
1100	0.02204	15.17	2.13E-05	9.66E-04	0.488	1.46E-03	0.662
1200	0.0202	15.37	2.26E-05	1.12E-03	0.528	1.70E-03	0.659
1300	0.01865	15.59	2.39E-05	1.28E-03	0.568	1.96E-03	0.655
1400	0.01732	15.81	2.51E-05	1.45E-03	0.61	2.23E-03	0.65
1500	0.01616	16.02	2.63E-05	1.63E-03	0.655	2.53E-03	0.643
1600	0.0152	16.28	2.74E-05	1.80E-03	0.697	2.82E-03	0.639
1700	0.0143	16.58	2.85E-05	1.99E-03	0.742	3.13E-03	0.637
1800	0.0135	16.96	2.96E-05	2.19E-03	0.786	3.44E-03	0.639
1900	0.0128	17.49	3.07E-05	2.40E-03	0.835	3.73E-03	0.643
2000	0.0121	18.25	3.18E-05	2.63E-03	0.878	3.98E-03	0.661

History

Main article: Timeline of hydrogen technologies

18th century

Robert Boyle, who discovered the reaction between iron filings and dilute acids

In 1671, Irish scientist Robert Boyle discovered and described the reaction between iron filings and dilute acids, which results in the production of hydrogen gas. ^{[62] [63]} Boyle did not note that the gas was inflammable, but hydrogen would play a key role in overturning the phlogiston theory of combustion. ^[64]

In 1766, Henry Cavendish was the first to recognize hydrogen gas as a discrete substance, by naming the gas from a metal-acid reaction "inflammable air". He speculated that "inflammable air" was in fact identical to the hypothetical substance "phlogiston" ^{[65] [66]} and further finding in 1781 that the gas produces water when burned. He is usually given credit for the discovery of hydrogen as an element. ^{[9] [10]}

Antoine Lavoisier, who identified the element that came to be known as hydrogen

In 1783, Antoine Lavoisier identified the element that came to be known as hydrogen ^[67] when he and Laplace reproduced Cavendish's finding that water is produced when hydrogen is burned. ^[10] Lavoisier produced hydrogen for his experiments on mass conservation by treating metallic iron with a steam of H₂ through an incandescent iron tube heated in a fire. Anaerobic oxidation of iron by the protons of water at high temperature can be schematically represented by the set of following reactions:

1) Fe + H₂O → FeO + H₂

2) Fe + 3 H₂O → Fe₂O₃ + 3 H₂

3) Fe + 4 H₂O → Fe₃O₄ + 4 H₂

Many metals react similarly with water leading to the production of hydrogen. ^[68] In some situations, this H₂-producing process is problematic as is the case of zirconium cladding on nuclear fuel rods. ^[69]

19th century

By 1806 hydrogen was used to fill balloons. ^[70] François Isaac de Rivaz built the first de Rivaz engine, an internal combustion engine powered by a mixture of hydrogen and oxygen in 1806. Edward Daniel Clarke invented the hydrogen gas blowpipe in 1819. The Döbereiner's lamp and limelight were invented in 1823.Hydrogen was liquefied for the first time by James Dewar in 1898 by using regenerative cooling and his invention, the vacuum flask. He produced solid hydrogen the next year. ^[10]

One of the first quantum effects to be explicitly noticed (but not understood at the time) was James Clerk Maxwell's observation that the specific heat capacity of H₂ unaccountably departs from that of a diatomic gas below room temperature and begins to increasingly resemble that of a monatomic gas at cryogenic temperatures. According to quantum theory, this behavior arises from the spacing of the (quantized) rotational energy levels, which are particularly wide-spaced in H₂ because of its low mass. These widely spaced levels inhibit equal partition of heat energy into rotational motion in hydrogen at low temperatures. Diatomic gases composed of heavier atoms do not have such widely spaced levels and do not exhibit the same effect. ^[71]

20th century

The existence of the hydride anion was suggested by Gilbert N. Lewis in 1916 for group 1 and 2 salt-like compounds. In 1920, Moers electrolyzed molten lithium hydride (LiH), producing a stoichiometric quantity of hydrogen at the anode. ^[72]

