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Contents
Articles
Overview 1
Hydrogen 1
Antihydrogen 18
Hydrogen atom 20
Hydrogen-like atom 26
Hydrogen spectral series 29
Liquid hydrogen 34
Solid hydrogen 38
Metallic hydrogen 39
Nascent hydrogen 43
Isotopes 45
Isotopes of hydrogen 45
Deuterium 49
Tritium 59
Hydrogen-4 69
Hydrogen-5 70
Spin isomers of hydrogen 71
Reactions 74
Bosch reaction 74
Hydrogen cycle 75
Hydrogenation 76
Dehydrogenation 84
Transfer hydrogenation 85
Hydrogenolysis 89
Hydron 90
Sabatier reaction 91
Risks 93
Hydrogen damage 93
Hydrogen embrittlement 96
Hydrogen leak testing 99
Hydrogen safety 100
Fuel 103
Timeline of hydrogen technologies 103
Biohydrogen 107
Hydrogen production 113
Hydrogen infrastructure 118
Hydrogen line 119
Hydrogen purity 124
References
Article Sources and Contributors 125
Image Sources, Licenses and Contributors 128
Article Licenses
License 130
1
Overview
Hydrogen
Hydrogen
Appearance
General properties
Pronunciation [1]
/ˈhaɪdrɵdʒɪn/ HYE-dro-jin
Electron configuration 1s
1
Physical properties
Color colorless
Phase gas
at T/K 15 20
Atomic properties
Oxidation states 1, -1
(amphoteric oxide)
Miscellanea
H 99.985%
1 1
H is stable with 0 neutron
2
H 0.015% 2
H is stable with 1 neutron
3
H trace 12.32 y β
− 0.01861 3
He
Hydrogen ( /ˈhaɪdrɵdʒɪn/ HYE-dro-jin)[4] is the chemical element with atomic number 1. It is represented by the
symbol H. With an average atomic weight of 1.00794 u (1.007825 u for Hydrogen-1), hydrogen is the lightest and
most abundant chemical element, constituting roughly 75 % of the Universe's elemental mass.[5] Stars in the main
sequence are mainly composed of hydrogen in its plasma state. Naturally occurring elemental hydrogen is relatively
rare on Earth.
The most common isotope of hydrogen is protium (name rarely used, symbol 1H) with a single proton and no
neutrons. In ionic compounds it can take a negative charge (an anion known as a hydride and written as H−), or as a
positively charged species H+. The latter cation is written as though composed of a bare proton, but in reality,
hydrogen cations in ionic compounds always occur as more complex species. Hydrogen forms compounds with most
elements and is present in water and most organic compounds. It plays a particularly important role in acid-base
chemistry with many reactions exchanging protons between soluble molecules. As the simplest atom known, the
hydrogen atom has been of theoretical use. For example, as the only neutral atom with an analytic solution to the
Schrödinger equation, the study of the energetics and bonding of the hydrogen atom played a key role in the
development of quantum mechanics.
Hydrogen gas (now known to be H2) was first artificially produced in the early 16th century, via the mixing of
metals with strong acids. In 1766–81, Henry Cavendish was the first to recognize that hydrogen gas was a discrete
substance,[6] and that it produces water when burned, a property which later gave it its name, which in Greek means
Hydrogen 3
"water-former." At standard temperature and pressure, hydrogen is a colorless, odorless, nonmetallic, tasteless,
highly combustible diatomic gas with the molecular formula H2.
Industrial production is mainly from the steam reforming of natural gas, and less often from more energy-intensive
hydrogen production methods like the electrolysis of water.[7] Most hydrogen is employed near its production site,
with the two largest uses being fossil fuel processing (e.g., hydrocracking) and ammonia production, mostly for the
fertilizer market.
Hydrogen is a concern in metallurgy as it can embrittle many metals,[8] complicating the design of pipelines and
storage tanks.[9]
Properties
Combustion
Hydrogen gas (dihydrogen or molecular hydrogen)[10] is highly flammable and
will burn in air at a very wide range of concentrations between 4% and 75% by
volume.[11] The enthalpy of combustion for hydrogen is −286 kJ/mol:[12]
2 H2(g) + O2(g) → 2 H2O(l) + 572 kJ (286 kJ/mol)[13]
Hydrogen gas forms explosive mixtures with air in the concentration range
4–74% (volume per cent of hydrogen in air) and with chlorine in the range
5–95%. The mixtures spontaneously detonate by spark, heat or sunlight. The
hydrogen autoignition temperature, the temperature of spontaneous ignition in
air, is 500 °C (932 °F).[14] Pure hydrogen-oxygen flames emit ultraviolet light
The Space Shuttle Main Engine and are nearly invisible to the naked eye, as illustrated by the faint plume of the
burns hydrogen with oxygen,
Space Shuttle main engine compared to the highly visible plume of a Space
producing a nearly invisible flame at
full thrust. Shuttle Solid Rocket Booster. The detection of a burning hydrogen leak may
require a flame detector; such leaks can be very dangerous. The destruction of
the Hindenburg airship was an infamous example of hydrogen combustion; the cause is debated, but the visible
flames were the result of combustible materials in the ship's skin.[15] Because hydrogen is buoyant in air, hydrogen
flames tend to ascend rapidly and cause less damage than hydrocarbon fires. Two-thirds of the Hindenburg
passengers survived the fire, and many deaths were instead the result of falls or burning diesel fuel.[16]
H2 reacts with every oxidizing element. Hydrogen can react spontaneously and violently at room temperature with
chlorine and fluorine to form the corresponding hydrogen halides, hydrogen chloride and hydrogen fluoride, which
are also potentially dangerous acids.[17]
Hydrogen 4
The uncatalyzed interconversion between para and ortho H2 increases with increasing temperature; thus rapidly
condensed H2 contains large quantities of the high-energy ortho form that converts to the para form very slowly.[25]
The ortho/para ratio in condensed H2 is an important consideration in the preparation and storage of liquid hydrogen:
the conversion from ortho to para is exothermic and produces enough heat to evaporate some of the hydrogen liquid,
leading to loss of liquefied material. Catalysts for the ortho-para interconversion, such as ferric oxide, activated
carbon, platinized asbestos, rare earth metals, uranium compounds, chromic oxide, or some nickel[26] compounds,
are used during hydrogen cooling.[27]
Hydrogen 5
A molecular form called protonated molecular hydrogen, or H , is found in the interstellar medium (ISM), where it
is generated by ionization of molecular hydrogen from cosmic rays. It has also been observed in the upper
atmosphere of the planet Jupiter. This molecule is relatively stable in the environment of outer space due to the low
temperature and density. H is one of the most abundant ions in the Universe, and it plays a notable role in the
chemistry of the interstellar medium.[28] Neutral triatomic hydrogen H3 can only exist in an excited from and is
unstable.[29]
Compounds
Hydrides
Compounds of hydrogen are often called hydrides, a term that is used fairly loosely. The term "hydride" suggests
that the H atom has acquired a negative or anionic character, denoted H−, and is used when hydrogen forms a
compound with a more electropositive element. The existence of the hydride anion, suggested by Gilbert N. Lewis in
1916 for group I and II salt-like hydrides, was demonstrated by Moers in 1920 with the electrolysis of molten lithium
hydride (LiH), that produced a stoichiometric quantity of hydrogen at the anode.[38] For hydrides other than group I
and II metals, the term is quite misleading, considering the low electronegativity of hydrogen. An exception in group
II hydrides is BeH2, which is polymeric. In lithium aluminium hydride, the AlH anion carries hydridic centers firmly
attached to the Al(III). Although hydrides can be formed with almost all main-group elements, the number and
combination of possible compounds varies widely; for example, there are over 100 binary borane hydrides known,
but only one binary aluminium hydride.[39] Binary indium hydride has not yet been identified, although larger
complexes exist.[40]
Hydrogen 6
Isotopes
Hydrogen has three naturally occurring isotopes, denoted 1H, 2H and
3
H. Other, highly unstable nuclei (4H to 7H) have been synthesized in
the laboratory but not observed in nature.[44] [45]
1
• H is the most common hydrogen isotope with an abundance of
Hydrogen discharge (spectrum) tube more than 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.[46]
2
• H, the other stable hydrogen isotope, is known as deuterium and
contains one proton and one neutron in its nucleus. Essentially all
deuterium in the universe is thought to have been produced at the
time of the Big Bang, and has endured since that time. Deuterium is
Deuterium discharge (spectrum) tube
not radioactive, and does not represent 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 1H-NMR
spectroscopy.[47] Heavy water is used as a neutron moderator and coolant for nuclear reactors. Deuterium is also a
potential fuel for commercial nuclear fusion.[48]
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.[37] Small amounts of tritium occur naturally because
of the interaction of cosmic rays with atmospheric gases; tritium has also been released during nuclear weapons
tests.[49] It is used in nuclear fusion reactions,[50] as a
Hydrogen 7
History
was destroyed in a midair fire over New Jersey on May 6, 1937.[60] 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. In the same year the first hydrogen-cooled turbogenerator went into service with gaseous
hydrogen as a coolant in the rotor and the stator in 1937 at Dayton, Ohio, by the Dayton Power & Light Co,[62]
because of the thermal conductivity of hydrogen gas this is the most common type in its field today. The nickel
hydrogen battery was used for the first time in 1977 aboard the U.S. Navy's Navigation technology satellite-2
(NTS-2).[63] For example, the ISS,[64] Mars Odyssey[65] and the Mars Global Surveyor[66] are equipped with
nickel-hydrogen batteries. The Hubble Space Telescope, at the time its original batteries were finally changed in
May 2009, more than 19 years after launch, led with the highest number of charge/discharge cycles.
One of the first quantum effects to be explicitly noticed (but not understood at the time) was a Maxwell observation
involving hydrogen, half a century before full quantum mechanical theory arrived. Maxwell observed 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.[68]
Natural occurrence
Hydrogen 9
Under ordinary conditions on Earth, elemental hydrogen exists as the diatomic gas, H2 (for data see table). However,
hydrogen gas is very rare in the Earth's atmosphere (1 ppm by volume) because of its light weight, which enables it
to escape from Earth's gravity more easily than heavier gases. However, hydrogen is the third most abundant element
on the Earth's surface.[72] Most of the Earth's hydrogen is in the form of chemical compounds such as hydrocarbons
and water.[37] Hydrogen gas is produced by some bacteria and algae and is a natural component of flatus, as is
methane, itself a hydrogen source of increasing importance.[73]
Production
H2 is produced in chemistry and biology laboratories, often as a by-product of other reactions; in industry for the
hydrogenation of unsaturated substrates; and in nature as a means of expelling reducing equivalents in biochemical
reactions.
Laboratory
In the laboratory, H2 is usually prepared by the reaction of acids on metals such as zinc with Kipp's apparatus.
Zn + 2 H+ → Zn2+ + H2
Aluminium can also produce H2 upon treatment with bases:
2 Al + 6 H2O + 2 OH− → 2 Al(OH) + 3 H2
The electrolysis of water is a simple method of producing hydrogen. A low voltage current is run through the water,
and gaseous oxygen forms at the anode while gaseous hydrogen forms at the cathode. Typically the cathode is made
from platinum or another inert metal when producing hydrogen for storage. If, however, the gas is to be burnt on
site, oxygen is desirable to assist the combustion, and so both electrodes would be made from inert metals. (Iron, for
instance, would oxidize, and thus decrease the amount of oxygen given off.) The theoretical maximum efficiency
(electricity used vs. energetic value of hydrogen produced) is between 80–94%.[74]
2 H2O(aq) → 2 H2(g) + O2(g)
In 2007, it was discovered that an alloy of aluminium and gallium in pellet form added to water could be used to
generate hydrogen. The process also creates alumina, but the expensive gallium, which prevents the formation of an
oxide skin on the pellets, can be re-used. This has important potential implications for a hydrogen economy, as
Hydrogen 10
Industrial
Hydrogen can be prepared in several different ways, but economically the most important processes involve removal
of hydrogen from hydrocarbons. Commercial bulk hydrogen is usually produced by the steam reforming of natural
gas.[76] At high temperatures (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
This reaction is favored at low pressures but is nonetheless conducted at high pressures (2.0 MPa, 20 atm or
600 inHg). This is 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 related 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
Consequently, steam reforming typically employs an excess of H2O. Additional hydrogen can be recovered from the
steam by use of carbon monoxide through the water gas shift reaction, especially with an iron oxide catalyst. This
reaction is also a common industrial source of carbon dioxide:[76]
CO + H2O → CO2 + H2
Other important methods for H2 production include partial oxidation of hydrocarbons:[77]
2 CH4 + O2 → 2 CO + 4 H2
and the coal reaction, which can serve as a prelude to the shift reaction above:[76]
C + H2O → CO + H2
Hydrogen is sometimes produced and consumed in the same industrial process, without being separated. In the
Haber process for the production of ammonia, hydrogen is generated from natural gas.[78] Electrolysis of brine to
yield chlorine also produces hydrogen as a co-product.[79]
Thermochemical
There are more than 200 thermochemical cycles which can be used for water splitting, around a dozen 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 are under research and in testing phase to produce hydrogen and
oxygen from water and heat without using electricity.[80] A number of laboratories (including in France, Germany,
Greece, Japan, and the USA) are developing thermochemical methods to produce hydrogen from solar energy and
water.[81]
Hydrogen 11
Anaerobic corrosion
Under anaerobic conditions, iron and steel alloys are slowly oxidized by the protons of water concomitantly reduced
in molecular hydrogen (H2). The anaerobic corrosion of iron leads first to the formation of ferrous hydroxide (green
rust) and can be described by the following reaction:
Fe + 2 H2O → Fe(OH)2 + H2
In its turn, under anaerobic conditions, the ferrous hydroxide (Fe(OH)2 ) can be oxidized by the protons of water to
form magnetite and molecular hydrogen. This process is described by the Schikorr reaction:
3 Fe(OH)2 → Fe3O4 + 2 H2O + H2
ferrous hydroxide → magnetite + water + hydrogen
The well crystallized magnetite (Fe3O4) is thermodynamically more stable than the ferrous hydroxide (Fe(OH)2 ).
This process occurs during the anaerobic corrosion of iron and steel in oxygen-free groundwater and in reducing
soils below the water table.
Applications
Large quantities of H2 are needed in the petroleum and chemical industries. The largest application of H2 is for the
processing ("upgrading") of fossil fuels, and in the production of ammonia. The key consumers of H2 in the
petrochemical plant include hydrodealkylation, hydrodesulfurization, and hydrocracking. H2 has several other
important uses. H2 is used as a hydrogenating agent, particularly in increasing the level of saturation of unsaturated
fats and oils (found in items such as margarine), and in the production of methanol. It is similarly the source of
hydrogen in the manufacture of hydrochloric acid. H2 is also used as a reducing agent of metallic ores.[82]
Hydrogen is highly soluble in many rare earth and transition metals[83] and is soluble in both nanocrystalline and
amorphous metals.[84] Hydrogen solubility in metals is influenced by local distortions or impurities in the crystal
lattice.[85] These properties may be useful when hydrogen is purified by passage through hot palladium disks, but the
gas serves as a metallurgical problem as hydrogen solubility contributes in an unwanted way to embrittle many
metals,[8] complicating the design of pipelines and storage tanks.[9]
Apart from its use as a reactant, H2 has wide applications in physics and engineering. It is used as a shielding gas in
welding methods such as atomic hydrogen welding.[86] [87] H2 is used as the rotor coolant in electrical generators at
power stations, because it has the highest thermal conductivity of any gas. Liquid H2 is used in cryogenic research,
including superconductivity studies.[88] Because H2 is lighter than air, having a little more than 1⁄15 of the density of
air, it was once widely used as a lifting gas in balloons and airships.[89]
In more recent applications, hydrogen is used pure or mixed with nitrogen (sometimes called forming gas) as a tracer
gas for minute leak detection. Applications can be found in the automotive, chemical, power generation, aerospace,
and telecommunications industries.[90] Hydrogen is an authorized food additive (E 949) that allows food package
Hydrogen 12
Energy carrier
Hydrogen is not an energy resource,[96] except in the hypothetical context of commercial nuclear fusion power plants
using deuterium or tritium, a technology presently far from development.[97] The Sun's energy comes from nuclear
fusion of hydrogen, but this process is difficult to achieve controllably on Earth.[98] Elemental hydrogen from solar,
biological, or electrical sources require more energy to make it than is obtained by burning it, so in these cases
hydrogen functions as an energy carrier, like a battery. Hydrogen may be obtained from fossil sources (such as
methane), but these sources are unsustainable.[96]
The energy density per unit volume of both liquid hydrogen and compressed hydrogen gas at any practicable
pressure is significantly less than that of traditional fuel sources, although the energy density per unit fuel mass is
higher.[96] Nevertheless, elemental hydrogen has been widely discussed in the context of energy, as a possible future
carrier of energy on an economy-wide scale.[99] For example, CO2 sequestration followed by carbon capture and
storage could be conducted at the point of H2 production from fossil fuels.[100] Hydrogen used in transportation
would burn relatively cleanly, with some NOx emissions,[101] but without carbon emissions.[100] However, the
infrastructure costs associated with full conversion to a hydrogen economy would be substantial.[102]
Semiconductor industry
Hydrogen is employed to saturate broken ("dangling") bonds of amorphous silicon and amorphous carbon that helps
stabilizing material properties.[103] It is also a potential electron donor in various oxide materials, including ZnO,[104]
[105]
SnO2, CdO, MgO,[106] ZrO2, HfO2, La2O3, Y2O3, TiO2, SrTiO3, LaAlO3, SiO2, Al2O3, ZrSiO4, HfSiO4, and
SrZrO3.[107]
Biological reactions
H2 is a product of some types of anaerobic metabolism and is produced by several microorganisms, usually via
reactions catalyzed by iron- or nickel-containing enzymes called hydrogenases. These enzymes catalyze the
reversible redox reaction between H2 and its component two protons and two electrons. Creation of hydrogen gas
occurs in the transfer of reducing equivalents produced during pyruvate fermentation to water.[108]
Water splitting, in which water is decomposed into its component protons, electrons, and oxygen, occurs in the light
reactions in all photosynthetic organisms. Some such 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.[109] Efforts have been undertaken to genetically modify
cyanobacterial hydrogenases to efficiently synthesize H2 gas even in the presence of oxygen.[110] Efforts have also
been undertaken with genetically modified alga in a bioreactor.[111]
Hydrogen 13
See also
• Hydrogen atom
• Hydrogen bond
• Hydrogen ion
• Hydrogen production
• Isotopes of hydrogen
• Liquid hydrogen
• Metallic hydrogen
• Solid hydrogen
• Fuel cell
Notes
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Hydrogen 14
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References
Further reading
• Chart of the Nuclides (http://chartofthenuclides.com/default.html). Fourteenth Edition. General Electric
Company. 1989.
• Ferreira-Aparicio, P; M. J. Benito, J. L. Sanz (2005). "New Trends in Reforming Technologies: from Hydrogen
Industrial Plants to Multifuel Microreformers". Catalysis Reviews 47: 491–588.
doi:10.1080/01614940500364958.
• Newton, David E. (1994). The Chemical Elements. New York, NY: Franklin Watts. ISBN 0-531-12501-7.
• Rigden, John S. (2002). Hydrogen: The Essential Element. Cambridge, MA: Harvard University Press.
ISBN 0-531-12501-7.
• Romm, Joseph, J. (2004). The Hype about Hydrogen, Fact and Fiction in the Race to Save the Climate. Island
Press. ISBN 1-55963-703-X. Author interview (http://www.globalpublicmedia.com/transcripts/635) at Global
Public Media.
• Scerri, Eric (2007). The Periodic System, Its Story and Its Significance,. New York, NY: Oxford University Press.
ISBN 0-19-530573-6.
External links
• Basic Hydrogen Calculations of Quantum Mechanics (http://www.physics.drexel.edu/~tim/open/hydrofin/)
• Hydrogen phase diagram (http://www.astro.washington.edu/users/larson/Astro150b/Lectures/
JupSatUraNep/hydrogen_phase.gif)
• Wavefunction of hydrogen (http://hyperphysics.phy-astr.gsu.edu/Hbase/quantum/hydwf.html#c3)
koi:Ваувтыр
Antihydrogen 18
Antihydrogen
Antihydrogen is the antimatter counterpart of hydrogen. Whereas the
common hydrogen atom is composed of an electron and proton, the
antihydrogen atom is made up of a positron and antiproton.
The standard symbol for antihydrogen is H that is, H with an overbar
(pronounced /ˌeɪtʃ ˈbɑr/ aitch-bar).
Characteristics
According to the CPT theorem of particle physics, antihydrogen atoms
Antihydrogen consists of an antiproton and a
should have many of the characteristics regular hydrogen atoms have,
positron
i.e. they should have the same mass, magnetic moment, and transition
frequencies (see Atomic spectroscopy) between its atomic quantum
states. For example, excited antihydrogen atoms are expected to glow with the same color as that of regular
hydrogen. Antihydrogen atoms should be attracted to other matter or antimatter gravitationally with a force of the
same magnitude as ordinary hydrogen atoms would experience. This would not be true if antimatter has negative
gravitational mass, which is considered highly unlikely, though not yet empirically disproven.
When antihydrogen atoms come into contact with ordinary matter, their constituents quickly annihilate. The
positron, which is an elementary particle, annihilates on electrons in ordinary matter and the rest mass of the
positrons and its annihilation partner is released as energy in the form of gamma rays. The antiproton on the other
hand is made up of antiquarks that combine with the quarks in either neutrons or protons in normal matter and the
annihilation results in high-energy particles called pions. These pions in turn quickly decay into other particles called
muons, neutrinos, positrons, and electrons, and these particles rapidly dissipate. If antihydrogen atoms were to be
suspended in a perfect vacuum, however, they should survive indefinitely.
Production
In 1995, the first antihydrogen was produced by a team of researchers under the lead of Walter Oelert at the CERN
laboratory in Geneva.[1] The experiment took place in the LEAR, where antiprotons, which were produced in a
particle accelerator, were shot at xenon clusters[2] . When an antiproton gets close to a xenon nucleus, an
electron-positron-pair can be produced, and with some probability the positron will be captured by the antiproton to
form antihydrogen. The probability for producing antihydrogen from one antiproton was only about × 10−19, so this
method is not well suited for the production of substantial amounts of antihydrogen, as detailed calculations had
shown before.[3]
The experiments done at CERN were later, in 1997, reproduced at Fermilab in the US where a somewhat different
cross section for the process was identified[4] . Both experiment resulted in highly energetic, or warm, antihydrogen,
which were unsuitable for detailed study. Subsequently CERN build the Antiproton Decelerator in order to support
efforts towards creating low energy antihydrogen which could be used for tests of fundamental symmetries.
Antihydrogen 19
Natural occurrence
Today, no conclusive spectral signature for the presence of antihydrogen could be reported, since measuring the
spectrum of antihydrogen, especially the 1S-2S interval, is exactly the goal of these CERN located collaborations.
See also
• Gravitational interaction of antimatter
References
[1] Freedman, David H.. "Antiatoms: Here Today . . ." (http:/ / discovermagazine. com/ 1997/ jan/ antiatomsheretod1029). Discover Magazine. .
[2] G.Baur, G.Boero, S.Brauksiepe, A.Buzzo, W.Eyrich, R.Geyer, D.Grzonka, J.Hauffe, K.Kilian, M.LoVetere, M. MacriM.Moosburger,
R.Nellen, W. Oelert, S.Passaggio, A.Pozzo, K.Röhrich, K.Sachs, G.Scheppers, T.Sefzick, R.S.Simon, R.Stratmann, F.Stinzing, M.Wolke
(1996). "Production of Antihydrogen". Physics Letters B 368: 251ff.
[3] A. Aste; G.Baur, D. Trautmann, K. Hencken (1993). "Electromagnetic Pair Production with Capture". Physical Review A 50: 3980ff.
[4] Blanford, G.; D.C. Christian, K. Gollwitzer, M. Mandelkern, C.T. Munger, J. Schultz, G. Zioulas (December 1997). "Observation of Atomic
Antihydrogen". Physical Review Letters (Fermi National Accelerator Laboratory). "FERMILAB-Pub-97/398-E E862 ... p and H experiments".
[5] M. Amoretti, C. Amsler, G. Bonomi, A. Bouchta, P. Bowe, C. Carraro, C. L. Cesar, M. Charlton, M. J. T. Collier, M. Doser, V. Filippini, K.
S. Fine, A. Fontana, M. C. Fujiwara, R. Funakoshi, P. Genova, J. S. Hangst, R. S. Hayano, M. H. Holzscheiter, L. V. Jørgensen, V.
Lagomarsino, R. Landua, D. Lindelöf, E. Lodi Rizzini, M. Macri, N. Madsen, G. Manuzio, M. Marchesotti, P. Montagna, H. Pruys, C.
Regenfus, P. Riedler, J. Rochet, A. Rotondi, G. Rouleau, G. Testera, A. Variola, T. L. Watson and D. P. van der Werf (2002). "Production and
detection of cold antihydrogen atoms" (http:/ / www. nature. com/ nature/ journal/ v419/ n6906/ full/ nature01096. html). Nature 419 (6906):
456ff. doi:10.1038/nature01096. PMID 12368849. .
[6] Gabrielse, G.; N. S. Bowden, P. Oxley, A. Speck, C. H. Storry, J. N. Tan, M.Wessels, D. Grzonka, W. Oelert, G. Schepers, T. Sefzick,
J.Walz, H. Pittner, T.W. Ha¨nsch, and E. A. Hessels (2 DECEMBER 2002). "Driven Production of Cold Antihydrogen and the First Measured
Distribution of Antihydrogen States". Ph Ysica L R Ev I Ew L et T Ers 89 (23): 233401. doi:10.1103/PhysRevLett.89.233401. "antihydrogen
(H)".
[7] N. Madsen (2010). "Cold antihydrogen: a new frontier in fundamental physics" (http:/ / rsta. royalsocietypublishing. org/ content/ 368/ 1924/
3671. full). Phil. Trans. R. Soc. A 368 (1924): 1924ff. doi:10.1098/rsta.2010.0026. PMID 20603376. .
Hydrogen atom 20
Hydrogen atom
Hydrogen-1
Full table
General
Neutrons 0
Protons 1
Nuclide Data
Half-life Stable
Spin ½+
equation goes much further than the Bohr model however, because it also yields the shape of the electron's wave
function ("orbital") for the various possible quantum-mechanical states, thus explaining the anisotropic character of
Hydrogen atom 21
atomic bonds.
The Schrödinger equation also applies to more complicated atoms and molecules. However, in most such cases the
solution is not analytical and either computer calculations are necessary or simplifying assumptions must be made.
Energy levels
The energy levels of hydrogen, including fine structure are given by
where α is the fine-structure constant and j is a number which is the total angular momentum eigenvalue; that is, ℓ ±
1/2 depending on the direction of the electron spin.
The value of 13.6 eV is called the Rydberg constant and can be found from the Bohr model, and is given by
where me is the mass of the electron, qe is the charge of the electron, h is the Planck constant, and ε0 is the vacuum
permittivity.
The Rydberg constant is connected to the fine-structure constant by the relation
Wavefunction
The normalized position wavefunctions, given in spherical coordinates
are:
where:
where is the representation of the wavefunction in Dirac notation, and is the Kronecker delta
[5]
function.