Hydrogen emission spectrum lines in the four visible lines of the Balmer series

Because of its simple atomic structure, consisting only of a proton and an electron, the hydrogen atom, together with the spectrum of light produced from it or absorbed by it, has been central to the development of the theory of atomic structure. ^[73] Hydrogen's unique position as the only neutral atom for which the Schrödinger equation can be directly solved, has significantly contributed to the understanding of quantum mechanics through the exploration of its energetics. ^[74] Furthermore, study of the corresponding simplicity of the hydrogen molecule and the corresponding cation H+2 brought understanding of the nature of the chemical bond, which followed shortly after the quantum mechanical treatment of the hydrogen atom had been developed in the mid-1920s.^{[ citation needed ]}

Hydrogen-lifted airship

The Hindenburg over New York City in 1937

The first hydrogen-filled balloon was invented by Jacques Charles in 1783. Hydrogen provided the lift for the first reliable form of air-travel following the 1852 invention of the first hydrogen-lifted airship by Henri Giffard. German count Ferdinand von Zeppelin promoted the idea of rigid airships lifted by hydrogen that later were called Zeppelins; the first of which had its maiden flight in 1900. ^[10] Regularly scheduled flights started in 1910 and by the outbreak of World War I in August 1914, they had carried 35,000 passengers without a serious incident. Hydrogen-lifted airships were used as observation platforms and bombers during the war.^{[ citation needed ]}

The first non-stop transatlantic crossing was made by the British airship R34 in 1919. Regular passenger service resumed in the 1920s and the discovery of helium reserves in the United States promised increased safety, but the U.S. government refused to sell the gas for this purpose. Therefore, H₂ was used in the Hindenburg airship, which was destroyed in a midair fire over New Jersey on 6 May 1937. ^[10] The incident was broadcast live on radio and filmed. Ignition of leaking hydrogen is widely assumed to be the cause, but later investigations pointed to the ignition of the aluminized fabric coating by static electricity. But the damage to hydrogen's reputation as a lifting gas was already done and commercial hydrogen airship travel ceased. Hydrogen is still used, in preference to non-flammable but more expensive helium, as a lifting gas for weather balloons.^{[ citation needed ]}

Deuterium and tritium

Deuterium was discovered in December 1931 by Harold Urey, and tritium was prepared in 1934 by Ernest Rutherford, Mark Oliphant, and Paul Harteck. ^[9] Heavy water, which consists of deuterium in the place of regular hydrogen, was discovered by Urey's group in 1932. ^[10]

Hydrogen-cooled turbogenerator

The first hydrogen-cooled turbogenerator went into service using gaseous hydrogen as a coolant in the rotor and the stator in 1937 at Dayton, Ohio, owned by the Dayton Power & Light Co. ^[75] This was justified by the high thermal conductivity and very low viscosity of hydrogen gas, thus lower drag than air. This is the most common coolant used for generators 60 MW and larger; smaller generators are usually air-cooled.^{[ citation needed ]}

Nickel–hydrogen battery

The nickel–hydrogen battery was used for the first time in 1977 aboard the U.S. Navy's Navigation technology satellite-2 (NTS-2). ^[76] The International Space Station, ^[77] Mars Odyssey ^[78] and the Mars Global Surveyor ^[79] are equipped with nickel-hydrogen batteries. In the dark part of its orbit, the Hubble Space Telescope is also powered by nickel-hydrogen batteries, which were finally replaced in May 2009, ^[80] more than 19 years after launch and 13 years beyond their design life. ^[81]

Chemistry

Laboratory syntheses

H₂ is produced in labs, often as a by-product of other reactions. Many metals react with water to produce H₂, but the rate of hydrogen evolution depends on the metal, the pH, and the presence of alloying agents. Most often, hydrogen evolution is induced by acids. The alkali and alkaline earth metals, aluminium, zinc, manganese, and iron react readily with aqueous acids. This reaction is the basis of the Kipp's apparatus, which once was used as a laboratory gas source:

Zn + 2 H⁺ → Zn²⁺ + H₂

In the absence of acid, the evolution of H₂ is slower. Because iron is widely used structural material, its anaerobic corrosion is of technological significance:

Fe + 2 H₂O → Fe(OH)₂ + H₂

Many metals, such as aluminium, are slow to react with water because they form passivated oxide coatings of oxides. An alloy of aluminium and gallium, however, does react with water. ^[82] At high pH, aluminium can produce H₂:

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

Reactions of H₂

A dihydrogen complex of iron, [HFe(H₂)(dppe)₂] .