Angular momentum
The eigenvalues for Angular momentum operator:
The "ground state", i.e. the state of lowest energy, in which the electron Probability densities through the xz-plane for the
electron at different quantum numbers (ℓ, across
is usually found, is the first one, the 1s state (principal quantum level n
top; n, down side; m = 0)
= 1, ℓ = 0).
An image with more orbitals is also available (up to higher numbers n and ℓ).
Black lines occur in each but the first orbital: these are the nodes of the wavefunction, i.e. where the probability
density is zero. (More precisely, the nodes are Spherical harmonics that appear as a result of solving Schrodinger's
equation in polar coordinates.)
The quantum numbers determine the layout of these nodes.[6] There are:
• total nodes,
• of which are angular nodes:
• angular nodes go around the axis (in the xy plane). (The figure above does not show these nodes since it plots
cross-sections through the xz-plane.)
• (the remaining angular nodes) occur on the (vertical) axis.
• (the remaining non-angular nodes) are radial nodes.
Hydrogen atom 24
Hydrogen ion
Hydrogen is not found without its electron in ordinary chemistry (room temperatures and pressures), as ionized
hydrogen is highly chemically reactive. When ionized hydrogen is written as "H+" as in the solvation of classical
acids such hydrochloric acid, the hydronium ion, H3O+, is meant, not a literal ionized single hydrogen atom. In that
case, the acid transfers the proton to H2O to form H3O+.
Ionized hydrogen without its electron, or free protons, are common in the interstellar medium, and solar wind.
Hydrogen atom 25
See also
• Atom
• Balmer series
• Bohr model
• Deuterium
• Helium atom
• Isotopes of hydrogen
• Proton decay
• Quantum chemistry
• Quantum field theory
• Quantum mechanics
• Quantum state
• Theoretical and experimental justification for the Schrödinger equation
• Trihydrogen cation
• Tritium
References
[1] Pauli, W (1926). "Über das Wasserstoffspektrum vom Standpunkt der neuen Quantenmechanik". Zeitschrift für Physik 36: 336–363.
doi:10.1007/BF01450175.
[2] Kleinert H. (1968). "Group Dynamics of the Hydrogen Atom". Lectures in TheoreticalPhysics, edited by W.E. Brittin and A.O. Barut,
Gordon and Breach, N.Y. 1968: 427–482. .
[3] Duru I.H., Kleinert H. (1979). "Solution of the path integral for the H-atom" (http:/ / www. physik. fu-berlin. de/ ~kleinert/ kleiner_re65/ 65.
pdf). Physics Letters B 84 (2): 185–188. doi:10.1016/0370-2693(79)90280-6. .
[4] Duru I.H., Kleinert H. (1982). "Quantum Mechanics of H-Atom from Path Integrals" (http:/ / www. physik. fu-berlin. de/ ~kleinert/
kleiner_re83/ 83. pdf). Fortschr. Phys 30 (2): 401–435. doi:10.1002/prop.19820300802. .
[5] Introduction to Quantum Mechanics, Griffiths 4.89
[6] Lecture notes on quantum numbers (http:/ / www. physics. byu. edu/ faculty/ durfee/ courses/ Summer2009/ physics222/
AtomicQuantumNumbers. pdf)
Books
• Griffiths, David J. (1995). Introduction to Quantum Mechanics. Prentice Hall. ISBN 0-13-111892-7.
Section 4.2 deals with the hydrogen atom specifically, but all of Chapter 4 is relevant.
• Bransden, B.H.; C.J. Joachain (1983). Physics of Atoms and Molecules. Longman. ISBN 0-582-44401-2.
• Kleinert, H. (2009). Path Integrals in Quantum Mechanics, Statistics, Polymer Physics, and Financial Markets,
4th edition, Worldscibooks.com (http://www.worldscibooks.com/physics/7305.html), World Scientific,
Singapore (also available online Physik.fi-berlin.de (http://www.physik.fu-berlin.de/~kleinert/re.html#B8)
External links
• Physics of hydrogen atom on Scienceworld (http://scienceworld.wolfram.com/physics/HydrogenAtom.html)
• Interactive graphical representation of orbitals (http://webphysics.davidson.edu/faculty/dmb/hydrogen/)
• Applet which allows viewing of all sorts of hydrogenic orbitals (http://www.falstad.com/qmatom/)
• The Hydrogen Atom: Wave Functions, and Probability Density "pictures" (http://panda.unm.edu/courses/
finley/P262/Hydrogen/WaveFcns.html)
• Basic Quantum Mechanics of the Hydrogen Atom (http://www.physics.drexel.edu/~tim/open/hydrofin)
Hydrogen-like atom 26
Hydrogen-like atom
A hydrogen-like ion is any atomic nucleus with one electron and thus is isoelectronic with hydrogen. Except for the
hydrogen atom itself (which is neutral) these ions carry the positive charge e(Z-1), where Z is the atomic number of
the atom. Examples of hydrogen-like ions are He+, Li2+, Be3+ and B4+. Because hydrogen-like ions are two-particle
systems with an interaction depending only on the distance between the two particles, their (non-relativistic)
Schrödinger equation can be solved in analytic form. The solutions are one-electron functions and are referred to as
hydrogen-like atomic orbitals.[1]
Hydrogen-like atomic orbitals are eigenfunctions of the one-electron angular momentum operator L and its z
component Lz. The energy eigenvalues do not depend on the corresponding quantum numbers, but solely on the
principal quantum number n. Hence, a hydrogen-like atomic orbital is uniquely identified by the values of: principal
quantum number n, angular momentum quantum number l, and magnetic quantum number m. To this must be added
the two-valued spin quantum number ms = ±½ in application of the Aufbau principle. This principle restricts the
allowed values of the four quantum numbers in electron configurations of more-electron atoms. In hydrogen-like
atoms all degenerate orbitals of fixed n and l, m and s varying between certain values (see below) form an atomic
shell.
The Schrödinger equation of atoms or atomic ions with more than one electron has not been solved analytically,
because of the computational difficulty imposed by the Coulomb interaction between the electrons. Numerical
methods must be applied in order to obtain (approximate) wavefunctions or other properties from quantum
mechanical calculations. Due to the spherical symmetry (of the Hamiltonian), the total angular momentum J of an
atom is a conserved quantity. Many numerical procedures start from products of atomic orbitals that are
eigenfunctions of the one-electron operators L and Lz. The radial parts of these atomic orbitals are sometimes
numerical tables or are sometimes Slater orbitals. By angular momentum coupling many-electron eigenfunctions of
J2 (and possibly S2) are constructed.
In quantum chemical calculations hydrogen-like atomic orbitals cannot serve as an expansion basis, because they are
not complete. The non-square-integrable continuum (E > 0) states must be included to obtain a complete set, i.e., to
span all of one-electron Hilbert space.[2]
Mathematical characterization
The atomic orbitals of hydrogen-like ions are solutions to the Schrödinger equation in a spherically symmetric
potential. In this case, the potential term is the potential given by Coulomb's law:
where
• ε0 is the permittivity of the vacuum,
• Z is the atomic number (number of protons in the nucleus),
• e is the elementary charge (charge of an electron),
• r is the distance of the electron from the nucleus.
After writing the wave function as a product of functions:
(in spherical coordinates), where are spherical harmonics, we arrive at the following Schrödinger equation:
where is, approximately, the mass of the electron. More accurately, it is the reduced mass of the system
consisting of the electron and the nucleus.
Hydrogen-like atom 27
Different values of l give solutions with different angular momentum, where l (a non-negative integer) is the
quantum number of the orbital angular momentum. The magnetic quantum number m (satisfying ) is
the (quantized) projection of the orbital angular momentum on the z-axis. See here for the steps leading to the
solution of this equation.
where:
Here, is the reduced mass of the nucleus-electron system, that is, where is the
mass of the nucleus. Typically, the nucleus is much more massive than the electron, so .
• .
Quantum numbers
The quantum numbers n, l and m are integers and can have the following values:
See for a group theoretical interpretation of these quantum numbers this article. Among other things, this article
gives group theoretical reasons why and .
Angular momentum
Each atomic orbital is associated with an angular momentum L. It is a vector operator, and the eigenvalues of its
square L2 ≡ Lx2 + Ly2 + Lz2 are given by:
The projection of this vector onto an arbitrary direction is quantized. If the arbitrary direction is called z, the
quantization is given by:
where m is restricted as described above. Note that L2 and Lz commute and have a common eigenstate, which is in
accordance with Heisenberg's uncertainty principle. Since Lx and Ly do not commute with Lz, it is not possible to find
a state which is an eigenstate of all three components simultaneously. Hence the values of the x and y components
are not sharp, but are given by a probability function of finite width. The fact that the x and y components are not
well-determined, implies that the direction of the angular momentum vector is not well determined either, although
its component along the z-axis is sharp.
Hydrogen-like atom 28
These relations do not give the total angular momentum of the electron. For that, electron spin must be included.
This quantization of angular momentum closely parallels that proposed by Niels Bohr (see Bohr model) in 1913,
with no knowledge of wavefunctions.
Notes
[1] In quantum chemistry an orbital is synonymous with "a one-electron function", a square integrable function of x, y, and z.
[2] This was observed as early as 1929 by E. A. Hylleraas, Z. f. Physik vol. 48, p. 469 (1929). English translation in H. Hettema, Quantum
Chemistry, Classic Scientific Papers, p. 81, World Scientific, Singapore (2000). Later it was pointed out again by H. Shull and P.-O. Löwdin,
J. Chem. Phys. vol. 23, p. 1362 (1955).
See also
• Rydberg atom
• Positronium
• Exotic atom
• Two-electron atom
References
• Tipler, Paul & Ralph Llewellyn (2003). Modern Physics (4th ed.). New York: W. H. Freeman and Company.
ISBN 0-7167-4345-0
Hydrogen spectral series 29
Physics
In physics, the spectral lines of hydrogen correspond to particular jumps of the electron between energy levels. The
simplest model of the hydrogen atom is given by the Bohr model. When an electron jumps from a higher energy to a
lower, a photon of a specific wavelength is emitted.
The spectral lines are grouped into
series according to n'. Lines are named
sequentially starting from the longest
wavelength/lowest frequency of the
series, using Greek letters within each
series. For example, the 2 → 1 line is
called "Lyman-alpha" (Ly-α), while
the 7 → 3 line is called
"Paschen-delta" (Pa-δ). Some
hydrogen spectral lines fall outside
these series, such as the 21 cm line;
these correspond to much rarer atomic
events such as hyperfine transitions.[1]
The fine structure also results in single
spectral lines appearing as two or more
Electron transitions and their resulting wavelengths for Hydrogen. Energy levels are not closely grouped thinner lines, due to
to scale. relativistic corrections.[2] Typically
one can only observe these series from
pure hydrogen samples in a lab. Many of the lines are very faint and additional lines can be caused by other elements
(such as helium if using sunlight, or nitrogen in the air). Lines outside of the visible spectrum typically cannot be
seen in observations of sunlight, as the atmosphere absorbs most infra-red and ultraviolet wavelengths.
Hydrogen spectral series 30
Rydberg formula
The energy differences between levels in the Bohr model, and hence the wavelengths of emitted/absorbed photons, is
given by the Rydberg formula[3] :
where n is the initial energy level, n′ is the final energy level, and R is the Rydberg constant.[4] Meaningful values
are returned only when n is greater than n′ and the limit of one over infinity is taken to be zero.
Series
All wavelengths are given to 3 significant figures.
λ (nm)
2 122
3 103
4 97.2
5 94.9
6 93.7
91.1
The series is named after its discoverer, Theodore Lyman, who discovered the spectral lines from 1906-1914. All the
wavelengths in the Lyman series are in the ultraviolet band.[5] [6]
λ (nm)
3 656
4 486
5 434
6 410
7 397
365
Named after Johann Balmer, who discovered the Balmer formula, an empirical equation to predict the Balmer
series, in 1885. Balmer lines are historically referred to as "H-alpha", "H-beta", "H-gamma" and so on, where H is
the element hydrogen.[7] Four of the Balmer lines are in the technically "visible" part of the spectrum, with
wavelengths longer than 400 nm. Parts of the Balmer series can be seen in the solar spectrum. H-alpha is an
important line used in astronomy to detect the presence of hydrogen.
λ (nm)
4 1870
5 1280
6 1090
7 1000
8 954
820
Named after the Austro-German physicist Friedrich Paschen who first observed them in 1908. The Paschen lines all
lie in the infrared band.[8]
λ (nm)
5 4050
6 2630
7 2170
8 1940
9 1820
1460
Named after the American physicist Frederick Sumner Brackett who first observed the spectral lines in 1922.[9]
λ (nm)
6 7460
7 4650
8 3740
9 3300
10 3040
2280
λ (nm)
7 12400
8 7500
9 5910
10 5130
11 4670
3280
See also
• Astronomical spectroscopy
• Bohr Theory and Balmer-Rydberg Equation
• Moseley's law
• Theoretical and experimental justification for the Schrödinger equation
References
[1] "The Hydrogen 21-cm Line" (http:/ / hyperphysics. phy-astr. gsu. edu/ hbase/ quantum/ h21. html). Hyperphysics. Georgia State University.
2004-10-30. . Retrieved 2009-03-18.
[2] Liboff, Richard L. (2002). Introductory Quantum Mechanics. Addison-Wesley. ISBN 0-8053-8714-5.
[3] Bohr, Niels (1985), "Rydberg's discovery of the spectral laws", in Kalckar, J., N. Bohr: Collected Works, 10, Amsterdam: North-Holland
Publ., pp. 373–9
[4] "CODATA Recommended Values of the Fundamental Physical Constants: 2006" (http:/ / physics. nist. gov/ cuu/ Constants/ codata. pdf)
(PDF). Committee on Data for Science and Technology (CODATA). NIST. .
[5] Lyman, Theodore (1906), "The Spectrum of Hydrogen in the Region of Extremely Short Wave-Length" (http:/ / www. jstor. org/ stable/
25058084), Memoirs of the American Academy of Arts and Sciences, New Series 13 (3): 125–146, ISSN 00966134,
[6] Lyman, Theodore (1914), "An Extension of the Spectrum in the Extreme Ultra-Violet", Nature 93: 241, doi:10.1038/093241a0
[7] Balmer, J. J. (1885), "Notiz uber die Spectrallinien des Wasserstoffs" (http:/ / www3. interscience. wiley. com/ journal/ 112487600/ abstract),
Annalen der Physik 261 (5): 80–87, doi:10.1002/andp.18852610506,
[8] Paschen, Friedrich (1908), "Zur Kenntnis ultraroter Linienspektra. I. (Normalwellenlängen bis 27000 Å.-E.)" (http:/ / www3. interscience.
wiley. com/ journal/ 112500956/ abstract), Annalen der Physik 332 (13): 537–570, doi:10.1002/andp.19083321303,
[9] Brackett, Frederick Sumner (1922), "Visible and infra-red radiation of hydrogen", Astrophysical Journal 56: 154, doi:10.1086/142697
[10] Pfund, A. H. (1924), "The emission of nitrogen and hydrogen in infrared", J. Opt. Soc. Am. 9 (3): 193–196, doi:10.1364/JOSA.9.000193
Hydrogen spectral series 33
[11] Humphreys, C.J. (1953), "Humphreys Series", J. Research Natl. Bur. Standards 50
External links
• Spectral series of hydrogen animation (http://www.bigs.de/BLH/en/index.php?option=com_content&
view=category&layout=blog&id=50&Itemid=221)
Liquid hydrogen 34
Liquid hydrogen
Liquid hydrogen
Identifiers
PubChem [2]
783
UNII [4]
7YNJ3PO35Z
UN number 1966
SMILES
InChI
InChI key
Properties
Molecular formula H2
Density [5]
67.8 kg·m-3 (4.23 lb./cu.ft)
Hazards
NFPA 704
Autoignition [5]
1060 °F = 571 °C
temperature
Infobox references
Liquid hydrogen 35
Liquid hydrogen (LH2 or LH2) is the liquid state of the element hydrogen. Hydrogen is found naturally in the
molecular H2 form.
To exist as a liquid, H2 must be pressurized above and cooled below hydrogen's Critical point, however for hydrogen
to be in a full liquid state without boiling off it needs to be cooled to 20.28 K[7] (−423.17 °F/−252.87°C)[8] [9] while
still pressurized. One common method of obtaining liquid hydrogen involves a compressor resembling a jet engine in
both appearance and principle. Liquid hydrogen is typically used as a concentrated form of hydrogen storage. As in
any gas, storing it as liquid takes less space than storing it as a gas at normal temperature and pressure. Once
liquefied it can be maintained as a liquid in pressurized and thermally insulated containers.
Liquid hydrogen consists of 99.79% parahydrogen, 0.21% orthohydrogen.[10]
History
1756 - The first documented public demonstration of artificial refrigeration by William Cullen[11] , Gaspard Monge
liquefied the first gas producing liquid sulfur dioxide in 1784. Michael Faraday liquefied ammonia to cause cooling,
Oliver Evans designed the first closed circuit refrigeration machine in 1805, Jacob Perkins patented the first
refrigerating machine in 1834 and John Gorrie patented his mechanical refrigeration machine in 1851 in the US to
make ice to cool the air[12] [13] , Siemens introduced the Regenerative cooling concept in 1857, Carl von Linde
patented equipment to liquefy air using tile Joule Thomson expansion process and regenerative cooling[14] in 1876,
in 1885 Zygmunt Florenty Wróblewski published hydrogen's critical temperature as 33 K; critical pressure, 13.3
atmospheres; and boiling point, 23 K.
Hydrogen was liquefied for the first time by James Dewar in 1898 by using regenerative cooling and his invention,
the vacuum flask. The first synthesis of the stable isomer form of liquid hydrogen, parahydrogen was achieved by
Paul Harteck and Karl Friedrich Bonhoeffer in 1929.
Uses
It is a common liquid rocket fuel for rocket applications. In most rocket engines fueled by liquid hydrogen, it first
cools the nozzle and other parts before being mixed with the oxidizer (usually liquid oxygen (LOX)) and burned to
produce water with traces of ozone and hydrogen peroxide. Practical H2/O2 rocket engines run fuel-rich so that the
exhaust contains some unburned hydrogen. This reduces combustion chamber and nozzle erosion. It also reduces the
molecular weight of the exhaust that can actually increase specific impulse despite the incomplete combustion.
Liquid hydrogen 36
RTECS MW8900000
Liquid hydrogen can be used as the fuel storage in an internal combustion engine or fuel cell. Various submarines
(Type 212 submarine, Type 214 submarine) and concept hydrogen vehicles have been built using this form of
hydrogen (see DeepC, BMW H2R). Due to its similarity, builders can sometimes modify and share equipment with
systems designed for LNG. However, because of the lower volumetric energy, the hydrogen volumes needed for
combustion are large. Unless LH2 is injected instead of gas, hydrogen-fueled piston engines usually require larger
fuel systems. Unless direct injection is used, a severe gas-displacement effect also hampers maximum breathing and
increases pumping losses.
Liquid hydrogen is also used to cool neutrons to be used in neutron scattering. Since neutrons and hydrogen nuclei
have similar masses, kinetic energy exchange per interaction is maximum (elastic collision).
Advantages
The byproduct of its combustion with oxygen alone is water vapor(although if its combustion is with oxygen and
nitrogen it can form toxic chemicals), which can be cooled with the some of liquid hydrogen. Since water is
considered harmless to the environment, the engine is considered "zero emissions." Liquid hydrogen also has a much
higher specific energy than gasoline, natural gas, or diesel[16] .
Drawbacks
The density of liquid hydrogen is only 70.99 g/L (at 20 K). Liquid hydrogen requires cryogenic storage technology
such as special thermally insulated containers and requires special handling common to all cryogenic fuels. This is
similar to, but more severe than liquid oxygen. Even with thermally insulated containers it is difficult to keep such a
low temperature, and the hydrogen will gradually leak away (Typically it will evaporate at a rate of 1% per day[17] ).
It also shares many of the same safety issues as other forms of hydrogen, as well as being cold enough to liquefy
(and possibly solidify) atmospheric oxygen which can be an explosion hazard.
Liquid hydrogen 37
See also
• Hydrogen safety
• Compressed hydrogen
• Cryo-adsorption
• Expansion ratio
• Gasoline gallon equivalent
• industrial gas
• Slush hydrogen
• Solid hydrogen
• Metallic hydrogen
• Hydrogen infrastructure
• Liquid hydrogen tank car
• Liquid hydrogen tanktainer Tank for liquid hydrogen of Linde, Museum Autovision,
• Liquid hydrogen tank truck Altlußheim, Germany
• Liquefaction of gases
References
[1] http:/ / www. commonchemistry. org/ ChemicalDetail. aspx?ref=1333-74-0
[2] http:/ / pubchem. ncbi. nlm. nih. gov/ summary/ summary. cgi?cid=783
[3] http:/ / www. chemspider. com/ 762
[4] http:/ / fdasis. nlm. nih. gov/ srs/ srsdirect. jsp?regno=7YNJ3PO35Z
[5] Information specific to liquid hydrogen (http:/ / www. safety. seas. harvard. edu/ services/ hydrogen. html), harvard.edu, accessed 2009-06-12
[6] http:/ / en. wikipedia. org/ wiki/ %3Aliquid_hydrogen
[7] IPTS-1968 (http:/ / media. iupac. org/ publications/ pac/ 1970/ pdf/ 2203x0555. pdf), iupac.org, accessed 2009-06-12
[8] Chemical elements data references
[9] Properties Of Gases (http:/ / www. roymech. co. uk/ Useful_Tables/ Matter/ Prop_Gas. htm)
[10] Liquid Air/LH2 (http:/ / www. astronautix. com/ props/ liqirlh2. htm)
[11] William Cullen, Of the Cold Produced by Evaporating Fluids and of Some Other Means of Producing Cold, in Essays and Observations
Physical and Literary Read Before a Society in Edinburgh and Published by Them, II, (Edinburgh 1756)
[12] 1851 John Gorrie (http:/ / www. myoutbox. net/ popch20. htm)
[13] 1851 Patent 8080 (http:/ / patimg2. uspto. gov/ . piw?Docid=00008080& homeurl=http:/ / patft. uspto. gov/ netacgi/
nph-Parser?Sect1=PTO1%26Sect2=HITOFF%26d=PALL%26p=1%26u=%252Fnetahtml%252FPTO%252Fsrchnum.
htm%26r=1%26f=G%26l=50%26s1=0008,080. PN. %26OS=PN/ 0008,080%26RS=PN/ 0008,080& PageNum=& Rtype=& SectionNum=&
idkey=NONE& Input=View+ first+ page)
[14] Hydrogen through the Nineteenth Century (http:/ / history. nasa. gov/ SP-4404/ app-a1. htm)
[15] Ortho-Para conversion. Pag. 13 (http:/ / www. mae. ufl. edu/ NasaHydrogenResearch/ h2webcourse/ L11-liquefaction2. pdf)
[16] http:/ / www. almc. army. mil/ alog/ issues/ MayJun00/ MS492. htm
[17] http:/ / www. almc. army. mil/ alog/ issues/ MayJun00/ MS492. htm
Solid hydrogen 38
Solid hydrogen
Solid hydrogen is the solid state of the element hydrogen, achieved by decreasing the temperature below hydrogen's
melting point of 14.01 K (−259.14 °C). It was collected for the first time by James Dewar in 1899 and published
with the title "Sur la solidification de l'hydrogène" in the Annales de Chimie et de Physique, 7th series, vol.18, Oct.
1899.[1] [2]
Research
• Solid-state physics
• 1972: The experimental determination of the melting characteristics of solid hydrogen [3]
See also
• Compressed hydrogen
• Liquid hydrogen
• Slush hydrogen
• Metallic hydrogen
• Timeline of hydrogen technologies
References
[1] Correspondence and General A-I DEWAR/Box D I (http:/ / www. nationalarchives. gov. uk/ A2A/ records. aspx?cat=116-dewar_1&
cid=-1& Gsm=2008-06-18#-1)
[2] Dewar, James (1899). "Sur la solidification de l'hydrogène" (http:/ / gallica. bnf. fr/ ark:/ 12148/ bpt6k349183/ f143. table). Annales de
Chimie et de Physique 18: 145–150. .
[3] " Melting Characteristics and Bulk Thermophysical Properties of Solid Hydrogen (http:/ / oai. dtic. mil/ oai/ oai?verb=getRecord&
metadataPrefix=html& identifier=AD0748847)" (1972)
External links
• " Properties of solid hydrogen at very low temperatures (http://sciencelinks.jp/j-east/article/200211/
000020021102A0308056.php)" (2001)
• " Solid hydrogen experiments for atomic propellants (http://gltrs.grc.nasa.gov/reports/2002/
TM-2002-211915.pdf)"
Metallic hydrogen 39
Metallic hydrogen
Metallic hydrogen is a state of hydrogen which results when it is sufficiently compressed and undergoes a phase
transition; it is an example of degenerate matter. Solid metallic hydrogen is predicted to consist of a crystal lattice of
hydrogen nuclei (namely, protons), with a spacing which is significantly smaller than the Bohr radius. Indeed, the
spacing is more comparable with the de Broglie wavelength of the electron. The electrons are unbound and behave
like the conduction electrons in a metal. In liquid metallic hydrogen, protons do not have lattice ordering; rather, it is
a liquid system of protons and electrons.
History
Theoretical predictions
Superconductivity
In 1968, Ashcroft put forward that metallic hydrogen may be a superconductor, up to room temperature (~290 K),
far higher than any other known candidate material. This stems from its extremely high speed of sound and the
expected strong coupling between the conduction electrons and the lattice vibrations.[7]
Experimental pursuit
Astrophysics
Metallic hydrogen is thought to be present in large amounts in the gravitationally compressed interiors of Jupiter,
Saturn, and some of the newly discovered extrasolar planets. Because previous predictions of the nature of those
interiors had taken for granted metallization at a higher pressure than the one at which we now know it to happen,
those predictions must now be adjusted. The new data indicate much more metallic hydrogen must exist inside
Jupiter than previously thought, that it comes closer to the surface, and that therefore, Jupiter's tremendous magnetic
field, the strongest of any planet in the solar system is, in turn, produced closer to the surface.
Applications
Nuclear power
One method of producing nuclear fusion, called inertial confinement fusion, involves aiming laser beams at pellets
of hydrogen isotopes. The increased understanding of the behavior of hydrogen in extreme conditions could help to
increase energy yields.
Fuel
It may be possible to produce substantial quantities of metallic hydrogen for practical purposes. The existence has
been theorized of a form called "Metastable Metallic Hydrogen", (abbreviated MSMH) which would not immediately
revert to ordinary hydrogen upon the release of pressure.
In addition, MSMH would make an efficient fuel itself and also a clean one, with only water as an end product. Nine
times as dense as standard hydrogen, it would give off considerable energy when reverting to standard hydrogen.
Burned more quickly, it could be a propellant with up to five times the efficiency of liquid H2/O2, the current Space
Shuttle fuel.[18] Unfortunately, the above-mentioned Lawrence Livermore experiments produced metallic hydrogen
too briefly to determine whether or not metastability is possible.[19]
Metallic hydrogen 42
See also
• Slush hydrogen
• Solid hydrogen
• Timeline of hydrogen technologies
References
[1] Wigner, E.; Huntington, H.B. (1935). "On the possibility of a metallic modification of hydrogen". Journal of Chemical Physics 3: 764.
doi:10.1063/1.1749590.
[2] Cornell News (6 May 1998). "High-pressure scientists 'journey' to the center of the Earth, but can't find elusive metallic hydrogen" (http:/ /
www. news. cornell. edu/ releases/ May98/ misbehaving. hydrogen. deb. html). Press release. . Retrieved 2010-01-02.
[3] Loubeyre, P.; et al. (1996). "X-ray diffraction and equation of state of hydrogen at megabar pressures". Nature 383: 702.
doi:10.1038/383702a0.
[4] "Peanut butter diamonds on display" (http:/ / news. bbc. co. uk/ 2/ hi/ uk_news/ scotland/ edinburgh_and_east/ 6244778. stm). BBC News. 27
June 2007. . Retrieved 2010-01-02.
[5] Ashcroft, N.W. (2000). Journal of Physics: Condensed Matter 12: A129. doi:10.1088/0953-8984/12/8A/314.
[6] Bonev, S.A.; et al. (2004). "A quantum fluid of metallic hydrogen suggested by first-principles calculations". Nature 431: 669.
doi:10.1038/nature02968.
[7] Ashcroft, N.W. (1968). "Metallic Hydrogen: A High-Temperature Superconductor?". Physical Review Letters 21: 1748.
doi:10.1103/PhysRevLett.21.1748.
[8] Babaev, E.; Ashcroft, N.W. (2007). "Violation of the London law and Onsager–Feynman quantization in multicomponent superconductors".
Nature Physics 3: 530. doi:10.1038/nphys646.
[9] Babaev, E.; Sudbø, A.; Ashcroft, N.W. (2004). "A superconductor to superfluid phase transition in liquid metallic hydrogen". Nature 431:
666. doi:10.1038/nature02910.
[10] Babaev; E. (2002). "Vortices with fractional flux in two-gap superconductors and in extended Faddeev model". Physical Review Letters 89:
067001. doi:10.1103/PhysRevLett.89.067001.
[11] Zurek, E.; et al. (2009). "A little bit of lithium does a lot for hydrogen". Proceedings of the National Academy of Sciences.
doi:10.1073/pnas.0908262106.
[12] Weir, S.T.; Mitchell, A.C.; Nellis, W. J. (1996). "Metallization of fluid molecular hydrogen at 140 GPa (1.4 Mbar)". Physical Review Letters
76: 1860. doi:10.1103/PhysRevLett.76.1860.
[13] Ruoff, A.L.; et al. (1998). "Solid hydrogen at 342 GPa: No evidence for an alkali metal". Nature 393: 46. doi:10.1038/29949.
[14] Baer, B.J.; Evans, W.J.; Yoo, C.-S. (2007). "Coherent anti-Stokes Raman spectroscopy of highly compressed solid deuterium at 300 K:
Evidence for a new phase and implications for the band gap". Physical Review Letters 98: 235503. doi:10.1103/PhysRevLett.98.235503.
[15] Badiei, S.; Holmlid, L. (2004). "Experimental observation of an atomic hydrogen material with H–H bond distance of 150 pm suggesting
metallic hydrogen". Journal of Physics: Condensed Matter 16: 7017. doi:10.1088/0953-8984/16/39/034.
[16] Deemyad, S.; Silvera, I.F (March 2008). "The melting line of hydrogen at high pressures". arΧiv:0803.2321.
[17] Eremets, M.I.; et al. (2008). "Superconductivity in hydrogen dominant materials: Silane". Science 319: 1506. doi:10.1126/science.1153282.
[18] Cole, I.F.; Silvera (2009). "Metallic Hydrogen Propelled Launch Vehicles for Lunar Missions" (http:/ / link. aip. org/ link/ ?APCPCS/ 1103/
117/ 1). AIP Conference Proceedings 1103: 117. doi:10.1063/1.3115485. .
[19] Nellis, W.J. (2001), "Metastable Metallic Hydrogen Glass" (http:/ / www. llnl. gov/ tid/ lof/ documents/ pdf/ 244531. pdf), Lawrence
Livermore Preprint UCRL-JC-142360, OSTI 15005772 (http:/ / www. osti. gov/ energycitations/ product. biblio. jsp?osti_id=15005772),
Nascent hydrogen 43
Nascent hydrogen
Atomic hydrogen (or nascent hydrogen)[1] is the species denoted by H (atomic), contrasted with dihydrogen, the
usual 'hydrogen' (H2) commonly involved in chemical reactions. It is claimed to exist transiently but long enough to
effect chemical reactions. According to one claim, nascent hydrogen is generated in situ usually by the reaction of
zinc with an acid, aluminium (Devarda's alloy) with sodium hydroxide, or by electrolysis at the cathode. Being
monoatomic, H atoms are much more reactive and thus a much more effective reducing agent than ordinary diatomic
H2, but again the key question is whether H atoms exist in any chemically meaningful way under the conditions
claimed. The concept is more popular in engineering and in older literature on catalysis. Atomic hydrogen is made of
individual hydrogen atoms which are not bound together like ordinary hydrogen into molecules.
In nature
Most interstellar hydrogen is in the form of atomic hydrogen because the atoms can seldom collide and combine.
They are the source of the important 21 cm hydrogen line in astronomy at 1420 MHz.[3]
Another meaning
Occasionally, hydrogen chemisorbed on metal surfaces is referred to as "nascent", although this terminology is
fading with time. Other views hold that such chemisorbed hydrogen is "a bit less reactive than nascent hydrogen
because of the bonds provided by the catalyst metal surface". Also, such catalyst provided atoms are not called
nascent hydrogen, because they do not need to be captured and reacted in their instantaneous, temporary, "just
generated" state, because the catalyst is able to reversibly generate them from the hydrogen gas supply at any time.
Nascent hydrogen 44
See also
• Cold fusion
• Devarda's alloy
• Marsh test
• Arsine
• Stibine
• James Marsh
• Lithium aluminium hydride
• Lithium borohydride
• Sodium borohydride
References
[1] Laborda, F.; E. Bolea, M. T. Baranguan, J. R. Castillo (2002). "Hydride generation in analytical chemistry and nascent hydrogen: when is it
going to be over?" (http:/ / www. sciencedirect. com/ science/ article/ B6THN-452FF7V-7/ 2/ 29eb1a70053dea76fb3ee7927530be6d).
Spectrochimica Acta Part B: Atomic Spectroscopy 57 (4): 797–802. doi:10.1016/S0584-8547(02)00010-1. ISSN 0584-8547. . Retrieved
2009-05-01.
[2] NASA/TM—2002-211915 : Solid Hydrogen Experiments for Atomic Propellants (http:/ / gltrs. grc. nasa. gov/ reports/ 2002/
TM-2002-211915. pdf)
[3] 21 cm Line (http:/ / mysite. du. edu/ ~jcalvert/ phys/ hydrogen. htm)
Further reading
• Tommasi, D. (1897). "Comment on the Note of R. Franchot entitled “Nascent Hydrogen”". The Journal of
Physical Chemistry 1 (9): 555. doi:10.1021/j150591a004. ISSN 1618-2642.
• Meija, Juris; Alessandro D’Ulivo (2008). "Nascent hydrogen challenge". Analytical and Bioanalytical Chemistry
391 (5): 1475. doi:10.1007/s00216-008-2143-4. ISSN 1618-2642. PMID 18488209.
• Meija, Juris; Alessandro D’Ulivo (2008). "Solution to nascent hydrogen challenge". Analytical and Bioanalytical
Chemistry 392 (5): 771–772. doi:10.1007/s00216-008-2356-6. ISSN 1618-2642. PMID 18795271.
45
Isotopes
Isotopes of hydrogen
Hydrogen (H) (Standard atomic mass: 1.00782504(7) u) has three
naturally occurring isotopes, sometimes denoted 1H, 2H, and 3H.
Other, highly unstable nuclei (4H to 7H) have been synthesized in the
laboratory but not observed in nature.[1] [2]
Hydrogen is the only element that has different names for its isotopes
in common use today. The 2H (or H-2) isotope is usually called
deuterium, while the 3H (or H-3) isotope is usually called tritium. The
symbols D and T (instead of 2H and 3H) are sometimes used for
deuterium and tritium. The IUPAC states that while this use is
common it is not preferred. The ordinary isotope of hydrogen, with no
neutrons, is sometimes called "protium". (During the early study of
radioactivity, some other heavy radioactive isotopes were given names Protium, the most common isotope of hydrogen,
- but such names are rarely used today). consists of one proton and one electron. Unique
among all stable isotopes, it has no neutrons. (see
diproton for a discussion of why others do not
1
H is the most common hydrogen isotope with an abundance of more than 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.
Hydrogen-2 (deuterium)
2
H, the other stable hydrogen isotope, is known as deuterium and contains one proton and one neutron in its nucleus.
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 enrichments (0.015% or 150 ppm) typical of
ocean water. Deuterium is not radioactive, and does not represent 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 1H-NMR spectroscopy. Heavy water
is used as a neutron moderator and coolant for nuclear reactors. Deuterium is also a potential fuel for commercial
nuclear fusion.
Isotopes of hydrogen 46
Hydrogen-3 (tritium)
3
H is known as tritium and contains one proton and two neutrons in its nucleus. It is radioactive, decaying into
helium-3 through β− decay with a half-life of 12.32 years.[3] Small 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 specialized in 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 (this has become
less common). 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 under massive temperatures.
Hydrogen-4 (quadrium)
4
H is a highly unstable isotope of hydrogen. The nucleus consists of a proton and three neutrons. It has been
synthesised in the laboratory by bombarding tritium with fast-moving deuterium nuclei.[4] In this experiment, the
tritium nuclei captured neutrons from the fast-moving deuterium nucleus. The presence of the hydrogen-4 was
deduced by detecting the emitted protons. Its atomic mass is 4.02781 ± 0.00011.[5] It decays through neutron
emission with a half-life of (1.39 ± 0.10) × 10−22 seconds.[6]
Hydrogen-5
5
H is a highly unstable isotope of hydrogen. The nucleus consists of a proton and four neutrons. It has been
synthesised in the laboratory by bombarding tritium with fast-moving tritium nuclei.[4] [7] In this experiment, one
tritium nucleus captures two neutrons from the other, becoming a nucleus with one proton and four neutrons. The
remaining proton may be detected, and the existence of hydrogen-5 deduced. It decays through double neutron
emission and has a half-life of at least 9.1 × 10−22 seconds.[6]
Hydrogen-6
6
H decays through triple neutron emission and has a half-life of 3×10−22 seconds. It consists of 1 proton and 5
neutrons.
Hydrogen-7
7
H consists of a proton and six neutrons. It was first synthesised in 2003 by a group of Russian, Japanese and French
scientists at RIKEN's RI Beam Science Laboratory by bombarding hydrogen with helium-8 atoms. In the resulting
reaction, the helium-8's neutrons were donated to the hydrogen's nucleus. The two remaining protons were detected
by the "RIKEN telescope", a device composed of several layers of sensors, positioned behind the target of the RI
Beam cyclotron.[2]
Isotopes of hydrogen 47
Table
[8]
Nuclide properties
1
H 1 0 1.00782503207(10) Stable
[13] 1 +
⁄2 0.999885(70) 0.999816–0.999974
2
H 1 1 2.0141017778(4) Stable 1+ 0.000115(70)
[14] 0.000026–0.000184
3
H 1 2 3.0160492777(25) 12.32(2) a 1 +
⁄2
4
H 1 3 4.02781(11) 1.39(10) × 10−22 s 2−
[4.6(9) MeV]
5
H 1 4 5.03531(11) >9.1 × 10−22 s ? (1⁄2+)
6
H 1 5 6.04494(28) 2.90(70) × 10−22 s 2−
[15]
[1.6(4) MeV]
7
H 1 6 7.05275(108)
[15]
2.3(6) × 10−23 s
[15]
1/2+
[15]
[15]
[20(5) MeV]
See also
• Isotopes of Helium
Notes
[1] Y. B. Gurov et al. (2004). "Spectroscopy of superheavy hydrogen isotopes in stopped-pion absorption by nuclei". Physics of Atomic Nuclei 68
(3): 491–497. doi:10.1134/1.1891200.
[2] A. A. Korsheninnikov et al. (2003). "Experimental Evidence for the Existence of 7H and for a Specific Structure of 8He". Physical Review
Letters 90: 082501. doi:10.1103/PhysRevLett.90.082501.
[3] G. L. Miessler, D. A. Tarr (2004). Inorganic Chemistry (3rd ed.). Pearson Prentice Hall.
[4] G. M. Ter-Akopian et al. (2002). "Hydrogen-4 and Hydrogen-5 from t+t and t+d transfer reactions studied with a 57.5-MeV triton beam".
AIP Conference Proceedings 610: 920. doi:10.1063/1.1470062.
[5] "The 2003 Atomic Mass Evaluation" (http:/ / www. nndc. bnl. gov/ amdc/ web/ masseval. html). Atomic Mass Data Center. . Retrieved
2008-11-15.
[6] G. Audi, A. H. Wapstra, C. Thibault, J. Blachot and O. Bersillon (2003). "The NUBASE evaluation of nuclear and decay properties" (http:/ /
www. nndc. bnl. gov/ amdc/ nubase/ Nubase2003. pdf). Nuclear Physics A 729: 3–128. doi:10.1016/j.nuclphysa.2003.11.001. .
[7] A. A. Korsheninnikov et al. (2001). "Superheavy Hydrogen 5H". Physical Review Letters 87: 92501. doi:10.1103/PhysRevLett.87.092501.
[8] Commercially available materials may have been subjected to an undisclosed or inadvertent isotopic fractionation. Substantial deviations
from the given mass and composition can occur.
[9] Uncertainties are given in concise form in parentheses after the corresponding last digits, and denote one standard deviation.
[10] Spins with weak assignment arguments are enclosed in parentheses.
[11] Representative isotopic composition (RIC): refers to that in water.
[12] Range of natural variation (RNV): The precision of the isotope abundances and atomic mass is limited through variations. The given ranges
should be applicable to any normal terrestrial material.
[13] Greater than 6.6 × 1033 a. See proton decay.
[14] Tank hydrogen has a 2H abundance as low as 3.2 × 10−5 (mole fraction).
[15] Value is not purely derived from experimental data, but at least partly from systematic trends.
Isotopes of hydrogen 48
References
• Isotope masses from:
• G. Audi, A. H. Wapstra, C. Thibault, J. Blachot and O. Bersillon (2003). "The NUBASE evaluation of nuclear
and decay properties" (http://www.nndc.bnl.gov/amdc/nubase/Nubase2003.pdf). Nuclear Physics A 729:
3–128. doi:10.1016/j.nuclphysa.2003.11.001.
• Isotopic compositions and standard atomic masses from:
• J. R. de Laeter, J. K. Böhlke, P. De Bièvre, H. Hidaka, H. S. Peiser, K. J. R. Rosman and P. D. P. Taylor
(2003). "Atomic weights of the elements. Review 2000 (IUPAC Technical Report)" (http://www.iupac.org/
publications/pac/75/6/0683/pdf/). Pure and Applied Chemistry 75 (6): 683–800.
doi:10.1351/pac200375060683.
• M. E. Wieser (2006). "Atomic weights of the elements 2005 (IUPAC Technical Report)" (http://iupac.org/
publications/pac/78/11/2051/pdf/). Pure and Applied Chemistry 78 (11): 2051–2066.
doi:10.1351/pac200678112051. Lay summary (http://old.iupac.org/news/archives/2005/
atomic-weights_revised05.html).
• Half-life, spin, and isomer data selected from the following sources. See editing notes on this article's talk page.
• G. Audi, A. H. Wapstra, C. Thibault, J. Blachot and O. Bersillon (2003). "The NUBASE evaluation of nuclear
and decay properties" (http://www.nndc.bnl.gov/amdc/nubase/Nubase2003.pdf). Nuclear Physics A 729:
3–128. doi:10.1016/j.nuclphysa.2003.11.001.
• National Nuclear Data Center. "NuDat 2.1 database" (http://www.nndc.bnl.gov/nudat2/). Brookhaven
National Laboratory. Retrieved September 2005.
• N. E. Holden (2004). "Table of the Isotopes". In D. R. Lide. CRC Handbook of Chemistry and Physics (85th
ed.). CRC Press. Section 11. ISBN 978-0849304859.
In fiction
In the 1955 satirical novel The Mouse That Roared, the name quadium was given to the hydrogen-4 isotope that
powered the Q-bomb that the Duchy of Grand Fenwick captured from the United States.
External links
• News of hydrogen-7 discovery (http://physicsweb.org/articles/news/7/3/3)
• Article on hydrogen-4 and hydrogen-5 (http://content.aip.org/APCPCS/v610/i1/920_1.html) (login required)
Deuterium 49
Deuterium
Hydrogen-2
Full table
General
Neutrons 1
Protons 1
Nuclide Data
Half-life Stable
Spin 1+
Deuterium, also called heavy hydrogen, is a stable isotope of hydrogen with a natural abundance in the oceans of
Earth of approximately one atom in 6400 of hydrogen (156 ppm). Deuterium thus accounts for approximately
0.0156% (alternately, on a mass basis: 0.0312%) of all naturally occurring hydrogen in the oceans on Earth (see
VSMOW; the abundance changes slightly from one kind of natural water to another).
The nucleus of deuterium, called a deuteron, contains one proton and one neutron, whereas the far more common
hydrogen nucleus contains no neutron. The isotope name is formed from the Greek deuteros meaning "second", to
denote the two particles composing the nucleus.[1]
Chemical symbol
Deuterium is frequently represented by the chemical symbol D. Since
it is an isotope of hydrogen with mass number 2, it is also represented
by 2H. IUPAC allows both D and 2H, although 2H is preferred.[2] A
distinct chemical symbol is used for convenience because of the
isotope's common use in various scientific processes. Also, its large Deuterium discharge (spectrum) tube
mass difference with protium (1H) (deuterium has a mass of
2.014102 u, compared to the mean hydrogen atomic weight of 1.007947 u, and protium's mass of 1.007825 u)
confers non-negligible chemical dissimilarities with protium-containing compounds, whereas the isotope weight
ratios within other chemical elements are largely insignificant in this regard.
Deuterium 50
Natural abundance
Deuterium occurs in trace amounts naturally as deuterium gas, written 2H2 or D2, but most natural occurrence in the
universe is bonded with a typical 1H atom, a gas called hydrogen deuteride (HD or 1H2H).[3]
The natural deuterium abundance seems to be a very similar fraction of hydrogen, wherever hydrogen is found.
Thus, the existence of deuterium at a low but constant fraction in all hydrogen, is one of the arguments in favor of
the Big Bang theory over the steady state theory of the universe. It is estimated that the abundances of deuterium
have not evolved significantly since their production about 13.7 bya.[4]
Deuterium abundance on Jupiter is about 2.25 × 10−5 (roughly 22 atoms in a million, or 15% of the terrestrial
deuterium-to-hydrogen ratio);[5] these ratios presumably reflect the early solar nebula ratios, and those after the Big
Bang. However, other sources suggest a much higher abundance of e.g. 6 × 10−4 (6 atoms in 10000 or 0.06% atom
basis).[6] There is thought to be little deuterium in the interior of the Sun and other stars, as at temperatures there
nuclear fusion reactions that consume deuterium happen much faster than the proton-proton reaction that creates
deuterium. However, it continues to persist in the outer solar atmosphere at roughly the same concentration as in
Jupiter.
The existence of deuterium on Earth, elsewhere in the solar system (as confirmed by planetary probes), and in the
spectra of stars, is an important datum in cosmology. Gamma radiation from ordinary nuclear fusion dissociates
deuterium into protons and neutrons, and there are no known natural processes other than the Big Bang
nucleosynthesis, which might have produced deuterium at anything close to the observed natural abundance of
deuterium (deuterium is produced by the rare cluster decay, and occasional absorption of naturally-occurring
neutrons by light hydrogen, but these are trivial sources).
Properties
Physical properties
The physical properties of deuterium compounds can exhibit significant kinetic isotope effects and other physical
and chemical property differences from the hydrogen analogs; for example, D2O is more viscous than H2O.[7]
Chemically, deuterium behaves similarly to ordinary hydrogen, but there are differences in bond energy and length
for compounds of heavy hydrogen isotopes which are larger than the isotopic differences in any other element.
Bonds involving deuterium and tritium are somewhat stronger than the corresponding bonds in hydrogen, and these
differences are enough to make significant changes in biological reactions.
Deuterium can replace the normal hydrogen in water molecules to form heavy water (D2O), which is about 10.6%
denser than normal water (enough that ice made from it sinks in ordinary water). Heavy water is slightly toxic in
eukaryotic animals, with 25% substitution of the body water causing cell division problems and sterility, and 50%
substitution causing death by cytotoxic syndrome (bone marrow failure and gastrointestinal lining failure).
Prokaryotic organisms, however, can survive and grow in pure heavy water (though they grow more slowly).[8]
Consumption of heavy water would not pose a health threat to humans, it was estimated that a 70 kg person might
drink 4.8 liters of heavy water without serious consequences.[9] Small doses of heavy water (a few grams in humans,
containing an amount of deuterium comparable to that normally present in the body) are routinely used as harmless
metabolic tracers in humans and animals.
Deuterium 51
Quantum properties
The deuteron has spin +1 ("triplet") and is thus a boson. The NMR frequency of deuterium is significantly different
from common light hydrogen. Infrared spectroscopy also easily differentiates many deuterated compounds, due to
the large difference in IR absorption frequency seen in the vibration of a chemical bond containing deuterium, versus
light hydrogen. The two stable isotopes of hydrogen can also be distinguished by using mass spectrometry.
The triplet deuteron nucleon barely is bound at EB = 2.23 MeV, so all the higher energy states are not bound. The
singlet deuteron is a virtual state, with a negative binding energy of 60 keV. There is no such stable particle, but this
virtual particle transiently exists during neutron-proton inelastic scattering, accounting for the unusually large
neutron scattering cross-section of the proton.[10]
This is a nucleus with one proton and one neutron, i.e. a deuterium nucleus. The triplet is
Deuterium 52
and thus consists of three types of nuclei, which are supposed to be symmetric: a deuterium nucleus (actually a
highly excited state of it), a nucleus with two protons, and a nucleus with two neutrons. The latter two nuclei are not
stable or nearly stable, and therefore so is this type of deuterium (meaning that it is indeed a highly excited state of
deuterium).
with
The measured value of the deuterium magnetic dipole moment, is 0.857 µN. This suggests that the state of the
deuterium is indeed only approximately s = 1, l = 0 state, and is actually a linear combination of (mostly) this state
with s = 1, l = 2 state.
The electric dipole is zero as usual.
The measured electric quadrupole of the deuterium is 0.2859 e·fm2. While the order of magnitude is reasonable,
since the deuterium radius is of order of 1 femtometer (see below) and its electric charge is e, the above model does
not suffice for its computation. More specifically, the electric quadrupole does not get a contribution from the l =0
state (which is the dominant one) and does get a contribution from a term mixing the l =0 and the l =2 states, because
the electric quadrupole operator does not commute with angular momentum. The latter contribution is dominant in
the absence of a pure l = 0 contribution, but cannot be calculated without knowing the exact spatial form of the
nucleons wavefunction inside the deuterium.
Higher magnetic and electric multipole moments cannot be calculated by the above model, for similar reasons.
Deuterium 54
Applications
Deuterium has a number of
commercial and scientific uses. These
include:
Nuclear reactors
Deuterium is useful in nuclear fusion
reactions, especially in combination
with tritium, because of the large
reaction rate (or nuclear cross section)
and high energy yield of the D–T
reaction. There is an even higher-yield
D–3He fusion reaction, though the
breakeven point of D–3He is higher
than that of most other fusion
reactions; together with the scarcity of
3 Ionized deuterium in an IEC fusion reactor giving off its characteristic pinkish-red glow.
He, this makes it implausible as a
practical power source until at least
D–T and D–D fusion reactions have
been performed on a commercial scale.
NMR spectroscopy
Deuterium NMR spectra are especially
informative in the solid state because
of its relatively small quadrupole
moment in comparison with those of Emission spectrum of an ultraviolet deuterium arc lamp.
bigger quadrupolar nuclei such as
chlorine-35, for example.
Tracing
In chemistry, biochemistry and environmental sciences, deuterium is used as a non-radioactive, stable isotopic tracer,
for example, in the doubly-labeled water test. In chemical reactions and metabolic pathways, deuterium behaves
somewhat similarly to ordinary hydrogen (with a few chemical differences, as noted). It can be distinguished from
ordinary hydrogen most easily by its mass, using mass spectrometry or infrared spectrometry. Deuterium can be
detected by femtosecond infrared spectroscopy, since the mass difference drastically affects the frequency of
molecular vibrations; deuterium-carbon bond vibrations are found in locations free of other signals.
Measurements of small variations in the natural abundances of deuterium, along with those of the stable heavy
oxygen isotopes 17O and 18O, are of importance in hydrology, to trace the geographic origin of Earth's waters. The
heavy isotopes of hydrogen and oxygen in rainwater (so-called meteoric water) are enriched as a function of the
Deuterium 55
environmental temperature of the region in which the precipitation falls (and thus enrichment is related to mean
latitude). The relative enrichment of the heavy isotopes in rainwater (as referenced to mean ocean water), when
plotted against temperature falls predictably along a line called the global meteoric water line (GMWL). This plot
allows samples of precipitation-originated water to be identified along with general information about the climate in
which it originated. Evaporative and other processes in bodies of water, and also ground water processes, also
differentially alter the ratios of heavy hydrogen and oxygen isotopes in fresh and salt waters, in characteristic and
often regionally-distinctive ways.[13]
Contrast properties
Neutron scattering techniques particularly profit from availability of deuterated samples: The H and D cross sections
are very distinct and different in sign, which allows contrast variation in such experiments. Further, a nuisance
problem of ordinary hydrogen is its large incoherent neutron cross section, which is nil for D. The substitution of
hydrogen atoms for deuterium atoms thus reduces scattering noise.
Hydrogen is an important and major component in all materials of organic chemistry and life science, but is barely
interacts with X-rays. As hydrogen (and deuterium) interact strongly with neutrons, neutron scattering techniques,
together with a modern deuteration facility, fills a niche in many studies of macromolecules in biology and many
other areas.
History
Name
Urey called the new isotope "deuterium", from the Greek deuteros (second), and the nucleus to be called "deuteron"
or "deuton". Isotopes and new elements were traditionally given the name that their discoverer decided, but some
British chemists, like Ernest Rutherford, wanted the isotope to be called "diplogen", from the Greek diploos
(double), and the nucleus to be called diplon. The British magazine Nature also published a letter where only the
denomination "diplogen" was used, perhaps annunciating that British could prefer that name over the name given by
its discoverer. Urey and his two co-discoverers sent a letter to Nature saying that they had already considered that
name and they had rejected it because "The compound NH1H2/2 would be called di-diplogen mono-hydrogen
nitride", which would repeat the syllable "di." They also said that the British seemed to object on the basis that
"neutron" and "deuton" could be confused with each other, and Urey pointed out that American workers were using
the terms and they didn't seem to be having any such confusion.[1]
Data
• Density: 0.180 kg/m3 at STP (0 °C, 101.325 kPa).
• Atomic weight: 2.0141017926 u.
• Mean abundance in ocean water (see VSMOW) about 0.0156 of H atoms = 1/6400 H atoms.