H₂ is relatively unreactive. The thermodynamic basis of this low reactivity is the very strong H–H bond, with a bond dissociation energy of 435.7 kJ/mol. ^[83] It does form coordination complexes called dihydrogen complexes. These species provide insights into the early steps in the interactions of hydrogen with metal catalysts. According to neutron diffraction, the metal and two H atoms form a triangle in these complexes. The H-H bond remains intact but is elongated. They are acidic. ^[84]

Although exotic on Earth, the H+3 ion is common in the universe. It is a triangular species, like the aforementioned dihydrogen complexes. It is known as protonated molecular hydrogen or the trihydrogen cation. ^[85]

Hydrogen directly reacts with chlorine, fluorine and bromine to give HF, HCl, and HBr, respectively. The conversion involves a radical chain mechanism. With heating, H₂ reacts efficiently with the alkali and alkaline earth metals to give the saline hydrides of the formula MH and MH₂, respectively. ^[86] One of the striking properties of H₂ is its inertness toward unsaturated organic compounds, such as alkenes and alkynes. These species only react with H₂ in the presence of catalysts. Especially active catalysts are the platinum metals ([[Pt], [[Rh], Pd, etc.). A major driver for the mining of these rare and expensive elements is their use as catalysts. ^[86]

Hydrogen-containing compounds

Main article: Hydrogen compounds

Most known compounds contain hydrogen, not as H₂, but as covalently bonded H atoms. This interaction is the basis of organic chemistry and biochemistry.Hydrogen forms many compounds with carbon, called the hydrocarbons. Hydrocarbons are called organic compounds. In nature, they almost always contain "heteroatoms" such as nitrogen, oxygen, and sulfur. ^[87] The study of their properties is known as organic chemistry ^[88] and their study in the context of living organisms is called biochemistry. ^[89] By some definitions, "organic" compounds are only required to contain carbon. However, most of them also contain hydrogen, and because it is the carbon-hydrogen bond that gives this class of compounds most of its particular chemical characteristics, carbon-hydrogen bonds are required in some definitions of the word "organic" in chemistry. ^[87] Millions of hydrocarbons are known, and they are usually formed by complicated pathways that seldom involve elemental hydrogen.^{[ citation needed ]}

Hydrides

Main article: Hydride

A sample of sodium hydride

Hydrogen forms compounds with less electronegative elements, such as metals and main group elements. In these compounds, hydrogen takes on a partial negative charge. The term "hydride" suggests that the H atom has acquired a negative or anionic character, denoted H⁻. Usually hydride refers to hydrogen in a compound with a more electropositive element. For hydrides other than group 1 and 2 metals, the term can be misleading, considering the low electronegativity of hydrogen. A well known hydride is lithium aluminium hydride, the [AlH₄]⁻ anion carries hydridic centers firmly attached to the Al(III). ^[90] Perhaps the most extensive series of hydrides are the boranes, compounds consisting only of boron and hydrogen. ^[91]

Hydrides can bond to these electropositive elements not only as a terminal ligand but also as bridging ligands. In diborane (B₂H₆), four H's are terminal and two bridge between the two B atoms. ^[45]

Protons and acids

Further information: Acid–base reaction

An "A-T base pair" in DNA illustrating how hydrogen bonds are critical to the genetic code. The drawing illustrates that in many chemical depictions, C-H bonds are not always shown explicitly, an indication of their pervasiveness.