Data at approximately 18 K for D2 (triple point):
• Density:
• Liquid: 162.4 kg/m3
• Gas: 0.452 kg/m3
• Viscosity: 12.6 µPa·s at 300 K (gas phase)
• Specific heat capacity at constant pressure cp:
• Solid: 2950 J/(kg·K)
• Gas: 5200 J/(kg·K)
Anti-deuterium
An antideuteron is the antiparticle of the nucleus of deuterium, consisting of an antiproton and an antineutron. The
antideuteron was first produced in 1965 at the Proton Synchrotron at CERN[16] and the Alternating Gradient
Synchrotron [17] at Brookhaven National Laboratory.[18] A complete atom, with a positron orbiting the nucleus,
would be called antideuterium, but as of 2005 antideuterium has not yet been created. The proposed symbol for
antideuterium is D, that is, D with an overbar.[19]
Pycnodeuterium
Deuterium atoms can be absorbed into a palladium (Pd) lattice. They are effectively solidified as an ultrahigh density
deuterium lump (Pycnodeuterium) inside each octahedral space within the unit cell of the palladium host lattice. It
was once reported that deuterium absorbed into palladium enabled nuclear cold fusion.[20] However, cold fusion by
this mechanism has not been generally accepted by the scientific community.[21]
Ultra-dense deuterium
The existence of ultra-dense deuterium is suggested by experiment. If its existence is confirmed, this material, at
density of 140 kg/cm3, would be a million times more dense than regular deuterium, denser than the core of the Sun.
This ultra-dense form of deuterium may facilitate achieving laser-induced fusion.[22] Only minute amounts of
ultra-dense deuterium have been produced thus far.[23] [24]
See also
• Isotopes of hydrogen
• Nuclear fusion
• Tokamak
• Tritium
• Heavy water
Deuterium 58
References
[1] "Science: Deuterium v. Diplogen" (http:/ / www. time. com/ time/ magazine/ article/ 0,9171,746988,00. html). Time. 1934-02-19. .
[2] "§ IR-3.3.2 Provisional Recommendations" (http:/ / www. iupac. org/ reports/ provisional/ abstract04/ connelly_310804. html). Nomenclature
of Inorganic Chemistry. Chemical Nomenclature and Structure Representation Division, IUPAC. . Retrieved 2007-10-03.
[3] IUPAC Commission on Nomenclature of Inorganic Chemistry (2001). "Names for Muonium and Hydrogen Atoms and their Ions" (http:/ /
www. iupac. org/ publications/ pac/ 2001/ pdf/ 7302x0377. pdf) (PDF). Pure and Applied Chemistry 73: 377–380.
doi:10.1351/pac200173020377. .
[4] The End of Cosmology?: Scientific American (http:/ / www. sciam. com/ article. cfm?id=the-end-of-cosmology& print=true)
[5] Lellouch, E; Bézard, B.; Fouchet, T.; Feuchtgruber, H.; Encrenaz, T.; De Graauw, T. (2001). "The deuterium abundance in Jupiter and Saturn
from ISO-SWS observations". Astronomy & Astrophysics 670: 610–622. doi:10.1051/0004-6361:20010259.
[6] "Hubble measures deuterium on Jupiter" (http:/ / findarticles. com/ p/ articles/ mi_m1200/ is_n14_v150/ ai_18757250). Science News – Find
Articles. 5 October 1996. . Retrieved 2007-09-10. As mentioned in this article, this value also agrees with the Galileo entry probe
measurement for Jupiter
[7] Lide, D. R., ed. (2005), CRC Handbook of Chemistry and Physics (86th ed.), Boca Raton (FL): CRC Press, ISBN 0-8493-0486-5
[8] D. J. Kushner, Alison Baker, and T. G. Dunstall (1999). "Pharmacological uses and perspectives of heavy water and deuterated compounds".
Can. J. Physiol. Pharmacol. 77 (2): 79–88. doi:10.1139/cjpp-77-2-79. PMID 10535697.
[9] ed. by Attila Vertes .... (2003). "Physiological effect of heavy water" (http:/ / books. google. com/ ?id=nQh7iGX1geIC& pg=PA111).
Elements and isotopes : formation, transformation, distribution.. Dordrecht: Kluwer Acad. Publ.. pp. 111– 112. ISBN 9781402013140. .
[10] Neutron-Proton Scattering (http:/ / mightylib. mit. edu/ Course Materials/ 22. 101/ Fall 2004/ Notes/ Part3. pdf)
[11] 2002 CODATA recommended value (http:/ / physics. nist. gov/ cgi-bin/ cuu/ Value?mdu)
[12] 2006 CODATA recommended value Mohr, Peter J.; Taylor, Barry N.; Newell, David B. (2008). "CODATA Recommended Values of the
Fundamental Physical Constants: 2006" (http:/ / physics. nist. gov/ cuu/ Constants/ codata. pdf). Rev. Mod. Phys. 80: 633–730.
doi:10.1103/RevModPhys.80.633. .
[13] "Oxygen – Isotopes and Hydrology" (http:/ / www. sahra. arizona. edu/ programs/ isotopes/ oxygen. html). SAHRA. . Retrieved
2007-09-10.
[14] Sherriff, Lucy (2007-06-01). "Royal Society unearths top secret nuclear research" (http:/ / www. theregister. co. uk/ 2007/ 06/ 01/
royal_soc_secret_physics/ ). The Register. Situation Publishing Ltd.. . Retrieved 2007-06-03.
[15] "The Battle for Heavy Water Three physicists' heroic exploits" (http:/ / bulletin. cern. ch/ eng/ articles. php?bullno=14/ 2002& base=art).
CERN Bulletin. European Organization for Nuclear Research. 2002-04-01. . Retrieved 2007-06-03.
[16] Massam, T; Muller, Th.; Righini, B.; Schneegans, M.; Zichichi, A. (1965). "Experimental observation of antideuteron production". Il Nuovo
Cimento 39: 10–14. doi:10.1007/BF02814251.
[17] http:/ / www. bnl. gov/ bnlweb/ facilities/ AGS. asp
[18] Dorfan, D. E; Eades, J.; Lederman, L. M.; Lee, W.; Ting, C. C. (June 1965). "Observation of Antideuterons". Phys. Rev. Lett. 14 (24):
1003–1006. doi:10.1103/PhysRevLett.14.1003.
[19] Chardonnet, P (1997). "The production of anti-matter in our galaxy" (http:/ / arxiv. org/ abs/ astro-ph/ 9705110v1). Physics Letters B 409:
313. doi:10.1016/S0370-2693(97)00870-8. .
[20] Arata Y, Zhang Y-C, Fujita H, Inoue A; Koon Gakkaishi 29(2) (2003). "Discovery of solid deuterium nuclear fusion of
pycnodeuterium-lumps solidified locally within nano-Pd particles". Formation of condensed metallic deuterium lattice and nuclear fusion
(2006/10/17) (http:/ / www. journalarchive. jst. go. jp/ english/ jnlabstract_en. php?cdjournal=pjab1977& cdvol=78& noissue=3&
startpage=57).
[21] Feder, Toni (2005). "Cold Fusion Gets Chilly Encore" (http:/ / scitation. aip. org/ journals/ doc/ PHTOAD-ft/ vol_58/ iss_1/ 31_1. shtml).
Physics Today 58 (January): 31. doi:10.1063/1.1881896. . Retrieved 2008-05-28.
[22] Andersson, Patrik U.; Holmlid, Leif (2009). "Ultra-dense deuterium: A possible nuclear fuel for inertial confinement fusion (ICF)". Physics
Letters A 373: 3067–3070. doi:10.1016/j.physleta.2009.06.046.
[23] Badiei, S; Andersson, P; Holmlid, L (2009). "Fusion reactions in high-density hydrogen: A fast route to small-scale fusion?". International
Journal of Hydrogen Energy 34: 487–495. doi:10.1016/j.ijhydene.2008.10.024.
[24] Badiei, Shahriar; Andersson, Patrik U.; Holmlid, Leif (2009). "High-energy Coulomb explosions in ultra-dense deuterium:
Time-of-flight-mass spectrometry with variable energy and flight length". International Journal of Mass Spectrometry 282: 70–76.
doi:10.1016/j.ijms.2009.02.014.
Deuterium 59
External links
• Nuclear Data Evaluation Lab (http://atom.kaeri.re.kr/)
• Mullins, Justin (27 April 2005). "Desktop nuclear fusion demonstrated with deuterium gas" (http://www.
newscientist.com/article.ns?id=dn7315). New Scientist. Retrieved 2007-09-10.
• Annotated bibliography for Deuterium from the Alsos Digital Library for Nuclear Issues (http://alsos.wlu.edu/
qsearch.aspx?browse=science/Deuterium)
• Missing Gas Found in Milky Way (http://space.com/scienceastronomy/060821_mystery_monday.html).
Space.com
Tritium
Tritium
Tritium
Full table
General
Neutrons 2
Protons 1
Nuclide data
Decay products 3
He
Spin 1 +
⁄2
Tritium (pronounced /ˈtrɪtiəm/ or English pronunciation: /ˈtrɪʃiəm/, symbol T or 3H, also known as hydrogen-3) is a
radioactive isotope of hydrogen. The nucleus of tritium (sometimes called a triton) contains one proton and two
neutrons, whereas the nucleus of protium (by far the most abundant hydrogen isotope) contains one proton and no
neutrons. Naturally-occurring tritium is extremely rare on Earth, where trace amounts are formed by the interaction
of the atmosphere with cosmic rays. The name of this isotope is formed from the Greek word "tritos" meaning
"third".
Tritium 60
Decay
While tritium has several different experimentally-determined values of its half-life, the National Institute of
Standards and Technology lists 4,500±8 days (approximately 12.32 years).[1] It decays into helium-3 by beta decay
as in this nuclear equation:
T → + e− + νe
He1+
and it releases 18.6 keV of energy in the process. The electron's kinetic energy varies, with an average of 5.7 keV,
while the remaining energy is carried off by the nearly-undetectable electron antineutrino. Beta particles from tritium
can penetrate only about 6.0 mm of air, and they are incapable of passing through the dead outermost layer of human
skin.[2]
Tritium is potentially dangerous if inhaled or ingested. It can combine with oxygen to form tritiated water molecules,
and those can be absorbed through pores in the skin.
The low energy of tritium's radiation makes it difficult to detect tritium-labelled compounds except by using liquid
scintillation counting.
Production
Lithium
Tritium is produced in nuclear reactors by neutron activation of lithium-6. This is possible with neutrons of any
energy, and is an exothermic reaction yielding 4.8 MeV. In comparison, the fusion of deuterium with tritium releases
about 17.6 MeV of energy.
Li + n → He ( 2.05 MeV ) + T ( 2.75 MeV )
High-energy neutrons can also produce tritium from lithium-7 in an endothermic reaction, consuming 2.466 MeV.
This was discovered when the 1954 Castle Bravo nuclear test produced an unexpectedly high yield.[3]
Li + n → He + T + n
High-energy neutrons irradiating boron-10 will also occasionally produce tritium.[4] The more common result of
boron-10 neutron capture is 7Li and a single alpha particle.[5]
B + n → 2 He + T
The reactions requiring high neutron energies are not attractive production methods.
Deuterium
Tritium is also produced in heavy water-moderated reactors whenever a deuterium nucleus captures a neutron. This
reaction has a quite small cross section, making heavy water a good neutron moderator, and relatively little tritium is
produced. Even so, cleaning tritium from the moderator may be desirable after several years to reduce the risk of its
escaping to the environment. The Ontario Power Generation's "Tritium Removal Facility" processes up to 2500 long
tons ( kg) of heavy water a year, and it separates out about 2.5 kg (5.5 lb) of tritium, making it available for other
uses.[6]
Deuterium's absorption cross section for thermal neutrons is about 0.52 millibarns, whereas that of oxygen-16 (
O) is about 0.19 millibarns and that of oxygen-17 ( O) is about 0.24 barn. O makes up about 0.038% of all
naturally-occurring oxygen, hence oxygen has an overall absorption cross section of about 0.28 millibarns.
Therefore, in deuterium oxide made with natural oxygen, 21% of neutron captures are by oxygen nuclei, a
Tritium 61
proportion that may rise further since the percentage of O increases from neutron captures by O. Also, O splits when
bombarded by the alpha particles emitted by decaying uranium, producing radioactive carbon-14 ( C), a dangerous
by-product, by the equation.
O + He → C + assorted smalled products
Fission
Tritium is an uncommon product of the nuclear fission of uranium-235, plutonium-239, and uranium-233, with a
production of about one per each 10,000 fissions.[7] [8] This means that the release or recovery of tritium needs to be
considered in the operation of nuclear reactors, especially in the reprocessing of nuclear fuels and in the storage of
spent nuclear fuel. The production of tritium was not a goal, but rather, it is just a side-effect.
Cosmic rays
Tritium occurs naturally due to cosmic rays interacting with atmospheric gases. In the most important reaction for
natural production, a fast neutron (which must have energy greater than 4.0 MeV[10] ) interacts with atmospheric
nitrogen:
N + n → C + T
Because of tritium's relatively short half-life, tritium produced in this manner does not accumulate over geological
timescales, and thus it occurs only in negligible quantities in nature.
Production history
According to the Institute for Energy and Environmental Research report in 1996 about the U.S. Department of
Energy, only 225 kg (500 lb) of tritium has been produced in the United States since 1955. Since it continually
decays into helium-3, the total amount remaining was about 75 kg (170 lb) at the time of the report.[3]
Tritium for American nuclear weapons was produced in special heavy water reactors at the Savannah River Site until
their close-downs in 1988. With the Strategic Arms Reduction Treaty (SALT) after the end of the Cold War, the
existing supplies were sufficient for the new, smaller number of nuclear weapons for some time.
The production of tritium was resumed with irradiation of rods containing lithium (replacing the usual control rods
containing boron, cadmium, or hafnium), at the reactors of the commercial Watts Bar Nuclear Generating Station in
2003 - 05 followed by extraction of tritium from the rods at the new Tritium Extraction Facility[11] at the Savannah
River Site beginning in November 2006.[12]
Tritium 62
Properties
Tritium has an atomic mass of 3.0160492. It is a gas (T2 or 3H2) at standard temperature and pressure. It combines
with oxygen to form a liquid called tritiated water, T2O, or partially tritiated water, THO.
Tritium figures prominently in studies of nuclear fusion because of its favorable reaction cross section and the large
amount of energy (17.6 MeV) produced through its reaction with deuterium:
T + D → He + n
All atomic nuclei, being composed of protons and neutrons, repel one another because of their positive charge.
However, if the atoms have a high enough temperature and pressure (for example, in the core of the Sun), then their
random motions can overcome such electrical repulsion (called the Coulomb force), and they can come close enough
for the strong nuclear force to take effect, fusing them into heavier atoms.
The tritium nucleus, containing one proton and two neutrons[7] , has the same charge as the nucleus of ordinary
hydrogen, and it experiences the same electrostatic repulsive force when brought close to another atomic nucleus.
However, the neutrons in the tritium nucleus increase the attractive strong nuclear force when brought close enough
to another atomic nucleus. As a result, tritium can more easily fuse with other light atoms, compared with the ability
of ordinary hydrogen to do so.
The same is true, albeit to a lesser extent, of deuterium. This is why brown dwarfs (so-called failed stars) cannot
utilize ordinary hydrogen, but they do fuse the small minority of deuterium nuclei together.
Like hydrogen, tritium is difficult to
confine. Rubber, plastic, and some kinds of
steel are all somewhat permeable. This has
raised concerns that if tritium were used in
large quantities, in particular for fusion
reactors, it may contribute to radioactive
contamination, although its short half-life
should prevent significant long-term
accumulation in the atmosphere.
Health risks
Tritium is an isotope of hydrogen, which makes it bind to hydroxyl radicals to form tritiated water (HTO), and that it
can bind with carbon atoms readily (C-T). The HTO and the carbon-tritium compounds are easily ingested by
drinking, or by eating organic or water-containing foodstuffs. Since tritium is not a very active beta emitter, it is not
dangerous externally, but it is a radiation hazard when inhaled, ingested via food, water, or absorbed through the
skin.[13] [14] [15] [16] HTO has a short biological half life in the human body of seven to 14 days, which both reduces
Tritium 63
the total effects of single-incident ingestion and precludes long-term bioaccumulation of HTO from the environment.
Regulatory limits
The legal limits for tritium in drinking water vary from country-to-country and from continent-to-continent. Some
figures are given below.
• Canada: 7,000 becquerel per liter (Bq/L).
• United States: 740 Bq/L or 20,000 picocurie per liter (pCi/L) (Safe Drinking Water Act)
• World Health Organization: 10,000 Bq/L.
• European Union: "investigative" limit of 100 Bq/L.
The American limit is calculated to yield a dose of 4.0 millirems (or 40 microsieverts in SI units) per year. This is
about 1.3% of the natural background radiation (roughly 3000 microsieverts).
Usage
Self-powered lighting
The emitted electrons from the radioactive decay of small amounts of
tritium cause phosphors to glow so as to make self-powered lighting
devices called betalights, which are now used in Firearms night sights,
watches (See Luminox for example), exit signs, map lights, and a
variety of other devices. This takes the place of radium, which can
cause bone cancer and has been banned in most countries for decades.
Commercial demand for tritium is 400 grams per year[3] and costs
approximately $US30,000 per gram[17]
Nuclear weapons
Tritium is widely used in multi-stage hydrogen bombs for boosting the
fission primary explosion of a thermonuclear weapon (It can be
similarly used for fission bombs.) as well as in external neutron
initiators.
Neutron initiator
Commander Analog Date tritium-illuminated
Actuated by an ultrafast switch like a krytron, a small particle
watch face
accelerator accelerates ions of tritium and deuterium to energies above
the 15 kilo-electron-volts or so needed for deuterium-tritium fusion and
directs them into a metal target where the tritium and deuterium are adsorbed as hydrides. High-energy fusion
neutrons from the resulting fusion radiate in all directions. Some of these strike plutonium or uranium nuclei in the
primary's pit, initiating nuclear chain reaction. The quantity of neutrons produced is large in absolute numbers,
allowing the pit to quickly achieve neutron levels that would otherwise need many more generations of chain
reaction, though still small compared to the total number of nuclei in the pit.
Tritium 64
Boosting
Before detonation, a few grams of tritium-deuterium gas are injected into the hollow "pit" of fissile plutonium or
uranium. The early stages of the fission chain reaction supply enough heat and compression to start
deuterium-tritium fusion, then both fission and fusion proceed in parallel, the fission assisting the fusion by
continuing heating and compression, and the fusion assisting the fission with highly energetic (14.1 MeV) neutrons.
As the fission fuel depletes and also explodes outward, it falls below the density needed to stay critical by itself, but
the fusion neutrons make the fission process progress faster and continue longer than it would without boosting.
Increased yield comes overwhelmingly from the increase in fission. The energy released by the fusion itself is much
smaller because the amount of fusion fuel is so much smaller. The effects of boosting include:
• increased yield (for the same amount of fission fuel, compared to detonation without boosting)
• the possibility of variable yield by varying the amount of fusion fuel
• allowing the bomb to require a smaller amount of the very expensive fissile material - and also eliminating the
risk of predetonation by nearby nuclear explosions
• allowing the primary to quickly release most of its power before it has expanded to a larger size difficult to retain
within a so-called "radiation case" (??).
• not so stringent requirements on the implosion setup, allowing for a smaller and lighter amount of high-explosives
to be used
The tritium in a warhead is continually undergoing radioactive decay, hence becoming unavailable for fusion.
Furthermore its decay product, helium-3, absorbs neutrons if exposed to the ones emitted by nuclear fission. This
potentially offsets or reverses the intended effect of the tritium, which was to generate many free neutrons, if too
much helium-3 has accumulated from the decay of tritium. Therefore, it is necessary to replenish tritium in boosted
bombs periodically. The estimated quantity needed is 4 grams per warhead.[3] To maintain constant levels of tritium,
about 0.20 grams per warhead per year must be suppiled to the bomb.
One mole of deuterium-tritium gas would contain about 3.0 grams of tritium and 2.0 grams of deuterium. In
comparison, the plutonium-239 of a 4.5 kilograms of a nuclear bomb contains about 20 moles of plutonium.
Analytical chemistry
Tritium is sometimes used as a radiolabel. It has the advantage that hydrogen appears in almost all organic chemicals
making it easy to find a place to put tritium on the molecule under investigation. It has the disadvantage of producing
a comparatively weak signal.
corresponds to a deepening rate of approximately 18 meters per year.[18] There are also tritium increases at 1,500
meters depth in the late 1970s and 2,500 meters in the middle of the 1980s, both of which correspond to cooling
events in the deep water and associated deep water ventilation.[18]
From a study in 1991, the tritium profile was used as a tool for studying the mixing and spreading of newly-formed
North Atlantic Deep Water (NADW), corresponding to tritium increases to 4 TU.[21] This NADW tends to spill over
sills that divide the Norwegian Sea from the North Atlantic Ocean and then flows to the west and equatorward in
deep boundary currents. This process was explained via the large-scale tritium distribution in the deep North Atlantic
between 1981 and 1983.[21] The sub-polar gyre tends to be freshened (ventilated) by the NADW and is directly
related to the high tritium values (> 1.5 TU). Also evident was the decrease in tritium in the deep western boundary
current by a factor of 10 from the Labrador Sea to the Tropics, which is indicative of loss to ocean interior due to
turbulent mixing and recirculation.[21]
History
Tritium was first predicted in the late 1920s by Walter Russell, using his "spiral" periodic table,[25] then produced in
1934 from deuterium, another isotope of hydrogen, by Ernest Rutherford, working with Mark Oliphant and Paul
Harteck. Rutherford was unable to isolate the tritium, a job that was left to Luis Alvarez and Robert Cornog, who
correctly deduced that the substance was radioactive.[26] Willard F. Libby discovered that tritium could be used for
dating water, and therefore wine.[27]
Tritium 68
See also
• Hypertriton
• Luminox
References
[1] L. L. Lucas, M. P. Unterweger (2000). "Comprehensive Review and Critical Evaluation of the Half-Life of Tritium" (http:/ / nvl. nist. gov/
pub/ nistpubs/ jres/ 105/ 4/ j54luc2. pdf). Journal of Research of the National Institute of Standards and Technology 105 (4): 541. .
[2] Nuclide safety data sheet: Hydrogen-3 (http:/ / www. ehso. emory. edu/ radiation/ Forms/ nuclide_data_safety_sheets. pdf)
[3] Hisham Zerriffi (January 1996). "Tritium: The environmental, health, budgetary, and strategic effects of the Department of Energy's decision
to produce tritium" (http:/ / www. ieer. org/ reports/ tritium. html#(11)). Institute for Energy and Environmental Research. .
[4] Greg Jones (2008). "Tritium Issues in Commercial Pressurized Water Reactors" (http:/ / www. new. ans. org/ store/ j_1824). Fusion Science
and Technology 54 (2): 329–332. .
[5] Carey Sublette (2006-05-17). "Nuclear Weapons FAQ Section 12.0 Useful Tables" (http:/ / nuclearweaponarchive. org/ Nwfaq/ Nfaq12.
html). Nuclear Weapons Archive. . Retrieved 2010-09-19.
[6] Dr. Jeremy Whitlock. "Section D: Safety and Liability - How does Ontario Power Generation manage tritium production in its CANDU
moderators?" (http:/ / www. nuclearfaq. ca/ cnf_sectionD. htm#x5). Canadian Nuclear FAQ. . Retrieved 2010-09-19.
[7] "Tritium (Hydrogen-3) - Human Health Fact sheet" (http:/ / www. ead. anl. gov/ pub/ doc/ tritium. pdf). Argonne National Laboratory.
2005-08. . Retrieved 2010-09-19.
[8] Serot, O.; Wagemans, C.; Heyse, J. (2005). "New Results on Helium and Tritium Gas Production From Ternary Fission". International
conference on nuclear data for science and technology. AIP Conference Proceedings 769: 857–860. doi:10.1063/1.1945141.
[9] "Helium-3 Neutron Proportional Counters" (http:/ / web. mit. edu/ 8. 13/ www/ tgm-neutron-detectors. pdf). .
[10] P.G Young and D.G Foster, Jr (1972-09). "An Evaluation of the Neutron and Gamma-ray Production Cross Sections for Nitrogen" (http:/ /
www. fas. org/ sgp/ othergov/ doe/ lanl/ lib-www/ la-pubs/ 00320217. pdf). Los Alamos Scientific Laboratory. . Retrieved 2010-09-19.
[11] Defense Programs (http:/ / www. srs. gov/ general/ programs/ dp/ index. htm)
[12] "Tritium Extraction Facility" (http:/ / www. srs. gov/ general/ news/ factsheets/ tef. pdf). Savannah River Site. 2007-12. . Retrieved
2010-09-19.
[13] Tritium Hazard Report: Pollution and Radiation Risk from Canadian Nuclear Facilities (http:/ / www. greenpeace. org/ raw/ content/ canada/
en/ documents-and-links/ publications/ tritium-hazard-report-pollu. pdf), I. Fairlie, 2007 June
[14] Review of the Greenpeace report: "Tritium Hazard Report: Pollution and Radiation Risk from Canadian Nuclear Facilities" (http:/ / www.
nuclearfaq. ca/ ReviewofGreenpeacereport_Final. pdf), R.V. Osborne, 2007 August
[15] Fact Sheet on Tritium, Radiation Protection Limits, and Drinking Water Standards (http:/ / www. nrc. gov/ reading-rm/ doc-collections/
fact-sheets/ tritium-radiation-fs. html), U.S. Nuclear Regulatory Commission
[16] Tritium Facts and Information (http:/ / www. dep. state. pa. us/ brp/ Radiation_Control_Division/ Tritium. htm), Pensilvania Department of
Environmental Protection
[17] Scott Willms (2003-01-14). Tritium Supply Considerations (http:/ / fire. pppl. gov/ fesac_dp_ts_willms. pdf). Los Alamos National
Laboratory. . Retrieved 2010-08-01.
[18] Jenkins, William J. et al, 1996: “Transient Tracers Track Ocean Climate Signals” (http:/ / www. whoi. edu/ oceanus/ viewArticle.
do?id=2330) Oceanus, Woods Hole Oceanographic Institution.
[19] Tamuly, A. (2007). "Dispersal of Tritium in Southern Ocean Waters" (http:/ / pubs. aina. ucalgary. ca/ arctic/ Arctic27-1-27. pdf). Arctic
(Arctic Institute of North America) 27: 27–40. .
[20] Lipps, Frank B. and Richard S. Hemler (1992). "On the Downward Transfer of Tritium to the Ocean by a Cloud Model" (http:/ / www. agu.
org/ pubs/ crossref/ 1992/ 92JD01062. shtml). Journal of Geophysical Research 97 (12): 12, 889–12, 900. .
[21] Doney, Scott C.; Williams, P (1992). "Bomb Tritium in the Deep North Atlantic" (http:/ / www. tos. org/ oceanography/ issues/
issue_archive/ issue_pdfs/ 5_3/ 5. 3_doney. pdf). Oceanography 5: 169–170. doi:10.1016/0012-821X(73)90013-7. .
[22] Kakiuchi, H.; Momoshima, N.; Okai, T.; Maeda, Y. (1999). "Tritium concentration in ocean". Journal of Radioanalytical and Nuclear
Chemistry 239: 523. doi:10.1007/BF02349062.
[23] Fine, Rana A. et al. (1981). "Circulation of Tritium in the Pacific Ocean". Journal of Physical Oceanography 11: 3–14.
doi:10.1175/1520-0485(1981)011<0003:COTITP>2.0.CO;2.
[24] Michel, Robert L. (2004). "Tritium hydrology of the Mississippi River basin". Hydrological Processes 18: 1255. doi:10.1002/hyp.1403.
[25] Hartmann, Christian (2004). "Sutherland und das “flüssige Licht”". DO - Deutsche Zeitschrift für Osteopathie 2: 33.
doi:10.1055/s-2004-836019.
[26] Alvarez, Luis W; Peter Trower, W (1987). Discovering Alvarez: selected works of Luis W. Alvarez, with commentary by his students and
colleagues (http:/ / books. google. com/ ?id=imidr-iFYCwC& pg=PA26). pp. 26–30. ISBN 9780226813042. .
[27] Kaufman, Sheldon; Libby, W. (1954). "The Natural Distribution of Tritium". Physical Review 93: 1337. doi:10.1103/PhysRev.93.1337.
Tritium 69
External links
• Annotated bibliography for tritium from the Alsos Digital Library (http://alsos.wlu.edu/qsearch.
aspx?browse=science/Tritium)
• NLM Hazardous Substances Databank – Tritium, Radioactive (http://toxnet.nlm.nih.gov/cgi-bin/sis/search/
r?dbs+hsdb:@term+@na+@rel+tritium,+radioactive)
• Nuclear Data Evaluation Lab (http://atom.kaeri.re.kr/)
• Review of risks from tritium. Report of the independent Advisory Group on Ionising Radiation. (http://www.hpa.
org.uk/web/HPAweb&HPAwebStandard/HPAweb_C/1197382220012). Health Protection Agency.
November 2007. RCE-4.
• Tritium on Ice: The Dangerous New Alliance of Nuclear Weapons and Nuclear Power by Kenneth D. Bergeron
(http://books.google.com/books?id=sYKYZaxg0RUC)
Hydrogen-4
Hydrogen-4
Full table
General
Neutrons 3
Protons 1
Nuclide data
Half-life [1]
(1.39 ± 0.10) × 10−22 seconds
Hydrogen-4 is a highly unstable isotope of hydrogen. The nucleus consists of a proton and three neutrons. It has
been synthesised in the laboratory by bombarding tritium with fast-moving deuterium nuclei.[3] In this experiment,
the tritium nuclei captured neutrons from the fast-moving deuterium nucleus. The presence of the hydrogen-4 was
deduced by detecting the emitted protons. Its atomic mass is 4.02781 ± 0.00011[2] . It decays through neutron
emission and has a half-life of (1.39 ± 0.10) × 10−22 seconds.[1]
Hydrogen-4 70
Quadium
In the 1955 satirical novel The Mouse That Roared, the name quadium was given to the hydrogen-4 isotope that
powered the Q-bomb that the Duchy of Grand Fenwick captured from the United States.
See also
• Isotopes of hydrogen
References
[1] p. 27, The NUBASE evaluation of nuclear and decay properties (http:/ / amdc. in2p3. fr/ nubase/ Nubase2003. pdf), G. Audi, O. Bersillon, J.
Blachot, and A. H. Wapstra, Nuclear Physics A 729 (2003), pp. 3–128.
[2] AME2003 atomic mass evaluation (http:/ / www. nndc. bnl. gov/ amdc/ web/ masseval. html), Atomic Mass Data Center. Accessed on line
November 15, 2008.
[3] Hydrogen-4 and Hydrogen-5 from t+t and t+d transfer reactions studied with a 57.5-MeV triton beam, G. M. Ter-Akopian et al., Nuclear
Physics in the 21st Century: International Nuclear Physics Conference INPC 2001, American Institute of Physics Conference Proceedings
610, pp. 920-924, doi:10.1063/1.1470062.
Hydrogen-5
Hydrogen-5
Full table
General
Neutrons 4
Protons 1
Nuclide data
Half-life [1]
>9.1 × 10−22 seconds
Spin (1/2+)
Hydrogen-5 is a highly unstable isotope of hydrogen. The nucleus consists of a proton and four neutrons. It has been
synthesised in the laboratory by bombarding tritium with fast-moving tritium nuclei.[3] In this experiment, one
tritium nucleus captures both neutrons from the other, becoming a nucleus with one proton and four neutrons. The
remaining proton may be detected, and the existence of hydrogen-5 deduced. It decays through emission of two
neutrons and has a half-life of more than 9.1 × 10−22 seconds.[1]
Hydrogen-5 71
See also
• Isotopes of hydrogen
References
[1] p. 27, The NUBASE evaluation of nuclear and decay properties (http:/ / amdc. in2p3. fr/ nubase/ Nubase2003. pdf), G. Audi, O. Bersillon, J.
Blachot, and A. H. Wapstra, Nuclear Physics A 729 (2003), pp. 3–128.
[2] AME2003 atomic mass evaluation (http:/ / www. nndc. bnl. gov/ amdc/ web/ masseval. html), Atomic Mass Data Center. Accessed on line
November 15, 2008.
[3] Hydrogen-4 and Hydrogen-5 from t+t and t+d transfer reactions studied with a 57.5-MeV triton beam, G. M. Ter-Akopian et al., Nuclear
Physics in the 21st Century: International Nuclear Physics Conference INPC 2001, American Institute of Physics Conference Proceedings
610, pp. 920-924, doi:10.1063/1.1470062.
Thermal properties
The permutational antisymmetry of the H2 wavefunction (protons are fermions) imposes restrictions on the possible
rotational states the two forms of H2 can adopt. Orthohydrogen, with symmetric nuclear spin functions, can only
have rotational wavefunctions that are antisymmetric with respect to permutation of the two protons. Conversely,
parahydrogen with an antisymmetric nuclear spin function, can only have rotational wavefunctions that are
symmetric with respect to permutation of the two protons. Applying the rigid rotor approximation, the energies and
degeneracies of the rotational states are given by[3]
However, as long as these two spin isomers are not in equilibrium, it is more useful to write separate partition
functions for each,
.
The factor of 3 in the partition function for orthohydrogen accounts for the spin degeneracy associated with the +1
spin state. When equilibrium between the spin isomers is possible, then a general partition function incorporating
this degeneracy difference can be written as
The molar rotational energies and heat capacities are derived for any of these cases from
Because of the antisymmetry-imposed restriction on possible rotational states, orthohydrogen has residual rotational
energy at low temperature wherein nearly all the molecules are in the J = 1 state (molecules in the symmetric
spin-triplet state can not fall into the lowest, symmetric rotational state) and possesses nuclear-spin entropy due to
the triplet state's threefold degeneracy. The residual energy is significant because the rotational energy levels are
relatively widely spaced in H2; the gap between the first two levels when expressed in temperature units is twice the
rotational temperature for H2,
This is the T = 0 intercept seen in the molar energy of orthohydrogen. This residual energy, 1091 J/mol, is somewhat
larger than the enthalpy of vaporization of normal hydrogen, 904 J/mol at the boiling point, Tb = 20.369 K (this
refers to the "normal", room-temperature, 3:1 ortho:para mixture).[4] Notably, the boiling points of parahydrogen
and normal (3:1) hydrogen are nearly equal; for parahydrogen ∆Hvap = 898 J/mol at Tb = 20.277 K. It follows that
nearly all the residual rotational energy of orthohydrogen is retained in the liquid state. Orthohydrogen is
consequently unstable at low temperatures and spontaneously converts into parahydrogen, but the process is slow in
Spin isomers of hydrogen 73
the absence of a magnetic catalyst to facilitate interconversion of the singlet and triplet spin states. At room
temperature, hydrogen contains 75% orthohydrogen, a proportion which the liquefaction process preserves if carried
out in the absence of a catalyst like ferric oxide, activated carbon, platinized asbestos, rare earth metals, uranium
compounds, chromic oxide, or some nickel compounds[5] to accelerate the conversion of the liquid hydrogen into
parahydrogen, or supply additional refrigeration equipment to absorb the heat that the orthohydrogen fraction will
release as it spontaneously converts into parahydrogen.
The first synthesis of pure parahydrogen was achieved by Paul Harteck and Karl Friedrich Bonhoeffer in 1929.
When used during hydrogenations, parahydrogen gives rise to hyperpolarized signals in the NMR spectrum. This
effect is called PHIP or PASADENA effect and was simultaneously discovered at two laboratories in Los Angeles
(USA) and Bonn (Germany) in 1995. It was subsequently utilized to study the mechanism of hydrogenation
reactions.
Modern isolation of pure parahydrogen has been achieved utilizing rapid in-vacuum deposition of millimeters thick
solid parahydrogen (pH2) samples which are notable for their excellent optical qualities.[6]
Further research regarding parahydrogen thinfilm quantum state polarization matrices for computation seems a likely
future prospect for these material sets.
References
[1] P. Atkins and J. de Paula, Atkins' Physical Chemistry, 8th edition (W.H.Freeman 2006), p.452
[2] Rock, Peter A. "Chemical Thermodynamics", MacMillan 1969, p.478
[3] F. T. Wall (1974). Chemical Thermodynamics, 3rd Edition. W. H. Freeman and Company.
[4] http:/ / webbook. nist. gov/ chemistry/ fluid/
[5] Ortho-Para conversion. Pag. 13 (http:/ / www. mae. ufl. edu/ NasaHydrogenResearch/ h2webcourse/ L11-liquefaction2. pdf)
[6] Rapid Vapor Deposition of Millimeters Thick Optically Transparent Solid Parahydrogen Samples for Matrix Isolation Spectroscopy (http:/ /
www. stormingmedia. us/ 72/ 7208/ A720893. html)
1. Tikhonov V. I., Volkov A. A. (2002). "Separation of water into its ortho and para isomers". Science 296 (5577):
2363. doi:10.1126/science.1069513. PMID 12089435.
2. Bonhoeffer KF, Harteck P (1929). "Para- and ortho hydrogen". Zeitschrift für Physikalische Chemie B 4 (1-2):
113–141.
3. A. Farkas (1935). Orthohydrogen, parahydrogen and heavy hydrogen,. The Cambridge series of physical
chemistry.
4. Mario E. Fajardo; Simon Tam (1997). Rapid Vapor Deposition of Millimeters Thick Optically Transparent Solid
Parahydrogen Samples for Matrix Isolation Spectroscopy. AIR FORCE RESEARCH LAB EDWARDS AFB CA
PROPULSION DIRECTORATE WEST.
74
Reactions
Bosch reaction
The Bosch reaction is a chemical reaction between carbon dioxide and hydrogen that produces elemental carbon
(graphite), water and a 10% return of invested heat. This reaction requires the introduction of iron as a catalyst and
requires a temperature level of 530-730 degrees Celsius.[1]
The overall reaction is as follows:
CO2(g) + 2 H2(g) → C(s) + 2 H2O(g)
The above reaction is actually the result of two reactions. The first reaction, the reverse water gas shift reaction, is a
fast one.
CO2 + H2 → CO + H2O
The second reaction controls the reaction rate.
CO + H2 → C + H2O
The overall reaction produces 2.3×103 joules for every gram of carbon produced at 650 °C. Reaction temperatures
are in the range of 450 to 600 °C.
The reaction can be accelerated in the presence of an iron, cobalt or nickel catalyst. Ruthenium also serves to speed
up the reaction.
Together with the Sabatier reaction the Bosch reaction is studied as a way to remove carbon dioxide and to generate
clean water aboard a space station [2]
The reaction is also used to produce graphite for radiocarbon dating with Accelerator Mass Spectrometry.
It is named after the German chemist Carl Bosch.
The Bosch reaction is being investigated for use in maintaining space station life support. Though the Bosch reaction
would present a completely closed hydrogen and oxygen cycle which only produces atomic carbon as waste,
difficulties maintaining its higher required temperature and properly handling carbon deposits mean significantly
more research will be required before a Bosch reactor could become a reality. One problem is that the production of
elemental carbon tends to foul the catalyst's surface, which is detrimental to the reaction's efficiency.
Notes
[1] Messerschmid, Ernst and Reinhold Bertrand. Space Stations. Springer. 1999.
[2] Methods of water production (http:/ / oregonstate. edu/ ~atwaterj/ h2o_gen. htm)
External links
• A carbon dioxide reduction unit using Bosch reaction (http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/
19710002858_1971002858.pdf)
Hydrogen cycle 75
Hydrogen cycle
Hydrogen is one of the constituents of water. It recycles as in other biogeochemical cycles. It is actively involved
with the other cycles like the carbon cycle, nitrogen cycle, sulfur cycle and oxygen cycle as well.
Anaerobic fermentation of organic substances to carbon dioxide and methane is a collaborative effort involving
many different biochemical reactions, processes and species of microorganisms. One of these many processes that
occur is termed "interspecies hydrogen transfer". This process has been described as integral to the symbiosis
between certain methane-producing bacteria (methanogens) and nonmethanogenic anaerobes. In this symbiosis, the
nonmethanogenic anaerobes degrade the organic substance and produce -among other things- molecular hydrogen
(H2). This hydrogen is then taken up by methanogens and converted to methane via methanogenesis. One important
characteristic of interspecies hydrogen transfer is that the H2 concentration in the microbial environment is very low.
Maintaining a low hydrogen concentration is important because the anaerobic fermentative process become
increasingly thermodynamically unfavorable as the partial pressure of hydrogen increases. A key difference
compared to other biogeochemical cycles is that because of its low molecular weight hydrogen can leave Earth's
atmosphere. It has been suggested that this occurred on a grand scale in the past and that this is why today the Earth
is mostly irreversibly oxidised.[1]
References
[1] http:/ / www. sciencemag. org/ cgi/ content/ abstract/ 293/ 5531/ 839 Biogenic Methane, Hydrogen Escape, and the Irreversible Oxidation of
Early Earth David C. Catling, Kevin J. Zahnle, and Christopher McKay (3 August 2001) Science 293 (5531), 839. [DOI:
10.1126/science.1061976]
External links
• A Lecture (http://www.biosci.ohio-state.edu/~mgonzalez/Micro521/19.html)
Bibliography
• "Microbiology and Biochemistry of Strict Anaerobes Involved in Interspecies Hydrogen Transfer" by Jean-Pierre
Bélaich; Mireille Bruschi; Jean-Louis Garcia; Federation of European Microbiological Societies. Published Nov
1990. ISBN 0306435179
• (http://whitman.myweb.uga.edu/coursedocs/mibo8610/de bok et al 04.pdf) F.A.M. de Bok, C.M. Plugge,
and A.J.M. Stams; "Interspecies electron transfer in methanogenic proprionate degrading consortia". Water
Research 38 (2004): 1368-1375
• (http://www.ingentaconnect.com/content/bsc/emi/2006/00000008/00000003/art00001) A.J.M. Stams et al.,
"Exocellular electron transfer in anaerobic microbial communities", Environmental Microbiology, 8
(2006):371-382
Hydrogenation 76
Hydrogenation
Catalysed hydrogenation
Process type Chemical
Industrial sector(s) Food industry, petrochemical industry, pharmaceutical industry, agricultural industry
Hydrogenation, to treat with hydrogen, also a form of chemical reduction, is a chemical reaction between molecular
hydrogen (H2) and another compound or element, usually in the presence of a catalyst. The process is commonly
employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of
hydrogen atoms to a molecule, generally an alkene. Catalysts are required for the reaction to be usable; non-catalytic
hydrogenation takes place only at very high temperatures. Hydrogen adds to double and triple bonds in
hydrocarbons.[1]
Because of the importance of hydrogen, many related reactions have been developed for its use. Most
hydrogenations use gaseous hydrogen (H2), but some involve the alternative sources of hydrogen, not H2: these
processes are called transfer hydrogenations. The reverse reaction, removal of hydrogen from a molecule, is called
dehydrogenation. A reaction where bonds are broken while hydrogen is added is called hydrogenolysis, a reaction
that may occur to carbon-carbon and carbon-heteroatom (O, N, X) bonds. Hydrogenation differs from protonation or
hydride addition: in hydrogenation, the products have the same charge as the reactants.
An illustrative example of a hydrogenation reaction is the addition of hydrogen to maleic acid to succinic acid
depicted on the right.[2] Numerous important applications are found in the petrochemical, pharmaceutical and food
industries. Hydrogenation of unsaturated fats produces saturated fats and, in some cases, trans fats.
Process
Hydrogenation has three components,
the unsaturated substrate, the hydrogen
(or hydrogen source) and, invariably, a
catalyst. The reaction is carried out at
different temperatures and pressures
depending upon the substrate and the activity of the catalyst.
Hydrogenation 77
Substrate
The addition of H2 to an alkene affords an alkane in the protypical reaction:
RCH=CH2 + H2 → RCH2CH3 (R = alkyl, aryl)
Hydrogenation is sensitive to steric hindrance explaining the selectivity for reaction with the exocyclic double bond
but not the internal double bond.
An important characteristic of alkene and alkyne hydrogenations, both the homogeneously and heterogeneously
catalyzed versions, is that hydrogen addition occurs with "syn addition", with hydrogen entering from the least
hindered side.[3] Typical substrates are listed in the table
Catalysts
With rare exception, no reaction below 480 °F occurs between H2 and organic compounds in the absence of metal
catalysts. The catalyst binds both the H2 and the unsaturated substrate and facilitates their union. Platinum group
metals, particularly platinum, palladium, rhodium, and ruthenium, form highly active catalysts, which operate at
lower temperatures and lower pressures of H2. Non-precious metal catalysts, especially those based on nickel (such
as Raney nickel and Urushibara nickel) have also been developed as economical alternatives, but they are often
slower or require higher temperatures. The trade-off is activity (speed of reaction) vs. cost of the catalyst and cost of
the apparatus required for use of high pressures. Notice that the Raney-nickel catalysed hydrogenations require high
pressures:[4] [5]
Two broad families of catalysts are
known - homogeneous catalysts and
heterogeneous catalysts. Homogeneous
catalysts dissolve in the solvent that
contains the unsaturated substrate.
Heterogeneous catalysts are solids that
are suspended in the same solvent with
the substrate or are treated with
gaseous substrate.
Hydrogenation 78
Homogeneous catalysts
Illustrative homogeneous catalysts include the rhodium-based compound known as Wilkinson's catalyst and the
iridium-based Crabtree's catalyst. An example is the hydrogenation of carvone:[6]
Hydrogenation is sensitive to steric
hindrance explaining the selectivity for
reaction with the exocyclic double bond but
not the internal double bond.
The activity and selectivity of homogeneous
catalysts is adjusted by changing the
ligands. For prochiral substrates, the
selectivity of the catalyst can be adjusted
such that one enantiomeric product is favored. Asymmetric hydrogenation is also possible via heterogeneous
catalysis on a metal that is modified by a chiral ligand.[7]
Heterogeneous catalysts
Heterogeneous catalysts for hydrogenation are more common industrially. As in homogeneous catalysts, the activity
is adjusted through changes in the environment around the metal, i.e. the coordination sphere. Different faces of a
crystalline heterogeneous catalyst display distinct activities, for example. Similarly, heterogeneous catalysts are
affected by their supports, i.e. the material upon with the heterogeneous catalyst is bound. In many cases, highly
empirical modifications involve selective "poisons". Thus, a carefully chosen catalyst can be used to hydrogenate
some functional groups without affecting others, such as the hydrogenation of alkenes without touching aromatic
rings, or the selective hydrogenation of alkynes to alkenes using Lindlar's catalyst. For example, when the catalyst
palladium is placed on barium sulfate and then treated with quinoline, the resulting catalyst reduces alkynes only as
far as alkenes. The Lindlar catalyst has been applied to the conversion of phenylacetylene to styrene.[8]
Asymmetric hydrogenation is also
possible via heterogeneous catalysis on
a metal that is modified by a chiral
ligand.[7]
Hydrogen sources
For hydrogenation, the obvious source of hydrogen is H2 gas itself, which is typically available commercially within
the storage medium of a pressurized cylinder. The hydrogenation process often uses greater than 1 atmosphere of H2,
usually conveyed from the cylinders and sometimes augmented by "booster pumps". Gaseous hydrogen is produced
industrially from hydrocarbons by the process known as steam reforming.[9]
Hydrogen may, in specialised applications, also be extracted ("transferred") from "hydrogen-donors" in place of H2
gas. Hydrogen donors, which often serve as solvents include hydrazine, dihydronaphthalene, dihydroanthracene,
isopropanol, and formic acid.[10] In organic synthesis, transfer hydrogenation is useful for the reduction of polar
unsaturated substrates, such as ketones, aldehydes, and imines.
Hydrogenation 79
Heterogeneous catalysis
On solids, the accepted mechanism today is called the Horiuti-Polanyi mechanism.
1. Binding of the unsaturated bond, and hydrogen dissociation into atomic hydrogen onto the catalyst
2. Addition of one atom of hydrogen; this step is reversible
3. Addition of the second atom; effectively irreversible under hydrogenating conditions.
Homogeneous catalysis
In many homogeneous hydrogenation processes,[12] the metal binds to both components to give an intermediate
alkene-metal(H)2 complex. The general sequence of reactions is assumed to be as follows or a related sequence of
steps:
• binding of the hydrogen to give a dihydride complex ("oxidative addition"):
LnM + H2 → LnMH2
• binding of alkene:
LnM(η2H2) + CH2=CHR → Ln-1MH2(CH2=CHR) + L
• transfer of one hydrogen atom from the metal to carbon (migratory insertion)
Ln-1MH2(CH2=CHR) → Ln-1M(H)(CH2-CH2R)
• transfer of the second hydrogen atom from the metal to the alkyl group with simultaneous dissociation of the
alkane ("reductive elimination")
Ln-1M(H)(CH2-CH2R) → Ln-1M + CH3-CH2R
Preceding the oxidative addition of H2 is the formation of a dihydrogen complex.
Inorganic substrates
The hydrogenation of nitrogen to give ammonia is conducted on a vast scale by the Haber-Bosch process, consuming
an estimated 1% of the world's energy supply.
Oxygen can be partially hydrogenated to give hydrogen peroxide,
although this process has not been commercialized.
Industrial applications
Catalytic hydrogenation has diverse industrial uses.
In petrochemical processes, hydrogenation is used to convert alkenes and aromatics into saturated alkanes (paraffins)
and cycloalkanes (napthenes). Hydrocracking of heavy residues into diesel is another application. In isomerization
and catalytic reforming processes, some hydrogen pressure is maintained to hydrogenolyze coke and prevent its
accumulation.
Xylitol, a polyol, is produced by hydrogenation of the sugar xylose, an aldehyde.
Hydrogenation 80
Health implications
A side effect of incomplete hydrogenation having implications for human health is the isomerization of the
remaining unsaturated carbon bonds. The cis configuration of these double bonds predominates in the unprocessed
fats in most edible fat sources, but incomplete hydrogenation partially converts these molecules to trans isomers,
which have been implicated in circulatory diseases including heart disease (see trans fats). The conversion from cis
to trans bonds is favored because the trans configuration has lower energy than the natural cis one. At equilibrium,
the trans/cis isomer ratio is about 2:1. Food legislation in the US and codes of practice in EU have long required
labels declaring the fat content of foods in retail trade and, more recently, have also required declaration of the trans
fat content. Furthermore, trans fats are banned in Denmark and New York City.[13] [14]
History
The earliest hydrogenation is that of platinum catalyzed addition of hydrogen to oxygen in the Döbereiner's lamp, a
device commercialized as early as 1823. The French chemist Paul Sabatier is considered the father of the
hydrogenation process. In 1897, building on the earlier work of James Boyce, an American chemist working in the
manufacture of soap products, he discovered that the introduction of a trace of nickel as a catalyst facilitated the
addition of hydrogen to molecules of gaseous hydrocarbons in what is now known as the Sabatier process. For this
work Sabatier shared the 1912 Nobel Prize in Chemistry. Wilhelm Normann was awarded a patent in Germany in
1902 and in Britain in 1903 for the hydrogenation of liquid oils, which was the beginning of what is now a world
wide industry. The commercially important Haber-Bosch process, first described in 1905, involves hydrogenation of
nitrogen. In the Fischer-Tropsch process, reported in 1922 carbon monoxide, which is easily derived from coal, is
hydrogenated to liquid fuels.
Also in 1922, Voorhees and Adams described an apparatus for performing hydrogenation under pressures above one
atmosphere.[15] The Parr shaker, the first product to allow hydrogenation using elevated pressures and temperatures,
was commercialized in 1926 based on Voorhees and Adams’ research and remains in widespread use. In 1924
Murray Raney developed a nickel fine powder catalyst named after him which is still widely used in hydrogenation
reactions such as conversion of nitriles to amines or the production of margarine. In 1938, Otto Roelen described the
oxo process which involves the addition of both hydrogen and carbon monoxide to alkenes, giving aldehydes. Since
this process entails C-C coupling, it and its many variations (see carbonylation) remains highly topical into the new
decade.[16] The 1960s witnessed the development of homogeneous catalysts, e.g., Wilkinson's catalyst. In the 1980s,
the Noyori asymmetric hydrogenation represented one of the first applications of hydrogenation in asymmetric
synthesis, a growing application in the production of fine chemicals.
Hydrogenation 81
Metal-free hydrogenation
For all practical purposes, hydrogenation requires a metal catalyst. Hydrogenation can, however, proceed from some
hydrogen donors without catalysts, illustrative hydrogen donors being diimide and aluminium isopropoxide. Some
metal-free catalytic systems have been investigated in academic research. One such system for reduction of ketones
consists of tert-butanol and potassium tert-butoxide and very high temperatures.[17] The reaction depicted below
describes the hydrogenation of benzophenone:
A chemical kinetics study[18] found this reaction is first-order in all three reactants suggesting a cyclic 6-membered
transition state.
Another system for metal-free hydrogenation is based on the phosphine-borane, compound 1, which has been called
a frustrated Lewis pair. It reversibly accepts dihydrogen at relatively low temperatures to form the phosphonium
borate 2 which can reduce simple hindered imines.[19]
The reduction of nitrobenzene to aniline has been reported to be catalysed by fullerene , its mono-anion, atmospheric
hydrogen and UV light.[20]
Hydrogenation 82
Flow hydrogenation
Flow hydrogenation has become a popular technique at the bench and increasingly the process scale. This technique
involves continuously flowing a dilute stream of dissolved reactant over a fixed bed catalyst in the presence of
hydrogen. Using established HPLC technology, this technique allows the application of pressures from atmospheric
to 1,450 PSI. Elevated temperatures may also be used. At the bench scale, systems use a range of pre-packed
catalysts which eliminates the need for weighing and filtering pyrophoric catalysts.
Industrial reactors
Catalytic hydrogenation is done in a tubular plug-flow reactor (PFR) packed with a supported catalyst. The pressures
and temperatures are typically high, although this depends on the catalyst. Catalyst loading is typically much lower
than in laboratory batch hydrogenation, and various promoters are added to the metal, or mixed metals are used, to
improve activity, selectivity and catalyst stability. The use of nickel is common despite its low activity, due to its low
cost compared to precious metals.
Hydrogenation 83
See also
• Dehydrogenation
• Transfer hydrogenation
• Hydrogenolysis
• Hydrodesulfurization, Hydrotreater and Oil desulfurization
• Timeline of hydrogen technologies
• Hydrogenated Oils-Silent Killers by columnist, David Lawrence Dewey. The first journalist in 1996 to warn
consumers about hydrogenated oils [21]
References
[1] Hudlický, Miloš (1996). Reductions in Organic Chemistry. Washington, D.C.: American Chemical Society. pp. 429. ISBN 0-8412-3344-6.