When bonded to a more electronegative element, particularly fluorine, oxygen, or nitrogen, hydrogen can participate in a form of medium-strength noncovalent bonding with another electronegative element with a lone pair, a phenomenon called hydrogen bonding that is critical to the stability of many biological molecules. ^{[92] [93]} H⁺ can also be obtained by oxidation of H₂. Under the Brønsted–Lowry acid–base theory, acids are proton donors, while bases are proton acceptors.^{[ citation needed ]}

A bare proton, H⁺ essentially cannot exist in anything other than a vacuum. Otherwise it attaches to other atoms, ions, or molecules. Even species as inert as methane can be protonated. The term 'proton' is used loosely and metaphorically to refer to refer to solvated {chem2|H+}}" without any implication that any single protons exist freely as a species. To avoid the implication of the naked proton in solution, acidic aqueous solutions are sometimes considered to contain the "hydronium ion" ([H₃O]⁺) or still more accurately, [H₉O₄]⁺. ^[94] Other oxonium ions are found when water is in acidic solution with other solvents. ^[95]

Occurrence

Cosmic

NGC 604, a giant region of ionized hydrogen in the Triangulum Galaxy

Hydrogen, as atomic H, is the most abundant chemical element in the universe, making up 75% of normal matter by mass and >90% by number of atoms. ^[96] In astrophysics, neutral hydrogen in the interstellar medium is called H I and ionized hydrogen is called H II. ^[97] Radiation from stars ionizes H I to H II, creating spheres of ionized H II around stars. In the chronology of the universe neutral hydrogen dominated until the birth of stars during the era of reionization led to bubbles of ionized hydrogen that grew and merged over 500 million of years. ^[98] They are the source of the 21-cm hydrogen line at 1420 MHz that is detected in order to probe primordial hydrogen. The large amount of neutral hydrogen found in the damped Lyman-alpha systems is thought to dominate the cosmological baryonic density of the universe up to a redshift of z = 4. ^[99]

Hydrogen is found in great abundance in stars and gas giant planets. Molecular clouds of H₂ are associated with star formation. Hydrogen plays a vital role in powering stars through the proton-proton reaction in lower-mass stars, and through the CNO cycle of nuclear fusion in case of stars more massive than the Sun. ^[100]

Hydrogen plasma states have properties quite distinct from those of molecular or atomic hydrogen. As a plasma, hydrogen's electron and proton are not bound together, resulting in very high electrical conductivity and high emissivity (producing the light from the Sun and other stars). The charged particles are highly influenced by magnetic and electric fields. For example, in the solar wind they interact with the Earth's magnetosphere giving rise to Birkeland currents and the aurora.^{[ citation needed ]}

A molecular form called protonated molecular hydrogen (H+3) is found in the interstellar medium, where it is generated by ionization of molecular hydrogen from cosmic rays. This ion has also been observed in the upper atmosphere of Jupiter. The ion is long-lived in outer space due to the low temperature and density. H+3 is one of the most abundant ions in the universe, and it plays a notable role in the chemistry of the interstellar medium. ^[101] Neutral triatomic hydrogen H₃ can exist only in an excited form and is unstable. ^[102] By contrast, the positive hydrogen molecular ion (H+2) is a rare in the universe.^{[ citation needed ]}

Terrestrial

Under ordinary conditions on Earth, elemental hydrogen exists as the diatomic gas, H₂. Hydrogen gas is very rare in Earth's atmosphere (around 0.53 ppm on a molar basis ^[103] ) because of its light weight, which enables it to escape the atmosphere more rapidly than heavier gases. However, hydrogen, usually in the form of water, is the third most abundant element on the Earth's surface, ^[104] mostly in the form of chemical compounds such as hydrocarbons and water. ^[45] Despite its low concentration in our atmosphere, terrestrial hydrogen is sufficiently abundant to support the metabolism of several bacteria. ^[105]

Deposits of hydrogen gas have been discovered in several countries including Mali, France and Australia. ^[106]

Production and storage

Main article: Hydrogen production

Industrial routes

Many methods exist for producing H₂, but three dominate commercially: steam reforming often coupled to water-gas shift, partial oxidation of hydrocarbons, and water electrolysis. ^[107]

Steam reforming

Inputs and outputs of steam reforming (SMR) and water gas shift (WGS) reaction of natural gas, a process used in hydrogen production

Hydrogen is mainly produced by steam methane reforming (SMR), the reaction of water and methane. ^{[108] [109] [110]} Thus, at high temperature (1000–1400 K, 700–1100 °C or 1300–2000 °F), steam (water vapor) reacts with methane to yield carbon monoxide and H₂.

CH₄ + H₂O → CO + 3 H₂

Steam reforming is also used for the industrial preparation of ammonia.^{[ citation needed ]}

This reaction is favored at low pressures, Nonetheless, conducted at high pressures (2.0 MPa, 20 atm or 600  inHg) because high-pressure H₂ is the most marketable product, and pressure swing adsorption (PSA) purification systems work better at higher pressures. The product mixture is known as "synthesis gas" because it is often used directly for the production of methanol and many other compounds. Hydrocarbons other than methane can be used to produce synthesis gas with varying product ratios. One of the many complications to this highly optimized technology is the formation of coke or carbon:

CH₄ → C + 2 H₂

Therefore, steam reforming typically employs an excess of H₂O. Additional hydrogen can be recovered from the steam by using carbon monoxide through the water gas shift reaction (WGS). This process requires an iron oxide catalyst: ^[110]

CO + H₂O → CO₂ + H₂

Hydrogen is sometimes produced and consumed in the same industrial process, without being separated. In the Haber process for ammonia production, hydrogen is generated from natural gas. ^[111]

Partial oxidation of hydrocarbons

Other methods for CO and H₂ production include partial oxidation of hydrocarbons: ^[29]

2 CH₄ + O₂ → 2 CO + 4 H₂

Although less important commercially, coal can serve as a prelude to the shift reaction above: ^[110]

C + H₂O → CO + H₂

Olefin production units may produce substantial quantities of byproduct hydrogen particularly from cracking light feedstocks like ethane or propane. ^[112]

Water electrolysis

Inputs and outputs of the electrolysis of water production of hydrogen

Electrolysis of water is a conceptually simple method of producing hydrogen.

2 H₂O(l) → 2 H₂(g) + O₂(g)

Commercial electrolyzers use nickel-based catalysts in strongly alkaline solution. Platinum is a better catalyst but is expensive. ^[113]

Electrolysis of brine to yield chlorine ^[114] also produces high purity hydrogen as a co-product, which is used for a variety of transformations such as hydrogenations. ^[115]

The electrolysis process is more expensive than producing hydrogen from methane without CCS and the efficiency of energy conversion is inherently low. ^[116]

Innovation in hydrogen electrolyzers could make large-scale production of hydrogen from electricity more cost-competitive. ^[117] Hydrogen produced in this manner could play a significant role in decarbonizing energy systems where there are challenges and limitations to replacing fossil fuels with direct use of electricity. ^[118]

Methane pyrolysis

Hydrogen can be produced by pyrolysis of natural gas (methane).

This route has a lower carbon footprint than commercial hydrogen production processes. ^{[119] [120] [121] [122]} Developing a commercial methane pyrolysis process could expedite the expanded use of hydrogen in industrial and transportation applications. Methane pyrolysis is accomplished by passing methane through a molten metal catalyst containing dissolved nickel. Methane is converted to hydrogen gas and solid carbon. ^{[123] [124]}

CH₄(g) → C(s) + 2 H₂(g) (ΔH° = 74 kJ/mol)

The carbon may be sold as a manufacturing feedstock or fuel, or landfilled.^{[ citation needed ]}

Further research continues in several laboratories, including at Karlsruhe Liquid-metal Laboratory ^[125] and at University of California – Santa Barbara. ^[126] BASF built a methane pyrolysis pilot plant. ^[127]

Thermochemical

Water splitting is the process by which water is decomposed into its components. Relevant to the biological scenario is this simple equation:

2 H₂O → 4 H⁺ + O₂ + 4e⁻

The reaction occurs in the light reactions in all photosynthetic organisms. A few organisms, including the alga Chlamydomonas reinhardtii and cyanobacteria, have evolved a second step in the dark reactions in which protons and electrons are reduced to form H₂ gas by specialized hydrogenases in the chloroplast. ^[128]