[2] Catalytic Hydrogenation of Maleic Acid at Moderate Pressures A Laboratory Demonstration Kwesi Amoa 1948 Journal of Chemical
Education • Vol. 84 No. 12 December 2007
[3] Advanced Organic Chemistry Jerry March 2nd Edition
[4] C. F. H. Allen and James VanAllan (1955), "m-Toylybenzylamine" (http:/ / www. orgsyn. org/ orgsyn/ orgsyn/ prepContent.
asp?prep=CV3P0827), Org. Synth., ; Coll. Vol. 3: 827
[5] A. B. Mekler, S. Ramachandran, S. Swaminathan, and Melvin S. Newman (1973), "2-Methyl-1,3-Cyclohexanedione" (http:/ / www. orgsyn.
org/ orgsyn/ orgsyn/ prepContent. asp?prep=CV5P0567), Org. Synth., ; Coll. Vol. 5: 743
[6] S. Robert E. Ireland and P. Bey (1988), "Homogeneous Catalytic Hydrogenation: Dihydrocarvone" (http:/ / www. orgsyn. org/ orgsyn/
orgsyn/ prepContent. asp?prep=CV6P0459), Org. Synth., ; Coll. Vol. 6: 459
[7] T. Mallet, E. Orglmeister, A. Baiker" Chemical Reviews, 2007, 107, 4863-4890. DOI: 10.1021/cr0683663
[8] H. Lindlar and R. Dubuis (1973), "Palladium Catalyst for Partial Reduction of Acetylenes" (http:/ / www. orgsyn. org/ orgsyn/ orgsyn/
prepContent. asp?prep=CV5P0880), Org. Synth., ; Coll. Vol. 5: 880
[9] Paul N. Rylander, "Hydrogenation and Dehydrogenation" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
[10] van Es, T.; Staskun, B. "Aldehydes from Aromatic Nitriles: 4-Formylbenzenesulfonamide" Org. Syn., Coll. Vol. 6, p.631 (1988). ( Article
(http:/ / www. orgsyn. org/ orgsyn/ prep. asp?prep=cv6p0631))
[11] Kubas, G. J., "Metal Dihydrogen and σ-Bond Complexes", Kluwer Academic/Plenum Publishers: New York, 2001
[12] Johannes G. de Vries, Cornelis J. Elsevier, eds. The Handbook of Homogeneous Hydrogenation Wiley-VCH, Weinheim, 2007. ISBN
978-3-527-31161-3
[13] "Deadly fats: why are we still eating them?" (http:/ / www. independent. co. uk/ life-style/ health-and-wellbeing/ healthy-living/
deadly-fats-why-are-we-still-eating-them-843400. html). The Independent. 2008-06-10. . Retrieved 2008-06-16.
[14] "New York City passes trans fat ban" (http:/ / www. msnbc. msn. com/ id/ 16051436/ ). msnbc. 2006-12-05. . Retrieved 2010-01-09.
[15] (http:/ / pubs. acs. org/ cgi-bin/ abstract. cgi/ jacsat/ 1922/ 44/ i06/ f-pdf/ f_ja01427a021. pdf)
[16] Perspective: Hydrogen-Mediated C-C Bond Formation: A Broad New Concept in Catalytic C-C Coupling Ming-Yu Ngai, Jong-Rock Kong,
and Michael J. Krische J. Org. Chem.; 2007, 72, pp. 1063–1072. doi:10.1021/jo061895m
[17] Homogeneous Hydrogenation in the Absence of Transition-Metal Catalysts Cheves Walling, Laszlo Bollyky J. Am. Chem. Soc.; 1964;
86(18); 3750–3752. doi:10.1021/ja01072a028
[18] Hydrogenation without a Transition-Metal Catalyst: On the Mechanism of the Base-Catalyzed Hydrogenation of Ketones Albrecht
Berkessel, Thomas J. S. Schubert, and Thomas N. Muller J. Am. Chem. Soc. 2002, 124, 8693–8698 doi:10.1021/ja016152r
[19] Metal-Free Catalytic Hydrogenation Preston A. Chase, Gregory C. Welch, Titel Jurca, and Douglas W. Stephan Angew. Chem. Int. Ed.
2007, 46, 8050–8053. doi:10.1002/anie.200702908
[20] A Nonmetal Catalyst for Molecular Hydrogen Activation with Comparable Catalytic Hydrogenation Capability to Noble Metal Catalyst
Baojun Li and Zheng Xu J. Am. Chem. Soc., 2009, 131 (45), pp 16380–16382. doi:10.1021/ja9061097
[21] http:/ / www. dldewey. com/ hydroil. htm
Hydrogenation 84
Further reading
• Jang ES, Jung MY, Min DB (2005). "Hydrogenation for Low Trans and High Conjugated Fatty Acids" (http://
members.ift.org/NR/rdonlyres/27B49B9B-EA63-4D73-BAB4-42FEFCD72C68/0/
crfsfsv4n1p00220030ms20040577.pdf) (PDF). Comprehensive Reviews in Food Science and Food Safety 1.
• examples of hydrogenation from Organic Syntheses:
• Organic Syntheses, Coll. Vol. 7, p.226 (1990). (http://orgsynth.org/orgsyn/pdfs/CV7P0226.pdf)
• Organic Syntheses, Coll. Vol. 8, p.609 (1993). (http://orgsynth.org/orgsyn/pdfs/CV8P0609.pdf)
• Organic Syntheses, Coll. Vol. 5, p.552 (1973). (http://orgsynth.org/orgsyn/pdfs/CV5P0552.pdf)
• Organic Syntheses, Coll. Vol. 3, p.720 (1955). (http://orgsynth.org/orgsyn/pdfs/CV4P0603.pdf)
• Organic Syntheses, Coll. Vol. 6, p.371 (1988). (http://orgsynth.org/orgsyn/pdfs/CV6P0371.pdf)
• early work on transfer hydrogenation: Davies, R. R.; Hodgson, H. H. J. Chem. Soc. 1943, 281. Leggether, B. E.;
Brown, R. K. Can. J. Chem. 1960, 38, 2363. Kuhn, L. P. J. Am. Chem. Soc. 1951, 73, 1510.
• Fred A. Kummerow (2008). Cholesterol Won't Kill You, But Trans Fat Could. Trafford. ISBN 142513808.
Dehydrogenation
Dehydrogenation is a chemical reaction that involves the elimination of hydrogen (H2). It is the reverse process of
hydrogenation. Dehydrogenation reactions may be either large scale industrial processes or smaller scale laboratory
procedures.
There are a variety of classes of dehydrogenations:
• Aromatization - Six-membered alicyclic rings can be aromatized in the presence of hydrogenation catalysts, the
elements sulfur and selenium, or quinones (such as DDQ).
• Oxidation - The conversion of alcohols to ketones or aldehydes can be effected by metal catalysts such as copper
chromite. In the Oppenauer oxidation, hydrogen is transferred from one alcohol to another to bring about the
oxidation.
• Dehydrogenation of amines - amines can be converted to nitriles using a variety of reagents, such as IF5.
• Dehydrogenation of paraffins and olefins - paraffins like n-pentane and isopentane can be converted to pentene
and isoprene using chromium (III) oxide as a catalyst at 500 degree C.
Dehydrogenation converts saturated fats to unsaturated fats.
Enzymes that catalyze dehydrogenation are called dehydrogenases.
References
• Advanced Organic Chemistry, Jerry March, 1162-1173.
Transfer hydrogenation 85
Transfer hydrogenation
Transfer hydrogenation is the addition of hydrogen (H2; dihydrogen in inorganic and organometallic chemistry) to
a molecule from a source other than gaseous H2. It is applied in industry and in organic synthesis, in part because of
the inconvenience and expense of using gaseous H2. One large scale application of transfer hydrogenation is coal
liquefaction using "donor solvents" such as tetralin.[1] [2]
Organometallic catalysts
In the area of organic synthesis, a useful family of hydrogen-transfer catalysts have been developed based on
ruthenium and rhodium complexes with diamine and phosphine ligands.[3] A representative catalyst precursor is
derived from (cymene)ruthenium dichloride dimer and the tosylated diphenylethylenediamine. These catalysts are
mainly employed for the reduction of ketones and imines to alcohols and amines, respectively. The hydrogen-donor
(transfer agent) is typically isopropanol, which coverts to acetone upon donation of hydrogen. Transfer
hydrogenations can proceed with high enantioselectivities when the starting material is prochiral:
RR'C=O + Me2CHOH → RR'C*H-OH + Me2C=O
where RR'C*H-OH is a chiral product. A typical catalyst is (cymene(R,R-HNCHPhCHPhNTs), where Ts =
SO2C6H4Me and R,R refers to the absolute configuration of the two chiral carbon centers. This work was recognized
with the 2001 Nobel Prize in Chemistry to Ryōji Noyori. Another family of hydrogen-transfer agents are those based
on aluminium alkoxides, such as Aluminium isopropoxide.
Hydrogen donors
A historically prominent transfer hydrogenation agent is diimide, which becomes oxidized to the very stable N2:
The diimide is generated from hydrazine. Two hydrocarbons that can serve as hydrogen donors are cyclohexene or
cyclohexadiene. In this case an alkane is formed along with the formation of benzene. The driving force of the
reaction being the gain of aromatic stabilization energy when benzene is formed. Pd can be used as a catalyst and a
temperature of 100 °C is employed. One limitation of using transfer hydrogenation for the production of alkane is
that it cannot be used to prepare methane as no unsaturated hydrocarbon contain only one carbon. More exotic
transfer hydrogenations have been reported, including this intramolecular one:
Transfer hydrogenation 86
Many reactions exist with alcohol as the hydrogen donor. Examples are the sodium metal mediated Birch reduction
(arenes) and the Bouveault-Blanc reduction (esters). The combination of magnesium and methanol is used in alkene
reductions, e.g. the synthesis of asenapine:[4]
In this particular reaction the substrate is an α,β-unsaturated carbonyl compound. The proton donor is oxidized to the
pyridine form and resembles the biochemically relevant coenzyme NADH. In the catalytic cycle for this reaction the
Transfer hydrogenation 87
amine and the aldehyde first form an iminium ion, then proton transfer is followed by hydrolysis of the iminium
bond regenerating the catalyst. By adopting a chiral imidazolidinone MacMillan organocatalyst an enantioselectivity
of 81% ee was obtained:
The group of MacMillan independently published a very similar asymmetric reaction in 2005 [6] :
In an interesting case of stereoconvergence, both the E-isomer and the Z-isomer in this reaction yield the
(S)-enantiomer.
Extending the scope of this reaction towards ketones or rather enones requires fine tuning of the catalyst (add a
benzyl group and replace the t-butyl group by a furan) and of the Hantzsch ester (add more bulky t-butyl groups) [7] :
With a different organocatalyst altogether, hydrogenation can also be accomplished for imines. In one particular
reaction the catalysts is a BINOL based phosphoric acid, the substrate a quinoline and the product a chiral
tetradehydroquinoline in a 1,4-addition, isomerization and 1,2-addition cascade reaction [8] :
Transfer hydrogenation 88
The first step in this reaction is protonation of the quinoline nitrogen atom by the phosphoric acid forming a transient
chiral iminium ion. It is noted that with most traditional metal based catalysts, hydrogenation of aromatic or
heteroaromatic substrates tend to fail.
References
[1] Speight, J. G. "The Chemistry and Technology of Coal" Marcel Dekker; New York, 1983; p. 226 ff. ISBN 0-8247-1915-8.
[2] Muñiz, Kilian (2005). "Bifunctional Metal-Ligand Catalysis: Hydrogenations and New Reactions within the Metal-(Di)amine Scaffold13".
Angewandte Chemie International Edition 44 (41): 6622–6627. doi:10.1002/anie.200501787. PMID 16187395.
[3] T. Ikariya, K. Murata, R. Noyori "Bifunctional Transition Metal-Based Molecular Catalysts for Asymmetric Syntheses" Org. Biomol. Chem.,
2006, volume 4, 393-406.
[4] Linden, M. V. D.; Roeters, T.; Harting, R.; Stokkingreef, E.; Gelpke, A. S.; Kemperman, G. (2008). "Debottlenecking the Synthesis Route of
Asenapine". Organic Process Research & Development 12: 196–201. doi:10.1021/op700240c.
[5] Yang; Hechavarria Fonseca, M.; List, B. (2004). "A metal-free transfer hydrogenation: organocatalytic conjugate reduction of
alpha,beta-unsaturated aldehydes". Angewandte Chemie (International ed. in English) 43 (48): 6660–6662. doi:10.1002/anie.200461816.
PMID 15540245.
[6] Ouellet; Tuttle, J.; MacMillan, D. (2005). "Enantioselective organocatalytic hydride reduction". Journal of the American Chemical Society
127 (1): 32–33. doi:10.1021/ja043834g. PMID 15631434.
[7] Tuttle; Ouellet, S.; MacMillan, D. (2006). "Organocatalytic transfer hydrogenation of cyclic enones". Journal of the American Chemical
Society 128 (39): 12662–12663. doi:10.1021/ja0653066. PMID 17002356.
[8] Rueping; Antonchick, A.; Theissmann, T. (2006). "A highly enantioselective Brønsted acid catalyzed cascade reaction: organocatalytic
transfer hydrogenation of quinolines and their application in the synthesis of alkaloids". Angewandte Chemie (International ed. in English) 45
(22): 3683–3686. doi:10.1002/anie.200600191. PMID 16639754.
See also
• Dehydrogenation
• Hydrogenation
• Hydrogenolysis
Hydrogenolysis 89
Hydrogenolysis
Hydrogenolysis is a chemical reaction whereby a carbon-carbon or carbon-heteroatom single bond is cleaved or
undergoes "lysis" by hydrogen.[1] The heteroatom may vary, but it usually is oxygen, nitrogen, or sulfur. A related
reaction is hydrogenation, where hydrogen is added to the molecule, without cleaving bonds. Usually hydrogenolysis
is conducted catalytically using hydrogen gas.
History
The term "hydrogenolysis" was coined by Carleton Ellis in reference to hydrogenolysis of carbon-carbon bonds.[1] [2]
Earlier, Sabatier had already observed the hydrogenolysis of benzyl alcohol to toluene,[3] and as early as 1906, Padoa
and Ponti had observed the hydrogenolysis of furfuryl alcohol.[4] Adkins and Connors were the first to call the
carbon-oxygen bond cleavage "hydrogenolysis".[1]
In the laboratory
In the laboratory, hydrogenolysis is used in organic synthesis. Debenzylation is most common and involves the
cleavage of benzyl ethers:[6]
ROCH2C6H5 + H2 → ROH + CH3C6H5
Thioketals undergo hydrogenolysis using Raney nickel, a catalyst that, conveniently, carries its own hydrogen.
Laboratory hydrogenolysis is operationally similar to hydrogenation, and may be accomplished at atmospheric
pressure by stirring the reaction mixture under a slight positive pressure of hydrogen gas, having flushed the
apparatus with more of this gas. The hydrogen may be provided by attaching a balloon to a needle, filling it from a
bottle, and inserting the needle into the reaction flask via a rubber septum. At high pressure, a hydrogenation
autoclave (i.e., a Parr hydrogenator) or similar piece of equipment is required.
References
[1] Ralph Connor, Homer Adkins. Hydrogenolysis Of Oxygenated Organic Compounds. J. Am. Chem. Soc.; 1932; 54(12); 4678-4690. DOI:
10.1021/ja01351a026
[2] Carleton Ellis. Hydrogenation of Organic Substances, 3rd ed., Van Nostrand Company, New York, 1930, p. 564 (as referred by Connor and
Adkins).
[3] Sabatier and Murat. Ann. Chim. [9] 4, 258, (1915), according to Connor and Adkins.
[4] Furfuryl alcohol hydrogenation is accompanied by hydrogenolysis into 2-methylfuran, which gives 2-methyltetrahydrofuran, and further
hydrogenolysis opens the ring to give 2-pentanol. Original: Padoa and Ponti. Atti. R. accad. Lincei, 15, [5] 610 (1906); Gazz. chim. ital. 37,
[2] 105 (1907), according to Kaufmann: W. E. Kaufmann, Roger Adams. The Use Of Platinum Oxide As A Catalyst In The Reduction Of
Organic Compounds. Iv. Reduction Of Furfural And Its Derivatives. J. Am. Chem. Soc.; 1923; 45(12); 3029-3044. DOI:
10.1021/ja01665a033
[5] Topsøe, H.; Clausen, B. S.; Massoth, F. E., Hydrotreating Catalysis, Science and Technology, Springer-Verlag: Berlin, 1996.
Hydrogenolysis 90
[6] For example Organic Syntheses, Coll. Vol. 7, p.386 (1990); Vol. 60, p.92 (1981). http:/ / orgsynth. org/ orgsyn/ pdfs/ CV7P0386. pdf. For
example of C-N scission, see Organic Syntheses, Coll. Vol. 8, p.152 (1993); Vol. 68, p.227 (1990). http:/ / orgsynth. org/ orgsyn/ pdfs/
CV8P0152. pdf
Hydron
In chemistry, hydron is the general name for the positive hydrogen H+ cation.
The term is recommended by IUPAC to be used instead of proton if no
distinction is made between the isotopes proton, deuteron and triton, all found
in naturally occurring undifferentiated isotope mixtures. The name proton is
primarily used for isotopically pure 1H+. [1]
Hydron was defined by IUPAC in 1988.[2] [3] Traditionally, the term "proton"
was and is used in place of "hydron". However, although 99.9 % of natural
hydrogen nuclei are protons, small amounts are deuterons and rare tritons.
Hydron was located and identified by Walter Russell and documented in his
1926 book "The Universal One".
The hydrated form of the hydrogen cation is the hydronium ion, H3O+(aq) The
negatively-charged counterpart of the hydron is the hydride anion, H-.
See also
• Hydrogen anion
References
[1] Nomenclature of Inorganic Chemistry-IUPAC Recommendations 2005 Red Book 2005.pdf (http:/ / www. iupac. org/ publications/ books/
rbook/ Red_Book_2005. pdf) IR-3.3.2, p.48
[2] IUPAC Gold Book internet edition: " hydron (http:/ / goldbook. iupac. org/ H02904. html)".
[3] Bunnet, J.F.; Jones, R.A.Y. (1968). "Names for hydrogen atoms, ions, and groups, and for reactions involving them (Recommendations
1988)" (http:/ / www. iupac. org/ publications/ pac/ 1988/ pdf/ 6007x1115. pdf). Pure Appl. Chem. 60 (7): 1115–6.
doi:10.1351/pac198860071115. .
Sabatier reaction 91
Sabatier reaction
The Sabatier reaction or Sabatier process involves the reaction of hydrogen with carbon dioxide at elevated
temperatures and pressures in the presence of a nickel catalyst to produce methane and water. Optionally ruthenium
on alumina (aluminum oxide) makes a more efficient catalyst. It is described by the following reaction:
CO2 + 4H2 → CH4 + 2H2O
It was discovered by the French chemist Paul Sabatier.
Another option is to make more methane than needed and pyrolyze the excess it into carbon and hydrogen (see
above section) where the hydrogen is recycled back into the reactor to produce further methane and water. In an
automated system, the carbon deposit may be removed by blasting with hot Martian CO2, oxidizing the carbon into
carbon monoxide, which is vented.
A fourth solution to the stoichiometry problem would be to combine the Sabatier reaction with the reverse water
gas-shift reaction in a single reactor as follows:
3CO2 + 6H2 → CH4 + 2CO + 4H2O
This reaction is slightly exothermic, and when the water is electrolyzed, an oxygen to methane ratio of 4:1 is
obtained, resulting in a large backup supply of oxygen. With only the light hydrogen transported from Earth, and the
heavy oxygen and carbon extracted locally, a mass leveraging of 18:1 is afforded with this scheme. This in-situ
resource utilization would result in massive weight and cost savings to any proposed manned Mars or sample return
missions.
See also
• In-Situ Resource Utilization
• Timeline of hydrogen technologies
References
[1] http:/ / www. nasaspaceflight. com/ 2010/ 10/ soyuz-01m-docking-iss-crews-conduct-hardware-installation/
[2] Giant Pool of Water Ice at Mars' South Pole (http:/ / www. space. com/ scienceastronomy/ 070315_martian_beach. html) Space.com article
External links
• A Crewed Mission to Mars (http://nssdc.gsfc.nasa.gov/planetary/mars/marssurf.html)
• Development of an improved Sabatier reactor (http://www.osti.gov/energycitations/product.biblio.
jsp?osti_id=5087687)
• Improved Sabatier Reactions for In Situ Resource Utilization on Mars Missions (http://www.isso.uh.edu/
publications/A9900/pdf/rich84.pdf)
93
Risks
Hydrogen damage
Hydrogen damage is the generic name given to a large number of metal degradation processes due to interaction
with hydrogen.
Hydrogen is present practically everywhere, in the atmosphere, several kilometres above the earth and inside the
earth. Engineering materials are exposed to hydrogen and they may interact with it resulting in various kinds of
structural damage. Damaging effects of hydrogen in metallic materials have been known since 1875 when W. H.
Johnson reported[1] “some remarkable changes produced in iron by the action of hydrogen and acids”. During the
intervening years many similar effects have been observed in different structural materials, such as steel, aluminium,
titanium, and zirconium. Because of the technological importance of hydrogen damage, many people explored the
nature, causes and control measures of hydrogen related degradation of metals. Hardening, embrittlement and
internal damage are the main hydrogen damage processes in metals. This article consists of a classification of
hydrogen damage, brief description of the various processes and their mechanisms, and some guidelines for the
control of hydrogen damage.
Importance
With advancing technology, use of high strength structural materials becomes a necessity. Depletion of fossil fuels
and the search for other sources of energy is a current activity of mankind. Hydrogen is believed to be a possible
future source of energy (Engineering note: Hydrogen could not be used as a "source" of energy but only as a means
to transport energy from one place to another) and a “hydrogen economy” is a strong possibility within the next 50
years. In such a scenario, large scale production, storage, transportation and use of hydrogen becomes necessary[2] .
Materials’ problems caused by hydrogen damage could limit the progress of such an economy. Hydrogen may be
picked up by metals during melting, casting, shaping and fabrication. They are also exposed to hydrogen during their
service life. Materials susceptible to hydrogen damage have ample opportunities to be degraded during all these
stages.
Classifications
Hydrogen damage may be of four types: solid solution hardening, creation of internal defects, hydride embrittlement,
and hydrogen embrittlement.[3] Each of these may further be classified into the various damaging processes.
Hydride embrittlement
In hydride forming metals like titanium, zirconium and vanadium, hydrogen absorption causes severe embrittlement.
At low concentrations of hydrogen, below the solid solubility limit, stress-assisted hydride formation causes the
embrittlement which is enhanced by slow straining. At hydrogen concentrations above the solubility limit, brittle
hydrides are precipitated on slip planes and cause severe embrittlement[5] . This latter kind of embrittlement is
Hydrogen damage 94
encouraged by increased strain-rates, decreased temperature and by the presence of notches in the material.
Blistering
Atomic hydrogen diffusing through metals may collect at internal defects like inclusions and laminations and form
molecular hydrogen. High pressures may be built up at such locations due to continued absorption of hydrogen
leading to blister formation, growth and eventual bursting of the blister. Such hydrogen induced blister cracking has
been observed in steels, aluminium alloys, titanium alloys and nuclear structural materials[3] .
Porosity
In metals like iron and steel, aluminium and magnesium whose hydrogen solubilities decrease with decreasing
temperature, liberation of excess hydrogen during cooling from the melt, (in ingots and castings) produces gas
porosity.
Hydrogen embrittlement
By far, the most damaging effect of hydrogen in structural materials is hydrogen embrittlement. Materials
susceptible to this process exhibit a marked decrease in their energy absorption ability before fracture in the presence
of hydrogen. This phenomenon is also known as hydrogen-assisted cracking, hydrogen-induced blister cracking. The
embrittlement is enhanced by slow strain rates and low temperatures, near room temperature.
See also
• Hydrogen piping
References
[1] W. H. Johnson, Proc. Royal Soc. (London), 23 (1875), 168
[2] J. O’M. Bockris, Int. J. Hydrogen Energy, 6 (1981), 223
[3] T. K. G. Namboodhiri, Trans. Indian Inst. Metals, 37(1984), 764
[4] B. A. Kolachev, Hydrogen embrittlement of non-ferrous metals, Translated from Russian, Israel Program for scientific translations, (1968)
[5] W. J. Pardee and N. E. Paton, Metall. Trans. 11A (1980), 1391
[6] G. A. Nelson, in Hydrogen Damage, C. D. Beachem (Ed.), American Society for Metals, Metals Park, Ohio, (1977), p. 377
[7] The Australian Institute for Non Destructive Testing (AINDT), Detection and Quantification of Hydrogen Damage (http:/ / www. ndt. net/
apcndt2001/ papers/ 1154/ 1154. htm)
[8] SGS Industrial Services, NDT-Hot Hydrogen Attack (http:/ / www. sgs. com/ ndt-hot-hydrogen-attack?serviceId=10149586& lobId=5550)
Hydrogen damage 96
External links
• A 39-page paper on hydrogen damage of metals by M.R. Louthan, "Hydrogen Embrittlement of Metals: A Primer
for the Failure Analyst", 2008, from U.S. DOE OSTI, 3.4MB available here (http://sti.srs.gov/fulltext/
WSRC-STI-2008-00062.pdf).
Hydrogen embrittlement
Hydrogen embrittlement is the process by which various metals, most importantly high-strength steel, become
brittle and fracture following exposure to hydrogen. Hydrogen embrittlement is often the result of unintentional
introduction of hydrogen into susceptible metals during forming or finishing operations.
Hydrogen embrittlement is also used to describe the formation of zircaloy hydride. Use of the term in this context is
common in the nuclear industry.
Process
The mechanism starts with lone hydrogen atoms diffusing through the metal. At high temperatures, the elevated
solubility of hydrogen allows hydrogen to diffuse into the metal (or the hydrogen can diffuse in at a low temperature,
assisted by a concentration gradient). When these hydrogen atoms re-combine in minuscule voids of the metal matrix
to form hydrogen molecules, they create pressure from inside the cavity they are in. This pressure can increase to
levels where the metal has reduced ductility and tensile strength up to the point where it cracks open (hydrogen
induced cracking, or HIC). High-strength and low-alloy steels, nickel and titanium alloys are most susceptible.
Austempered iron is also susceptible. Steel with an ultimate tensile strength of less than 1000 MPa or hardness of
less than 30 HRC are not generally considered susceptible to hydrogen embrittlement. Jewett et al.[1] reports the
results of tensile tests carried out on several structural metals under high-pressure molecular hydrogen environment.
These tests have shown that austenitic stainless steels, aluminum (including alloys), copper (including alloys, e.g.
beryllium copper) are not susceptible to hydrogen embrittlement along with few other metals[2] . For example of a
severe embrittlement measured by Jewett, the elongation at failure of 17-4PH precipitation hardened stainless steel
was measured to drop from 17% to only 1.7% when smooth specimens were exposed to high-pressure hydrogen.
Hydrogen embrittlement can occur during various manufacturing operations or operational use - anywhere that the
metal comes into contact with atomic or molecular hydrogen. Processes that can lead to this include cathodic
protection, phosphating, pickling, and electroplating. A special case is arc welding, in which the hydrogen is released
from moisture (for example in the coating of the welding electrodes; to minimize this, special low-hydrogen
electrodes are used for welding high-strength steels). Other mechanisms of introduction of hydrogen into metal are
galvanic corrosion, chemical reactions of metal with acids, or with other chemicals (notably hydrogen sulfide in
sulfide stress cracking, or SSC, a process of importance for the oil and gas industries).