Efforts have been undertaken to genetically modify cyanobacterial hydrogenases to more efficiently generate H₂ gas even in the presence of oxygen. ^[129] Efforts have also been undertaken with genetically modified alga in a bioreactor. ^[130]

Relevant to the thermal water-splitting scenario is this simple equation:

2 H₂O → 2 H₂ + O₂

More than 200 thermochemical cycles can be used for water splitting. Many of these cycles such as the iron oxide cycle, cerium(IV) oxide–cerium(III) oxide cycle, zinc zinc-oxide cycle, sulfur-iodine cycle, copper-chlorine cycle and hybrid sulfur cycle have been evaluated for their commercial potential to produce hydrogen and oxygen from water and heat without using electricity. ^[131] A number of labs (including in France, Germany, Greece, Japan, and the United States) are developing thermochemical methods to produce hydrogen from solar energy and water. ^[132]

Natural routes

Biohydrogen

Further information: Biohydrogen and Biological hydrogen production (Algae)

H₂ is produced by enzymes called hydrogenases. This process allows the host organism to use fermentation as a source of energy. ^[133] These same enzymes also can oxidize H₂, such that the host organisms can subsist by reducing oxidized substrates using electrons extracted from H₂.^{[ citation needed ]}

The hydrogenase enzyme feature iron or nickel-iron centers at their active sites. ^[134] The natural cycle of hydrogen production and consumption by organisms is called the hydrogen cycle. ^[135]

Some bacteria such as Mycobacterium smegmatis can use the small amount of hydrogen in the atmosphere as a source of energy when other sources are lacking. Their hydrogenase are designed with small channels that exclude oxygen and so permits the reaction to occur even though the hydrogen concentration is very low and the oxygen concentration is as in normal air. ^{[103] [136]}

Confirming the existence of hydrogenases in the human gut, H₂ occurs in human breath. The concentration in the breath of fasting people at rest is typically less than 5 parts per million (ppm) but can be 50 ppm when people with intestinal disorders consume molecules they cannot absorb during diagnostic hydrogen breath tests. ^[137]

Serpentinization

Serpentinization is a geological mechanism that produce highly reducing conditions. ^[138] Under these conditions, water is capable of oxidizing ferrous (Fe²⁺
) ions in fayalite. The process is of interest because it generates hydrogen gas: ^{[16] [139] [140]}

Fe₂SiO₄ + H₂O → 2 Fe₃O₄ + SiO₂ +H₂

Closely related to this geological process is the Schikorr reaction:

3 Fe(OH)₂ → Fe₃O₄ + 2 H₂O + H₂

This process also is relevant to the corrosion of iron and steel in oxygen-free groundwater and in reducing soils below the water table.^{[ citation needed ]}

Storage

Hydrogen produced when there is a surplus of variable renewable electricity could in principle be stored and later used to generate heat or to re-generate electricity. ^[141] The hydrogen created through electrolysis using renewable energy is commonly referred to as "green hydrogen". ^[142] It can be further transformed into synthetic fuels such as ammonia and methanol. ^[143] Disadvantages of hydrogen as an energy carrier include high costs of storage and distribution due to hydrogen's explosivity, its large volume compared to other fuels, and its tendency to make pipes brittle. ^[144]

If H₂ is to used as an energy source, its storage is important. It dissolves only poorly in solvents. For example at room temperature and 0.1 Mpascal, ca. 0.05 moles dissolves in one kilogram of diethyl ether. ^[86] The H₂ can be stored in compressed form, although compressing costs energy. Liquifaction is impractical given its low critical temperature. In contrast, ammonia and many hydrocarbons can be liquified at room temperature under pressure. For these reasons, hydrogen carriers - materials that reversibly bind H₂ - have attracted much attention. The key question is then the weight percent of H₂-equivalents within the carrier material. For example, hydrogen can be reversibly absorbed into many rare earth and transition metals ^[145] and is soluble in both nanocrystalline and amorphous metals. ^[146] Hydrogen solubility in metals is influenced by local distortions or impurities in the crystal lattice. ^[147] These properties may be useful when hydrogen is purified by passage through hot palladium disks, but the gas's high solubility is also a metallurgical problem, contributing to the embrittlement of many metals, ^[148] complicating the design of pipelines and storage tanks. ^[149]

The most problematic aspect of metal hydrides for storage is their modest H₂ content, often on the order of 1%. For this reason, there is interest in storage of H₂ in compounds of low molecular weight. For example, ammonia borane (H₃N−BH₃) contains 19.8 weight percent of H₂. The problem with this material is that after release of H₂, the resulting boron nitride does not re-add H₂, i.e. ammonia borane is an irreversible hydrogen carrier. ^[150] More attractive, somewhat ironically, are hydrocarbons such as tetrahydroquinoline, which reversibly release some H₂ when heated in the presence of a catalyst: ^[151]

C₉H₁₀NH ⇌ C₉H₇N + 2H₂

Applications

See also: Hydrogen economy

Some projected uses in the medium term, but analysts disagree

Petrochemical industry

Large quantities of H₂ are used in the "upgrading" of fossil fuels. Key consumers of H₂ include hydrodesulfurization, and hydrocracking. Many of these reactions can be classified as hydrogenolysis, i.e., the cleavage of bonds by hydrogen. Illustrative is the separation of sulfur from liquid fossil fuels: ^[107]

R₂S + 2 H₂ → H₂S + 2 RH

Hydrogenation

Hydrogenation, the addition of H₂ to various substrates, is done on a large scale. Hydrogenation of N₂ to produce ammonia by the Haber process, consumes a few percent of the energy budget in the entire industry. The resulting ammonia is used to supply most of the protein consumed by humans. ^[153] Hydrogenation is used to convert unsaturated fats and oils to saturated fats and oils. The major application is the production of margarine. Methanol is produced by hydrogenation of carbon dioxide. It is similarly the source of hydrogen in the manufacture of hydrochloric acid. H₂ is also used as a reducing agent for the conversion of some ores to the metals. ^[154]

Coolant

Main article: Hydrogen-cooled turbo generator

Hydrogen is commonly used in power stations as a coolant in generators due to a number of favorable properties that are a direct result of its light diatomic molecules. These include low density, low viscosity, and the highest specific heat and thermal conductivity of all gases.^{[ citation needed ]}

Fuel

Hydrogen (H₂) is widely discussed as a carrier of energy with potential to help to decarbonize economies and mitigate greenhouse gas emissions. ^{[118] [116]} This scenario requires the efficient production and storage of hydrogen.

Hydrogen fuel can produce the intense heat required for industrial production of steel, cement, glass, and chemicals, thus contributing to the decarbonisation of industry alongside other technologies, such as electric arc furnaces for steelmaking. ^[155] However, it is likely to play a larger role in providing industrial feedstock for cleaner production of ammonia and organic chemicals. ^[118] For example, in steelmaking, hydrogen could function as a clean energy carrier and also as a low-carbon catalyst, replacing coal-derived coke (carbon): ^[156]

2FeO + C → 2Fe + CO₂

vs

FeO + H₂ → Fe + H₂O

Hydrogen used to decarbonise transportation is likely to find its largest applications in shipping, aviation and, to a lesser extent, heavy goods vehicles, through the use of hydrogen-derived synthetic fuels such as ammonia and methanol and fuel cell technology. ^[118] For light-duty vehicles including cars, hydrogen is far behind other alternative fuel vehicles, especially compared with the rate of adoption of battery electric vehicles, and may not play a significant role in future. ^[157]

Liquid hydrogen and liquid oxygen together serve as cryogenic propellants in liquid-propellant rockets, as in the Space Shuttle main engines. NASA has investigated the use of rocket propellant made from atomic hydrogen, boron or carbon that is frozen into solid molecular hydrogen particles suspended in liquid helium. Upon warming, the mixture vaporizes to allow the atomic species to recombine, heating the mixture to high temperature. ^[158]