Counteractions
If the metal has not yet started to crack, the condition can be reversed by removing the hydrogen source and causing
the hydrogen within the metal to diffuse out, possibly at elevated temperatures. Susceptible alloys, after chemical or
electrochemical treatments where hydrogen is produced, are often subjected to heat treatment to remove absorbed
hydrogen. There is a 4-hour time limit for baking out entrapped hydrogen after acid treating the parts. This is the
time between the end of acid exposure and the beginning of the heating cycle in the baking furnace. This per SAE
AMS 2759/9 Section 3.3.3.1 which calls out the correct procedure for eliminating entrapped hydrogen.
In the case of welding, often pre- and post-heating the metal is applied to allow the hydrogen to diffuse out before it
can cause any damage. This is specifically done with high-strength steels and low alloy steel such as the
Hydrogen embrittlement 97
chrome/molybdenum/vanadium alloys. Due to the time needed to re-combine hydrogen atoms into the harmful
hydrogen molecules, hydrogen cracking due to welding can occur over 24 hours after the welding operation is
completed.
Products such as ferrosilicates can be used to treat surfaces normally subject to hydrogen embrittlement in order to
prevent it from taking place.
Related phenomena
If steel is exposed to hydrogen at high temperatures, hydrogen will diffuse into the alloy and combine with carbon to
form tiny pockets of methane at internal surfaces like grain boundaries and voids. This methane does not diffuse out
of the metal, and collects in the voids at high pressure and initiates cracks in the steel. This selective leaching process
is known as hydrogen attack, or high temperature hydrogen attack and leads to decarburization of the steel and loss
of strength and ductility.
Copper alloys which contain oxygen can be embrittled if exposed to hot hydrogen. The hydrogen diffuses through
the copper and reacts with inclusions of Cu2O, forming H2O (water), which then forms pressurized bubbles at the
grain boundaries. This process can cause the grains to literally be forced away from each other, and is known as
steam embrittlement (because steam is produced, not because exposure to steam causes the problem).
Testing
There are two ASTM standards for testing embrittlement due to hydrogen gas. The standard ASTM F1459-06
Standard Test Method for Determination of the Susceptibility of Metallic Materials to Hydrogen Gas Embrittlement
(HGE) Test [3] uses a diaphragm loaded with a differential pressure. The test ASTM G142-98(2004) Standard Test
Method for Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing Environments at
High Pressure, High Temperature, or Both [4] uses a cylindrical tensile specimen tested into an enclosure pressurized
with hydrogen or helium.
Another ASTM standard exists for quantitatively testing for the Hydrogen Embrittlement threshold stress for the
onset of Hydrogen-Induced Cracking due to platings and coatings from Internal Hydrogen Embrittlement (IHE) and
Environmental Hydrogen Embrittlement (EHE) [5] - F1624-06 Standard Test Method for Measurement of Hydrogen
Embrittlement Threshold in Steel by the Incremental Step Loading Technique. References: ASTM STP
543,"Hydrogen Embrittlement Testing" [6] and ASTM STP 962,"Hydrogen Embrittlement: Prevention and Control."
[7]
• NACE TM0284-2003 (NACE International) Resistance to Hydrogen-Induced Cracking
• ISO 11114-4:2005 (ISO)Test methods for selecting metallic materials resistant to hydrogen embrittlement [8].
• ASTM F1940-07a [9]- Standard Test Method for Process Control Verification to Prevent Hydrogen Embrittlement
in Plated or Coated Fasteners
• ASTM F519-06e2 [10]-Standard Test Method for Mechanical Hydrogen Embrittlement Evaluation of
Plating/Coating Processes and Service Environments
Hydrogen embrittlement 98
See also
• Hydrogen analyzer
• Hydrogen damage
• Hydrogen piping
• Hydrogen safety
• Low hydrogen annealing
• Nascent hydrogen
References
[1] Jewett, R.P. (1973). Hydrogen Environment Embrittlement of Metals. NASA CR-2163.
[2] Overview of interstate hydrogen pipeline systems-Pag.13 (http:/ / corridoreis. anl. gov/ documents/ docs/ technical/
APT_61012_EVS_TM_08_2. pdf)
[3] http:/ / www. astm. org/ Standards/ F1459. htm
[4] http:/ / www. astm. org/ Standards/ G142. htm
[5] http:/ / www. astm. org/ cgi-bin/ SoftCart. exe/ STORE/ filtrexx40. cgi?U+ mystore+ yvst4574+ -L+ ASTMF1624:06+ / usr6/ htdocs/ astm.
org/ DATABASE. CART/ REDLINE_PAGES/ F1624. htm
[6] http:/ / www. astm. org/ cgi-bin/ SoftCart. exe/ DIGITAL_LIBRARY/ STP/ SOURCE_PAGES/ STP543. htm?L+ mystore+ hsjb1846+
1193986997
[7] http:/ / www. astm. org/ cgi-bin/ SoftCart. exe/ BOOKSTORE/ PUBS/ 652. htm?E+ mystore
[8] http:/ / www. iso. org/ iso/ en/ CatalogueDetailPage. CatalogueDetail?CSNUMBER=41281& ICS1=23& ICS2=20& ICS3=30
[9] http:/ / www. astm. org/ cgi-bin/ SoftCart. exe/ DATABASE. CART/ REDLINE_PAGES/ F1940. htm?L+ mystore+ yvst4574+ 1196145312
[10] http:/ / www. astm. org/ cgi-bin/ SoftCart. exe/ STORE/ filtrexx40. cgi?U+ mystore+ yvst4574+ -L+ F519+ / usr6/ htdocs/ astm. org/
DATABASE. CART/ REDLINE_PAGES/ F519. htm
Further reading
• ASM international, ASM Handbook #13: Corrosion, ASM International, 1998
External links
• Hydrogen embrittlement, revisited by in situ electrochemical nanoindentation (http://www.shaker.de/
online-Gesamtkatalog/details.asp?ID=8533580&CC=50968&ISBN=3-8322-7834-6)
• Hydrogen embrittlement (http://www.uni-saarland.de/fak8/wwm/research/phd_barnoush/hydrogen.pdf)
• Corrosion-Doctors.org Hydrogen embrittlement (http://www.corrosion-doctors.org/Forms-HIC/embrittlement.
htm)
• Hydrogen purity plays a critical role (http://www.hydrogen.energy.gov/pdfs/progress05/v_a_4_adams.pdf)
• A Sandia National Lab technical reference manual. (http://www.sandia.gov/matlsTechRef/)
Hydrogen leak testing 99
See also
• Hydrogen analyzer
• Hydrogen piping
• Hydrogen safety
• Tubing (material)
• Hydrogen station
• Tracer-gas leak testing method
External links
• Fibre gratings for hydrogen sensing [2]
• Wide-Range Hydrogen Sensor [3]
• Wireless sensor [4]
• / Hydrogen leak tester [5]
References
[1] http:/ / www. reedlink. com/ SingleArticle~ContentId~11957~pub~IA. html
[2] http:/ / ej. iop. org/ links/ q63/ ,,,vhEqvhL1tjxru6ReiaQ/ mst6_5_s31. pdf
[3] http:/ / www. sandia. gov/ mstc/ technologies/ microsensors/ hydrogensensor. html
[4] http:/ / news. ufl. edu/ 2006/ 05/ 24/ hydrogen-sensor/
[5] http:/ / www. directindustry. com/ prod/ ateq/ hydrogen-leak-detector-7689-258533. html
Hydrogen safety 100
Hydrogen safety
Hydrogen safety covers the safe use and handling of hydrogen. Hydrogen poses unique challenges due to its ease of
leaking, low-energy ignition, wide range of combustible fuel-air mixtures, buoyancy, and its ability to embrittle
metals that must be accounted for to ensure safe operation. Liquid hydrogen poses additional challenges due to its
increased density and extremely low temperatures.
Guidelines
The current ANSI/AIAA standard for hydrogen safety guidelines is AIAA G-095-2004, Guide to Safety of
Hydrogen and Hydrogen Systems[2] . As NASA has been one of the world's largest users of hydrogen, this evolved
from NASA's earlier guidelines, NSS 1740.16 (8719.16).[3] These documents cover both the risks posed by hydrogen
in its different forms and how to ameliorate them.
Ignition
• "Hydrogen-air mixtures can ignite with very low energy input, 1/10th that required igniting a gasoline-air
mixture. For reference, an invisible spark or a static spark from a person can cause ignition."
• "Although the autoignition temperature of hydrogen is higher than those for most hydrocarbons, hydrogen's lower
ignition energy makes the ignition of hydrogen–air mixtures more likely. The minimum energy for spark ignition
at atmospheric pressure is about 0.02 millijoules."
Mixtures
• "The flammability limits based on the volume percent of hydrogen in air at 14.7 psia (1 atm, 101 kPa) are 4.0 and
75.0. The flammability limits based on the volume percent of hydrogen in oxygen at 14.7 psia (1 atm, 101 kPa)
are 4.0 and 94.0."
• "Explosive limits of hydrogen in air are 18.3 to 59 percent by volume"
• "Flames in and around a collection of pipes or structures can create turbulence that causes a deflagration to evolve
into a detonation, even in the absence of gross confinement."
(For comparison: Deflagration limit of gasoline in air: 1.4–7.6%; of acetylene in air[4] , 2.5% to 82%)
Hydrogen safety 101
Leaks
• Leakage, diffusion, and buoyancy: These hazards result from the difficulty in containing hydrogen. Hydrogen
diffuses extensively, and when a liquid spill or large gas release occurs, a combustible mixture can form over a
considerable distance from the spill location.
• Hydrogen, in both the liquid and gaseous states, is particularly subject to leakage because of its low viscosity and
low molecular weight (leakage is inversely proportional to viscosity). Because of its low viscosity alone, the
leakage rate of liquid hydrogen is roughly 100 times that of JP-4 fuel, 50 times that of water, and 10 times that of
liquid nitrogen.
• Hydrogen leaks can support combustion at very low flow rates, as low as 4 micrograms/s.[5]
Liquid hydrogen
• "Condensed and solidified atmospheric air, or trace air accumulated in manufacturing, contaminates liquid
hydrogen, thereby forming an unstable mixture. This mixture may detonate with effects similar to those produced
by trinitrotoluene (TNT) and other highly explosive materials"
Liquid Hydrogen requires complex storage technology such as the special thermally insulated containers and
requires special handling common to all cryogenic substances. This is similar to, but more severe than liquid oxygen.
Even with thermally insulated containers it is difficult to keep such a low temperature, and the hydrogen will
gradually leak away. (Typically it will evaporate at a rate of 1% per day.[6])
Prevention
Hydrogen collects under roofs and overhangs, where it forms an explosion hazard; any building that contains a
potential source of hydrogen should have good ventillation, strong ignition suppression systems for all electric
devices, and preferably be designed to have a roof that can be safely blown away from the rest of the structure in an
explosion. It also enters pipes and can follow them to their destinations. Hydrogen pipes should be located above
other pipes to prevent this occurrence. Hydrogen sensors allow for rapid detection of hydrogen leaks to ensure that
the hydrogen can be vented and the source of the leak tracked down. As in natural gas, an odorant can be added to
hydrogen sources to enable leaks to be detected by smell. While hydrogen flames can be hard to see with the naked
eye, they show up readily on UV/IR flame detectors.
Accidents
Hydrogen has been feared in the popular press as a relatively more dangerous fuel, and hydrogen in fact has the
widest explosive/ignition mix range with air of all the gases except acetylene. However this can be mitigated by the
fact that hydrogen rapidly rises and disperses before ignition. Unless the escape is in an enclosed, unventilated area,
it is unlikely to be serious. Hydrogen also usually rapidly escapes after containment breach. Additionally, hydrogen
flames are difficult to see, so may be difficult to fight. An experiment performed at the University of Miami
attempted to counter this by showing that hydrogen escapes while gasoline remains by setting alight hydrogen- and
petrol-fuelled vehicles.[7]
In a more recent event, an explosion of compressed hydrogen during delivery at the Muskingum River Coal Plant
(owned and operated by AEP) caused significant damage and killed one person.[8] [9] For more information on
incidents involving hydrogen, visit the US DOE's Hydrogen Incident Reporting and Lessons Learned page. [10]
Hydrogen safety 102
See also
• Hydrogen embrittlement
• Hydrogen economy
• Compressed hydrogen
• Liquid hydrogen
• Slush hydrogen
• Metallic hydrogen
References
[1] HySafe Initial Guidance for Using Hydrogen in Confined Spaces (http:/ / www. hysafe. org/ download/ 1710/ HYSAFE_D113_version_1. 1.
pdf)
[2] "AIAA G-095-2004, Guide to Safety of Hydrogen and Hydrogen Systems" (http:/ / aero-defense. ihs. com/ document/ abstract/
GFEIHBAAAAAAAAAA) (PDF). AIAA. . Retrieved 2008-07-28.
[3] Gregory, Frederick D. (Feb. 12, 1997). "Safety Standard for Hydrogen and Hydrogen Systems" (http:/ / www. hq. nasa. gov/ office/ codeq/
doctree/ canceled/ 871916. pdf) (PDF). NASA. . Retrieved 2008-05-09.
[4] http:/ / www. msha. gov/ alerts/ hazardsofacetylene. htm
[5] M.S. Butler, C.W. Moran, Peter B. Sunderland, R.L. Axelbaum, Limits for Hydrogen Leaks that Can Support Stable Flames, International
Journal of Hydrogen Energy 34 (2009) 5174-5182.
[6] http:/ / www. almc. army. mil/ alog/ issues/ MayJun00/ MS492. htm
[7] "Hydrogen Car Fire Surprise" (http:/ / www. evworld. com/ article. cfm?storyid=482). January 18, 2003. . Retrieved 2008-05-09.
[8] Williams, Mark (January 8, 2007). ""Ohio Power Plant Blast Kills 1, Hurts 9"" (http:/ / www. washingtonpost. com/ wp-dyn/ content/ article/
2007/ 01/ 08/ AR2007010800350. html). Associated Press. . Retrieved 2008-05-09.
[9] "Muskingum River Plant Hydrogen Explosion January 8, 2007" (http:/ / web. archive. org/ web/ 20080409155509/ http:/ / www. eei. org/
meetings/ nonav_2007-04-29-cs/ Citations_Accident_Review. pdf) (PDF). American Electric Power. November 11, 2006. Archived from the
original (http:/ / www. eei. org/ meetings/ nonav_2007-04-29-cs/ Citations_Accident_Review. pdf) on 2008-04-09. . Retrieved 2008-05-09.
[10] ""Hydrogen Incident Reporting and Lessons Learned"" (http:/ / www. h2incidents. org/ ). .
External links
• Hysafe (http://www.hysafe.org/)
• Hydrogen and fuelcell safety (http://www.hydrogenandfuelcellsafety.info)
• DOE-Hydrogen safety for First Responders (http://www.ehammertraining.us/energy/h2_login/login.cfm)
• First Responders - Emergency Response Guidebook - Guide 115 (http://hazmat.dot.gov/pubs/erg/
erg2008_eng.pdf)
• World's First Higher Educational Programme in Hydrogen Safety Engineering (http://www.hysafe.org/
MScHSE)
103
Fuel
Timeline
1600s
• 1625 - First description of hydrogen by Johann Baptista van Helmont. First to use the word "gas".
• 1650 - Turquet de Mayerne obtained by the action of dilute sulphuric acid on iron a gas or "inflammable air".
• 1662 - Boyle's law (gas law relating pressure and volume)
• 1670 - Robert Boyle produced hydrogen by reacting metals with acid.
• 1672 - "New Experiments touching the Relation between Flame and Air" by Robert Boyle.
• 1679 - Denis Papin - safety valve
1700s
• 1700 - Nicolas Lemery showed that the gas produced in the sulfuric acid/iron reaction was explosive in air
• 1755 - Joseph Black confirmed that different gases exist. / Latent heat
• 1766 - Henry Cavendish published in "On Factitious Airs" a description of "dephlogisticated air" by reacting zinc
metal with hydrochloric acid and isolated a gas 7 to 11 times lighter than air.
• 1774 - Joseph Priestley isolated and categorized oxygen.
• 1780 - Felice Fontana discovers the water gas shift reaction
• 1783 - Antoine Lavoisier gave hydrogen its name (Gk: hydro = water, genes = born of)
• 1783 - Jacques Charles made the first flight with his hydrogen balloon "La Charlière".
• 1783 - Antoine Lavoisier and Pierre Laplace measured the heat of combustion of hydrogen using an ice
calorimeter.
• 1784 - Jean-Pierre Blanchard, attempted a dirigible hydrogen balloon, but it would not steer.
• 1784 - The invention of the Lavoisier Meusnier iron-steam process[1] , generating hydrogen by passing water
vapor over a bed of red-hot iron at 600 °Cdoi:10.1080/00033798300200381.
• 1785 - Jean-François Pilâtre de Rozier built the hybrid Rozière balloon.
• 1787 - Charles's law (Gas law, relating volume and temperature)
• 1789 - Jan Rudolph Deiman and Adriaan Paets van Troostwijk using a electrostatic machine and a Leyden jar for
the first electrolysis of water.
Timeline of hydrogen technologies 104
1800s
• 1800 - William Nicholson and Anthony Carlisle decomposed water into hydrogen and oxygen by electrolysis
with a voltaic pile.
• 1800 - Johann Wilhelm Ritter duplicated the experiment with a rearranged set of electrodes to collect the two
gases separately.
• 1806 - François Isaac de Rivaz built the first internal combustion engine powered by a mixture of hydrogen and
oxygen.
• 1809 - Thomas Foster observed with a theodolite the drift of small free pilot balloons filled with "inflammable
gas"[2] [3]
• 1809 - Gay-Lussac's law (Gas law, relating temperature and pressure)
• 1811 - Amedeo Avogadro - Avogadro's law a gas law
• 1819 - Edward Daniel Clarke invented the hydrogen gas blowpipe.
• 1820 - W. Cecil wrote a letter "On the application of hydrogen gas to produce a moving power in machinery"[4]
[5]
1900s
• 1900 - Count Ferdinand von Zeppelin launched the first hydrogen-filled Zeppelin LZ1 airship.
• 1901 - Wilhelm Normann introduced the hydrogenation of fats.
• 1903 - Konstantin Eduardovich Tsiolkovskii published "The Exploration of Cosmic Space by Means of Reaction
Devices"[8]
• 1907 - Lane hydrogen producer
• 1909 - Count Ferdinand Adolf August von Zeppelin made the first long distance flight with the Zeppelin LZ5.
• 1909 - Linde-Frank-Caro process
• 1910 - The first Zeppelin passenger flight with the Zeppelin LZ7.
• 1910 - Fritz Haber patented the Haber process.
• 1912 - The first scheduled international Zeppelin passenger flights with the Zeppelin LZ13.
• 1919 - The first Atlantic crossing by airship with the Beardmore HMA R34.
• 1920 - Hydrocracking, a plant for the commercial hydrogenation of brown coal is commissioned at Leuna in
Germany[9] .
• 1923 - Steam reforming, the first synthetic methanol is produced by BASF in Leuna
• 1923 - J. B. S. Haldane envisioned in Daedalus; or, Science and the Future "great power stations where during
windy weather the surplus power will be used for the electrolytic decomposition of water into oxygen and
hydrogen."
• 1926 - Partial oxidation, Vandeveer and Parr at the University of Illinois used oxygen in the place of air for the
production of syngas.
• 1926 - Cyril Norman Hinshelwood described the phenomenon of chain reaction.
• 1926 - Umberto Nobile made the first flight over the north pole with the hydrogen airship Norge
• 1929 - Paul Harteck and Karl Friedrich Bonhoeffer achieve the first synthesis of pure parahydrogen.
• 1930 - Rudolf Erren - Erren engine - GB patent GB364180 - Improvements in and relating to internal combustion
engines using a mixture of hydrogen and oxygen as fuel[10]
• 1935 - Eugene Wigner and H.B. Huntington predicted metallic hydrogen.
• 1937 - The Zeppelin LZ 129 Hindenburg was destroyed by fire.
• 1937 - The Heinkel HeS 1 experimental gaseous hydrogen fueled centrifugal jet engine is tested at Hirth in
March- the first working jet engine
• 1937 - The first hydrogen-cooled turbogenerator went into service at Dayton, Ohio.
• 1938 - The first 240 km hydrogen pipeline Rhine-Ruhr [11] .
• 1938 - Igor Sikorsky from Sikorsky Aircraft proposed liquid hydrogen as a fuel.
• 1939 - Rudolf Erren - Erren engine - US patent 2,183,674 - Internal combustion engine using hydrogen as fuel
• 1939 - Hans Gaffron discovered that algae can switch between producing oxygen and hydrogen.
• 1943 - Liquid hydrogen is tested as rocket fuel at Ohio State University.
• 1943 - Arne Zetterström describes hydrox
• 1949 - Hydrodesulfurization (Catalytic reforming is commercialized under the name Platforming process)
• 1952 - Hydrogen maser
• 1952 - Non-Refrigerated transport Dewar
• 1955 - W. Thomas Grubb modified the fuel cell design by using a sulphonated polystyrene ion-exchange
membrane as the electrolyte.
• 1957 - Pratt & Whitney's model 304 jet engine using liquid hydrogen as fuel tested for the first time as part of the
Lockheed CL-400 Suntan project.[12]
• 1957 - The specifications for the U-2 a double axis liquid hydrogen semi-trailer were issued[13] .
• 1958 - Leonard Niedrach devised a way of depositing platinum onto the membrane, this became known as the
Grubb-Niedrach fuel cell
• 1958 - Allis-Chalmers demonstrated the D 12, the first 15 kW fuel cell tractor[14] .
Timeline of hydrogen technologies 106
• 1959 - Francis Thomas Bacon built the Bacon Cell, the first practical 5 kW hydrogen-air fuel cell to power a
welding machine.
• 1960 - Allis-Chalmers builds the first fuel cell forklift[15]
• 1961 - RL-10 liquid hydrogen fuelled rocket engine first flight
• 1964 - Allis-Chalmers built a 750-watt fuel cell to power a one-man underwater research vessel[16] .
• 1965 - The first commercial use of a fuel cell in Project Gemini.
• 1965 - Allis-Chalmers builds the first fuel cell golf carts.
• 1966 - Slush hydrogen
• 1966 - J-2 (rocket engine) liquid hydrogen rocket engine flies
• 1967 - Akira Fujishima discovers the Honda-Fujishima effect which is used for photocatalysis in the
photoelectrochemical cell.
• 1967 - Hydride compressor
• 1970 - Nickel hydrogen battery [17]
• 1970 - John Bockris or Lawrence W. Jones coined the term hydrogen economy [18] [19]
• 1973 - The 30 km hydrogen pipeline in Isbergues
• 1973 - Linear compressor
• 1975 - John Bockris - Energy The Solar-Hydrogen Alternative - ISBN 0470084294
• 1979 - HM7B rocket engine
• 1981 - Space Shuttle main engine first flight
• 1990 - The first solar-powered hydrogen production plant Solar-Wasserstoff-Bayern became operational.
• 1996 - Vulcain rocket engine
• 1997 - Anastasios Melis discovered that the deprivation of sulfur will cause algae to switch from producing
oxygen to producing hydrogen
• 1998 - Type 212 submarine
• 1999 - Hydrogen pinch
2000s
• 2000 - Peter Toennies demonstrates superfluidity of hydrogen at 0.15 K
• 2001 - The first type IV hydrogen tanks for compressed hydrogen at 700 Bar (10000 PSI) were demonstrated.
• 2002 - Type 214 submarine
• 2004 - DeepC
• 2005 - Ionic liquid piston compressor
See also
• Timeline of low-temperature technology
• List of timelines
References
[1] 1784 Experiments (http:/ / moro. imss. fi. it/ lavoisier/ Lavoisier_Experiments2Gb. asp?anno=1784)
[2] 1809 - Fleming, History of Meteorology 25 Pag. 25 (http:/ / www. colby. edu/ sts/ st215/ history_of_meteorology. pdf)
[3] 1809 - Pilot balloon resources (http:/ / www. csulb. edu/ ~mbrenner/ history. htm)
[4] 1820 Cecil engine (http:/ / www. eng. cam. ac. uk/ DesignOffice/ projects/ cecil/ engine. html)
[5] 1820 Cecil the letter (http:/ / www. eng. cam. ac. uk/ DesignOffice/ projects/ cecil/ cecil. pdf)
[6] 1874 - Jules Verne, The Mysterious Island (http:/ / www. online-literature. com/ verne/ mysteriousisland/ 33/ )
[7] 1896 Weather balloon (http:/ / www. metoffice. gov. uk/ corporate/ pressoffice/ anniversary/ balloon. html)
[8] Tsiolkovsky's Исследование мировых пространств реактивными приборами - The Exploration of Cosmic Space by Means of Reaction
Devices (Russian paper) (http:/ / epizodsspace. testpilot. ru/ bibl/ dorev-knigi/ ciolkovskiy/ issl-03st. html)
[9] 1920 - Hydrocracking (http:/ / www. cheresources. com/ refining5. shtml)
Timeline of hydrogen technologies 107
[10] Improvements in and relating to internal combustion engines using a mixture of hydrogen and oxygen as fuel (http:/ / www. wikipatents.
com/ gb/ 0364180. html)
[11] The Technological Steps of Hydrogen Introduction - pag 24 (http:/ / www. storhy. net/ train-in/ PDF-TI/
03_StorHy-Train-IN-Session-1_3_JToepler. pdf)
[12] Sloop, John L. (1978). Liquid hydrogen as a propulsion fuel, 1945-1959.(The NASA history series) (NASA SP-4404) (http:/ / www. hq. nasa.
gov/ office/ pao/ History/ SP-4404/ ch8-9. htm). National Aeronautics and Space Administration. pp. 154–157. .
[13] NASA-LIQUID HYDROGEN AS A PROPULSION FUEL,1945-1959 (http:/ / history. nasa. gov/ SP-4404/ ch8-11. htm)
[14] 1958 D 12 - Pag. 7 (http:/ / www. fuelcelltoday. com/ media/ pdf/ archive/ Article_1152_Fuel Cell History part 2 with illustrations. pdf)
[15] 1960 -Fleet module Pag.3 (http:/ / www. hydrogenassociation. org/ general/ fleet_Module7. pdf)
[16] 1964 Allis Chalmers Pag.1 (http:/ / www. aesc-inc. com/ download/ Ishii_Fuel_Cell_Paper. pdf)
[17] Nickel-Hydrogen Battery Technology—Development and Status (http:/ / pdf. aiaa. org/ jaPreview/ JE/ 1982/ PVJAPRE62569. pdf)
[18] History of Hydrogen (http:/ / www. getenergysmart. org/ Files/ Schools/ Hydrogen/ 3HistoryofHydrogen. pdf)
[19] Lawrence W. Jones Toward a liquid hydrogen fuel economy (http:/ / deepblue. lib. umich. edu/ handle/ 2027. 42/ 5800), University of
Michigan Engineering Technical Report UMR2320, March 13, 1970
Biohydrogen
Biohydrogen is defined as hydrogen produced biologically, most commonly
by bacteria. Biohydrogen is a potential biofuel obtainable from waste organic
materials.[1] More generally the term biohydrogen describes the hydrogen
produced via a number of biological processes.