Semiconductor industry

Hydrogen is employed to saturate broken ("dangling") bonds of amorphous silicon and amorphous carbon that helps stabilizing material properties. ^[159] It is also a potential electron donor in various oxide materials, including ZnO, ^{[160] [161]} SnO₂, CdO, MgO, ^[162] ZrO₂, HfO₂, La₂O₃, Y₂O₃, TiO₂, SrTiO₃, LaAlO₃, SiO₂, Al₂O₃, ZrSiO₄, HfSiO₄, and SrZrO₃. ^[163]

Niche and evolving uses

• Shielding gas: Hydrogen is used as a shielding gas in welding methods such as atomic hydrogen welding. ^{[164] [165]}

• Cryogenic research: Liquid H₂ is used in cryogenic research, including superconductivity studies. ^[166]

• Buoyant lifting: Because H₂ is only 7% the density of air, it was once widely used as a lifting gas in balloons and airships. ^[167]
• Leak detection: Pure or mixed with nitrogen (sometimes called forming gas), hydrogen is a tracer gas for detection of minute leaks. Applications can be found in the automotive, chemical, power generation, aerospace, and telecommunications industries. ^[168] Hydrogen is an authorized food additive (E 949) that allows food package leak testing, as well as having anti-oxidizing properties. ^[169]

• Neutron moderation: Deuterium (hydrogen-2) is used in nuclear fission applications as a moderator to slow neutrons.
• Nuclear fusion fuel: Deuterium is used in nuclear fusion reactions. ^[10]
• Isotopic labeling: Deuterium compounds have applications in chemistry and biology in studies of isotope effects on reaction rates. ^[170]

• Tritium uses: Tritium (hydrogen-3), produced in nuclear reactors, is used in the production of hydrogen bombs, ^[171] as an isotopic label in the biosciences, ^[51] and as a source of beta radiation in radioluminescent paint for instrument dials and emergency signage. ^[46]

Safety and precautions

Main article: Hydrogen safety

Hydrogen

Hazards
GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H220
Precautionary statements	P202, P210, P271, P377, P381, P403 [172]
NFPA 704 (fire diamond)	0 4 0

Hydrogen poses few hazards to human safety. The chief hazards are for detonations and asphyxiation, but both are mitigated by its high diffusivity. Because hydrogen has been intensively investigated as a fuel, there is extensive documentation on the risks. ^[173] Because H₂ reacts with very few substrates, it is nontoxic as evidenced by the fact that humans exhale small amounts of it.

See also

• Combined cycle hydrogen power plant
• Hydrogen economy  – Using hydrogen to decarbonize more sectors
• Hydrogen production  – Industrial production of molecular hydrogen
• Hydrogen safety  – Procedures for safe production, handling and use of hydrogen
• Hydrogen technologies  – Technologies that relating to the production & use of hydrogen
• Hydrogen transport
• Methane pyrolysis  – Thermal decomposition of materialsPages displaying short descriptions of redirect targets (for hydrogen)
• Natural hydrogen  – Molecular hydrogen naturally occurring on Earth
• Pyrolysis  – Thermal decomposition of materials

Notes

1. 286 kJ/mol: energy per mole of the combustible material (molecular hydrogen).

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Further reading

• The Hyperfine Splitting in Hydrogen - The Feynman Lectures on Physics
• Chart of the Nuclides (17th ed.). Knolls Atomic Power Laboratory. 2010. ISBN   978-0-9843653-0-2.
• Newton, David E. (1994). The Chemical Elements. New York: Franklin Watts. ISBN   978-0-531-12501-4.
• Rigden, John S. (2002). Hydrogen: The Essential Element. Cambridge, Massachusetts: Harvard University Press. ISBN   978-0-531-12501-4.
• Romm, Joseph J. (2004). The Hype about Hydrogen, Fact and Fiction in the Race to Save the Climate. Island Press. ISBN   978-1-55963-703-9.
• Scerri, Eric (2007). The Periodic System, Its Story and Its Significance . New York: Oxford University Press. ISBN   978-0-19-530573-9.

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