Introduction
Currently, there is a huge demand of the chemical hydrogen. There is no log
on the production volume and use of hydrogen world-wide. However the
estimated consumption of hydrogen is expected to reach 900 billion cubic
meters in 2011[2]
Refineries are large-volume producers and consumers of hydrogen. Today
96% of all hydrogen is derived from fossil fuels, with 48% from natural gas,
Microbial hydrogen production.
30% from hydrocarbons, 18% from coal and about 4% from electrolysis.
Oil-sands processing, gas-to-liquids and coal gasification projects that are
ongoing, require a huge amount of hydrogen and is expected to boost the requirement significantly within the next
few years. Environmental regulations implemented in most countries, increase the hydrogen requirement at refineries
for gas-line and diesel desulfurization[2] [3]
A important future application of hydrogen could be as an alternative for fossil fuels, once the oil deposits are
depleted.[4] This application is however dependent on the development of storage techniques to enable proper
storage, distribution and combustion of hydrogen.[4] If the cost of hydrogen production, distribution, and end-user
technologies decreases, hydrogen as a fuel could be entering the market in 2020.[5]
Industrial fermentation of hydrogen, or whole-cell catalysis, requires a limited amount of energy, since fission of
water is achieved with whole cell catalysis, to lower the activation energy.[6] This allows hydrogen to be produced
from any organic material that can be derived through whole cell catalysis since this process does not depend on the
energy of substrate.
Biohydrogen 108
Process requirements
If hydrogen by fermentation is to be introduced as an industry, the fermentation process will dependent on organic
acids as substrate for photo-fermentation. The organic acids are necessary for high hydrogen production rates.[6] [7]
The organic acids can be derived from any organic material source such as sewage waste waters or agricultural
wastes.[7] The most important organic acids are acetic acid (HAc), butyric acid (HBc) and propionic acid (HPc). A
huge advantage is that production of hydrogen by fermentation does not require glucose as substrate.[7]
The fermentation of hydrogen has to be a continuous fermentation process, in order sustain high production rates,
since the amount of time for the fermentation to enter high production rates are in days.[6]
Fermentation
Several strategies for the production of hydrogen by fermentation in lab-scale has been found in literature. However
no strategies for industrial-scale productions has been found. In order to define a industrial-scale production, the
information from lab-scale experiments has been scaled to a industrial-size production on a theoretical basis. In
general, the method of hydrogen fermentation are referred to in three main categories. The first category is
dark-fermentation, which is fermentation, which does not involve light. The second category is photo-fermentation,
which is fermentation, which require light as the source of energy. The third is combined-fermentation, which refers
to the two fermentations combined.
Dark-fermentation
There are several bacteria with a potential for hydrogen production. The Gram-positive bacteria of the Clostridium
genus, is promising because it has a natural high hydrogen production rate. In addition, it is fast growing and capable
of forming spores, which make the bacteria easy to handle in industrial application.[8]
Species of the Clostridium genus allow hydrogen production in mixed cultures, under mesophilic or thermophilic
conditions within a pH range of 5.0 to 6.5.[8] Dark-fermentation with mixed cultures seems promising since a mixed
bacterial environment within the fermenter, allows cooperation of different species to efficiently degrade and convert
organic waste materials into hydrogen, accompanied by the formation of organic acids.[8]
For the fermentation to be sustainable in industrial-scale, we need to be able to control the bacterial environment
inside the fermenter. If the fermentation process is feed with sugar waste, we have a risk, that the feed will contain
micro-organisms, which could change the bacterial environment inside the fermenter.[9] A way to prevent harmful
micro-organisms from gaining control of the bacterial environment inside the fermenter could be through addition of
probiotics which favors or promotes the intended bacterial environment and prevents harmful micro-organisms from
gaining control of the fermenter.[9]
The dilution rate has to ensure that the amount of biomass inside the fermenter is stable and that the organic acids are
removed properly with the outlet stream. The organic acids are toxic to the bacteria and huge amounts will
interrupted the fermentation process.[8] This fermentation of hydrogen is accompanied production of carbon-dioxide
which can be separated from hydrogen with a passive separation process.[10]
The fermentation will convert some of the sugar waste into biomass instead of hydrogen.[8] The biomass is however
a carbohydrate-rich by-product which can be fed back into the fermenter, to ensure that the process is sustainable.[11]
Fermentation of hydrogen by dark-fermentation is restricted by incomplete degradation of organic material, into
organic acids and this is why we need the photo-fermentation.[8]
The separation of organic acids from biomass in the outlet stream can be done with a settler tank in the outlet stream,
where the sludge (biomass) is pumped back into the fermenter to increase the rate of hydrogen production.[11]
Biohydrogen 109
Photo-fermentation
Photo-fermentation refers to the method of fermentation where light is required as the source of energy. This
fermentation relies on photosynthesis to maintain the cellular energy levels. Fermentation by photosynthesis
compared to other fermentations has the advantage of light as the source of energy instead of sugar. Sugars are
usually available in limited quantities.
All plants, algae and some bacteria are capable of utilizing light as the source of energy. Cyanobacteria which is an
algae, is frequently mentioned capable of hydrogen production by photosynthesis.[12] However the purple
non-sulphur (PNS) bacteria genus Rhodobacter, holds significant promise for the production of hydrogen by
fermentation.[6]
Studies have shown that Rhodobacter sphaeroides is highly capable of hydrogen production while feeding on
organic acids, consuming 98% to 99% of the organic acids during hydrogen production.[6]
As for the dark-fermentation the separation of biomass can be done with a settler tank in the outlet stream, where the
sludge (biomass) is pumped back into the fermenter to increase the rate of hydrogen production .[11]
Currently there is limited experience with photo-fermentation at industrial-scale. Photo-fermentation require light in
the ultra-violet (UV) range up to 400 nm.[13] The distribution of light within the industrial scale photo-fermenter has
to be designed to prevent self-shading inside the fermenter and to ensure sustainable hydrogen production.
A method to ensure proper light distribution and limit self-shading within the fermenter, could be to distribute the
light with an optic fiber where light is transferred into the fermenter and distributed from within the fermenter.[14]
Photo-fermentation with Rhodobacter sphaeroides require mesophilic conditions.[15] The optic fiber will transfer
light and thus heat into the fermenter, but the heat transferred is limited.[14]
The design with an ultra-violent light-source has a huge advantage to other fermentations since ultra-violent light has
the potential to eliminate foreign micro-organisms and to prevent contamination. This will limit the need of cleaning
procedures. However the production rates with photo-fermentation is not as high as with dark-fermentation.
Combined fermentation
Combining dark- and photo-fermentation has shown to be the most efficient method to produce hydrogen through
fermentation.[16] The combined fermentation allows the organic acids produced during dark-fermentation of waste
materials, to be used as substrate in the photo-fermentation process.[6]
For industrial fermentation of hydrogen to be economical feasible, by-products of the fermentation process has to be
minimized. Combined fermentation has the unique advantage of allowing reuse of the otherwise useless chemical,
organic acids, through photosynthesis.
As the method for hydrogen production, this method currently holds significant promise.[6]
Metabolic processes
The metabolic process for hydrogen production are dependent on the reduction of the metabolite ferredoxin.[17]
For this process to run, ferredoxin has to be recycled through oxidation. The recycling process is dependent on the
transfer of electrons from nicotinamide adenine dinucleotide (NADH) to ferredoxin.[17]
The enzymes that catalyse this recycling process are referred to as hydrogen-forming enzymes and have complex
metalloclusters in their active site and require several maturation proteins to attain their active form.[17] The
hydrogen-forming enzymes are inactivated by molecular oxygen and most be separated from oxygen, to produce
hydrogen.[17]
Biohydrogen 110
The three main classes of hydrogen-forming enzymes are [FeFe]-hydrogenase, [NiFe]-hydrogenase and
nitrogenase.[17] These enzymes behaves differently in dark-fermentation with Clostridium and photo-fermentation
with Rhodobacter. The interplay of these enzymes are the key in hydrogen production by fermentation.
Clostridium
The interplay of the hydrogen-forming enzymes in Clostridium is very unique with little or no involvement of
nitrogenase. The hydrogen production in this bacteria is mostly due to [FeFe]-hydrogenase, which activity is a
hundred times higher than [NiFe]-hydrogenase and a thousand times higher than nitrogenase. [FeFe]-hydrogenase
has a Fe-Fe catalytic core with a variety of electron donors and acceptors.[6] [17]
The enzyme [NiFe]-hydrogenase in Clostridium, catalyse a reversible oxidation of hydrogen. [NiFe]-hydrogenase is
responsible for hydrogen uptake, utilizing the electrons from hydrogen for cellular maintenance.[17]
In Clostridium, glucose is broken down into pyruvate and nicotinamide adenine dicleotide (NADH). The formed
pyruvate is then further converted to acetyl-CoA and hydrogen by pyruvate ferredoxin oxidoreductase with the
reduction of ferredoxin.[17] Acetyl-CoA is then converted to acetate, butyrate and propionate.[17] [18]
Acetate fermentation processes are well understood and have a maximum yield of 4 mol hydrogen pr. mol glucose.[6]
The yield of hydrogen from the conversion of acetyl-CoA to butyrate, has half the yield as the conversion to
acetate.[6] [17] In mixed cultures of Clostridium the reaction is a combined production of acetate, butyrate and
propionate.[16] The organic acids which are the by-product of fermentation with Clostridium, can be further
processed as substrate for hydrogen production with Rhodobacter.
Rhodobacter
The purple non-sulphur bacteria Rhodobacter spharoids is able to produce hydrogen from organic acids and
ultra-violet light.[17] The photo-system required for hydrogen production in Rhodobacter (PS-I), differ from its
oxygenic photosystem (PS-II) due to the requirement of organic acids and the inability to oxidize water.[17]
In Rhodobacter, the hydrogen production is due to catalysis by nitrogenase. The production of hydrogen by
[FeFe]-hydrogenase is less than 10 times the hydrogen uptake by [NiFe]-hydrogenase.[19]
The interplay of hydrogenase and nitrogenase in this bacteria is responsible for the production of hydrogen and
require nitrogen-deficient conditions to produce hydrogen.[17] [19]
The main photosynthetic membrane complex is PS-I which accounts
for most of the light-harvest. The photosynthetic membrane complex
PS-II produces oxygen, which inhibit hydrogen production and thus
low partial pressures of oxygen most be sustained during
fermentation.[17]
To attain high production rates of hydrogen, the hydrogen production
by nitrogenase has to exceed the hydrogen uptake by hydrogenase.[19]
Rhodobacter hydrogen metabolism
The substrate is oxidized through the tricarboxylic acids circle and the
produced electrons are transferred to the nitrogenase catalysed
reduction of protons to hydrogen, through the electron transport chain.[17] [19]
Biohydrogen 111
LED-fermenter
A cheap way to build a industrial-size photo-fermenter could be to build a fermenter with ultra-violet light emitting
diodes (UV-LED) as light source. This design prevents self-shading within the fermenter, require limited energy to
maintain photosynthesis and has very low installation costs. This design would also allow cheap models to be built
for educational purpose.
Metabolic engineering
There is a huge potential for improving hydrogen yield by metabolic engineering. The bacteria Clostridium could be
improved for hydrogen production by disabling the uptake hydrogenase, or disabling the oxygen system. This will
make the hydrogen production robust and increase the hydrogen yield in the dark-fermentation step.
The photo-fermentation step with Rhodobacter, is the step which is likely to gain the most from metabolic
engineering. An option could be to disable the uptake-hydrogenase or to disable the photosynthetic membrane
system II (PS-II). Another improvement could be to decrease the expression of pigments, which shields of the
photo-system.
See also
• Hyvolution
• Biological hydrogen production (Algae)
• Photobiology
• Electrohydrogenesis
• Microbial fuel cell
• Caldicellulosiruptor saccharolyticus
References
[1] Demirbas, A. (2009). Biohydrogen: For Future Engine Fuel Demands. Trabzon: Springer. ISBN 1848825102
[2] Stefan Schlag, Bala Suresh, Masahiro Yoneyama (October 2007). "SRI Consulting CEH Report – Hydrogen" (http:/ / www. sriconsulting.
com/ CEH/ Public/ Reports/ 743. 5000/ ). SRI Consulting. . Retrieved 2010-07-01.
[3] "The National Hydrogen Association" (http:/ / www. hydrogenassociation. org/ general/ faqs. asp#howmuchproduced).
Hydrogenassociation.org. 2004-08-13. . Retrieved 2010-07-01.
[4] "Transport and the Hydrogen Economy" (http:/ / www. world-nuclear. org/ info/ inf70. html). World-nuclear.org. . Retrieved 2010-07-01.
[5] The iea energy technology essentials are regularly-updated briefs that draw together the best-available, consolidated information on energy
technologies from the iea network, April 2007.
[6] Tao, Yongzhen; Chen, Yang; Wu, Yongqiang; He, Yanling; Zhou, Zhihua (February 2007). "High hydrogen yield from a two-step process of
dark- and photo-fermentation of sucrose" (http:/ / www. sciencedirect. com/ science/ article/ B6V3F-4KGPP8H-1/ 2/
a2e03311e524ba2baeb47e720d9c47e5). International Journal of Hydrogen Energy 32 (2): 200–206. doi:10.1016/j.ijhydene.2006.06.034.
ISSN 0360-3199. .
[7] Kapdan, Ilgi Karapınar; Kargı, Fikret (2006). "Biohydrogen production from waste materials" (http:/ / www. ichet. org/ ihec2005/ files/
manuscripts/ Kargi F. -Tr. pdf). Enzyme and Microbial Technology. .
[8] Krupp, M.; Widmann, R (May 2009). "Biohydrogen production by dark fermentation: Experiences of continuous operation in large lab
scale". International Journal of Hydrogen Energy 34 (10, Sp. Iss.SI): 4509–4516. doi:10.1016/j.ijhydene.2008.10.043.
[9] Verschuere, L; Rombaut,, G; Sorgeloos, P; Verstraete, W (December 2000). "Probiotic bacteria as biological control agents in aquaculture".
Microbiology and Molecular Biology Reviews 64 (4): 655+. doi:10.1128/MMBR.64.4.655-671.2000.
[10] Watanabe, Hisanori; Yoshino, Hidekichi (May 2010). "Biohydrogen using leachate from an industrial waste landfill as inoculum".
Renewable Energy 35 (5): 921–924. doi:10.1016/j.renene.2009.10.033.
[11] Villadsen, John; Nielsen, Jens Høiriis; Lidén, Gunnar (2003). Bioreaction Engineering Principles (http:/ / books. google. com/
?id=htUeM34b7KgC& lpg=PP1& dq=Bioreaction Engineering Principles& pg=PP1#v=onepage& q) (2 ed.). Springer. ISBN 9780306473494.
.
[12] Lee, Jae-Hwa; Lee, Dong-Geun; Park, Jae-Il; Kim, Ji-Youn (JAN 2010). "Biohydrogen production from a marine brown algae and its
bacterial diversity". Korean Journal of Chemical Engineering 27 (1): 187–192. doi:10.1007/s11814-009-0300-x.
Biohydrogen 112
[13] Kahn, Amanda E.; Durako, Michael J. (October 2009). "Wavelength-specific photo-synthetic responses of Halophila johnsonii from
marine-influenced versus river-influenced habitats". Aquatic Botany 91 (3): 245–249. doi:10.1016/j.aquabot.2009.06.004.
[14] THE NORTH STATE, www.thenorthstate.com. "Sunlight Direct" (http:/ / www. sunlight-direct. com). Sunlight Direct. . Retrieved
2010-07-01.
[15] Nath, K; Kumar, A; Das, D (September 2005). "Hydrogen production by Rhodobacter sphaeroides strain OU001 using spent media of
Enterobacter cloacae strain DM11". Applied Microbiology and Biotechnology 68 (4): 533–541. doi:10.1007/s00253-005-1887-4.
PMID 15666144.
[16] Yang, Honghui; Guo,, Liejin; Liu, Fei (March 2010). "Enhanced bio-hydrogen production from corncob by a two-step process: Dark- and
photo-fermentation". Bioresource Technology 101 (6): 2049–2052. doi:10.1016/j.biortech.2009.10.078. PMID 19963373.
[17] Mathews, Juanita; Wang, Guangyi (September 2009). "Metabolic pathway engineering for enhanced biohydrogen production". International
Journal of Hydrogen Energy 34 (17, Sp. Iss. SI): 7404–7416. doi:10.1016/j.ijhydene.2009.05.078.
[18] "KEGG PATHWAY: Pyruvate metabolism - Clostridium acetobutylicum" (http:/ / www. genome. jp/ kegg-bin/ show_pathway?cac00620).
Genome.jp. . Retrieved 2010-07-01.
[19] Koku, H; Eroglu, I; Gunduz, U; Yucel, M; Turker, L (2002). "Aspects of the metabolism of hydrogen production by Rhodobacter
sphaeroides". International Journal of Hydrogen Energy 27 (11-12): 1315–1329. doi:10.1016/S0360-3199(02)00127-1.
External links
• Fermentation of hydrogen (http://www.youtube.com/watch?v=wKfx3-CpqTQ)
• Production of hydrogen with bacteria (http://www.youtube.com/watch?v=n_h08Vbdjt4)
• 1999 - Biohydrogen RITE Biological Hydrogen Program (http://www.springerlink.com/content/
p3u912048n600315/)
• GTL (http://genomicsgtl.energy.gov/benefits/biohydrogen.shtml)
• EU & Dutch Biohydrogen research page (http://www.biohydrogen.nl)
• wasteintoenergy.org (http://www.wasteintoenergy.org)
• University of California Davis -New Technology Turns Food Leftovers Into Electricity, Vehicle Fuels (http://
www.news.ucdavis.edu/search/news_detail.lasso?id=7915)
• Onsite Power Systems (http://www.onsitepowersystems.com/)
• "Appendix 2: Biohydrogen" (http://completebiogas.com/BiogasHandbook_A02_biohydrogen.pdf) from The
Complete Biogas Handbook
• BBSRC- Our Science- Bacteria Make Light Work of Hydrogen Production (http://www.bbsrc.ac.uk/science/
our_science_explained/0906_bacteria_make_light_work_of_hydrogen_production.html)
• Biowaste2energy Ltd is applying biohydrogen (http://www.bw2e.com)
Hydrogen production 113
Hydrogen production
Hydrogen production is the industrial method for generating hydrogen. Currently the dominant technology for
direct production is steam reforming from hydrocarbons. Hydrogen is also produced as a byproduct of other
processes and managed with hydrogen pinch[1] . Many other methods are known including electrolysis and
thermolysis. The discovery and development of less expensive methods of production of bulk hydrogen is relevant to
the establishment of a hydrogen economy.[2]
From hydrocarbons
Steam reforming
Fossil fuel currently is the main source of hydrogen production[3] . Hydrogen can be generated from natural gas with
approximately 80% efficiency, or from other hydrocarbons to a varying degree of efficiency. Specifically, bulk
hydrogen is usually produced by the steam reforming of methane or natural gas[4] At high temperatures
(700–1100 °C), steam (H2O) reacts with methane (CH4) to yield syngas.
CH4 + H2O → CO + 3 H2 + 191.7 kJ/mol[5]
In a second stage, further hydrogen is generated through the
lower-temperature water gas shift reaction, performed at about 130 °C:
CO + H2O → CO2 + H2 - 40.4 kJ/mol
Essentially, the oxygen (O) atom is stripped from the additional water
(steam) to oxidize CO to CO2. This oxidation also provides energy to
maintain the reaction. Additional heat required to drive the process is
generally supplied by burning some portion of the methane.
Gasification
Steam reforming generates carbon dioxide (CO2). Since the production
is concentrated in one facility, it is possible to separate the CO2 and
dispose of it properly, for example by injecting it in an oil or gas reservoir (see carbon capture), although this is not
currently done in most cases. A carbon dioxide injection project has been started by a Norwegian company
StatoilHydro in the North Sea, at the Sleipner field. However, even if the carbon dioxide is not sequestered, overall
producing hydrogen from natural gas and using it for a hydrogen vehicle only emits half the carbon dioxide that a
gasoline car would. (This is disputed in The Hype about Hydrogen: Fact and Fiction in the Race to Save the
Climate, a book by Joseph J. Romm, published in 2004 by Island Press and updated in 2005. Romm says that
directly burning fossil fuels generates less CO2 than hydrogen production.)
Integrated steam reforming / co-generation - It is possible to combine steam reforming and co-generation of steam
and power into a single plant. This can deliver benefits for an oil refinery because it is more efficient than separate
hydrogen, steam and power plants. Air Products recently built an integrated steam reforming / co-generation plant in
Port Arthur, Texas.[6]
Hydrogen production 114
Partial oxidation
The partial oxidation reaction occurs when a substoichiometric fuel-air mixture is partially combusted in a reformer,
creating a hydrogen-rich syngas. A distinction is made between thermal partial oxidation (TPOX) and catalytic
partial oxidation (CPOX).
Plasma reforming
The Kværner-process or Kvaerner carbon black & hydrogen process (CB&H)[3] is a plasma reforming method,
developed in the 1980s by a Norwegian company of the same name, for the production of hydrogen and carbon
black from liquid hydrocarbons (CnHm). Of the available energy of the feed, approximately 48% is contained in the
hydrogen, 40% is contained in activated carbon and 10% in superheated steam.[7] CO2 is not produced in the process.
A variation of this process is presented in 2009 using plasma arc waste disposal technology for the creation of
hydrogen, heat and carbon from methane and natural gas in a plasma converter[8]
Coal
Coal can be converted into syngas and methane, also known as town gas, via coal gasification. Syngas consists of
hydrogen and carbon monoxide.[9] . Another method for conversion is low temperature and high temperature coal
carbonization[10] .
From water
Sulfur-Iodine Cycle
The sulfur-iodine cycle (S-I cycle) is a thermochemical process which generates hydrogen from water, but at a much
higher efficiency than water splitting. The sulfur and iodine used in the process are recovered and reused, and not
consumed by the process. It is well suited to production of hydrogen by high-temperature nuclear reactors.
From urine
Hydrogen can also be made from urine. Using urine, hydrogen production is 332% more energy efficient than using
water.[12] [13] The research was conducted by Geraldine Botte from the Ohio University. Recently, Dr. Shanwen Tao
of the Heriot-Watt University has invented a Carbamide Power System Fuel Cell that can immediatelly convert urine
into electricity.[14]
Hydrogen production 115
Biohydrogen routes
Biomass and waste streams can be converted into biohydrogen with biomass gasification, steam reforming or
biological conversion like biocatalysed electrolysis or fermentative hydrogen production:
Biocatalysed electrolysis
Besides dark fermentation, electrohydrogenesis (electrolysis using microbes)
is another possibility. Using microbial fuel cells, wastewater or plants can be
used to generate power. Biocatalysed electrolysis should not be confused with
biological hydrogen production, as the latter only uses algae and with the
latter, the algae itself generates the hydrogen instantly, where with
A microbial electrolysis cell
biocatalysed electrolysis, this happens after running through the microbial
fuel cell and a variety of aquatic plants[21] can be used. These include reed
sweetgrass, cordgrass, rice, tomatoes, lupines, algae [22]
Hydrogen production 116
Other methods
• Synthetic biology [23] [24] [25]
See also
• Ammonia production
• Biological hydrogen production
• Hydrogen
• Hydrogen analyzer
• Hydrogen compressor
• Hydrogen economy
• Hydrogen embrittlement
• Hydrogen leak testing
• Hydrogen pipeline transport
• Hydrogen piping
• Hydrogen purifier
• Hydrogen purity
• Hydrogen safety
• Hydrogen sensor
• Hydrogen storage
• Hydrogen station
• Hydrogen tank
• Hydrogen tanker
• Hydrogen technologies
• Hydrogen valve
• Industrial gas
• Liquid Hydrogen
• Next Generation Nuclear Plant (partly for hydrogen production)
• The Phoenix Project: Shifting from Oil To Hydrogen (book)
• Renewable energy
• The Hype about Hydrogen
• Lane hydrogen producer
• Linde-Frank-Caro process
• Liquid nitrogen production
• Underground hydrogen storage
Hydrogen production 117
References
[1] Waste hydrogen purification and supply (http:/ / www. hydrogenhighway. ca/ code/ navigate. asp?doi=224)
[2] Peter Häussinger1, Reiner Lohmüller2, Allan M. Watson “Hydrogen” Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH,
Weinheim.
[3] Bellona-HydrogenReport (http:/ / www. interstatetraveler. us/ Reference-Bibliography/ Bellona-HydrogenReport. html)
[4] Fossil fuel processor (http:/ / auto. howstuffworks. com/ fuel-processor. htm)
[5] "HFCIT Hydrogen Production: Natural Gas Reforming" (http:/ / www1. eere. energy. gov/ hydrogenandfuelcells/ production/ natural_gas.
html). U.S. Department of Energy. 2008-12-15. .
[6] Port Arthur II Integrated Hydrogen/Cogeneration Facility, Port Arthur, Texas (http:/ / www. airproducts. com/ nr/ rdonlyres/
6226ec23-a536-4603-ab37-2b2ff3f9d45b/ 0/ port_arthur_122212258eprint. pdf) Power magazine, September 2007
[7] https:/ / www. hfpeurope. org/ infotools/ energyinfos__e/ hydrogen/ main03. html
[8] Kværner-process with plasma arc waste disposal technology (http:/ / fuelcellsworks. com/ news/ 2009/ 10/ 12/
hydrogen-breakthrough-for-norwegian-company/ )
[9] "HFCIT Hydrogen Production: Coal Gasification" (http:/ / www1. eere. energy. gov/ hydrogenandfuelcells/ production/ coal_gasification.
html). U.S. Department of Energy. 2008-12-12. .
[10] [pubs.acs.org/cgi-bin/jtext?enfuem/15/i03/abs/ef990178a Internal gas pressure characteristics generated during coal carbonization in a coke
oven]
[11] "Electrolysis of water and the concept of charge" (http:/ / www. practicalphysics. org/ go/ Experiment_677. html). .
[12] Hydrogen from urine (http:/ / www. physorg. com/ news165836803. html)
[13] 1,23V/0,37V
[14] Carbamide Power System Fuel Cell (http:/ / www. outlookseries. com/ N8/ Science/
3753_Shanwen_Tao_Heriot-Watt_University_Carbamide_Power_System_Fuel_Cell_Turns_Urine_Electricity_Water_Shanwen_Tao. htm)
[15] High hydrogen yield from a two-step process of dark-and photo-fermentation of sucrose (http:/ / cat. inist. fr/ ?aModele=afficheN&
cpsidt=18477081)
[16] (http:/ / dx. doi. org/ 10. 1371/ journal. pone. 0000456)
[17] (http:/ / dx. doi. org/ 10. 1002/ bit. 22630)
[18] (http:/ / dx. doi. org/ 10. 1016/ j. copbio. 2010. 05. 005)
[19] (http:/ / dx. doi. org/ 10. 1002/ cssc. 200900017)
[20] (http:/ / dx. doi. org/ 10. 1039/ b818694d)
[21] aquatic plants (http:/ / www. glastuinbouw. wur. nl/ UK/ expertise/ energy/ innovations/ plantenergy/ )
[22] Power from plants using microbial fuel cell (http:/ / translate. google. com/ translate?js=n& prev=_t& hl=nl& ie=UTF-8& u=http:/ / www.
resource-online. nl/ achtergrond. php?id=147& sl=nl& tl=en& history_state0=)
[23] Synthetic biology and hydrogen (http:/ / www. highbeam. com/ doc/ 1G1-163896478. html)
[24] Synthetic biology to make hydrogen (http:/ / www. guardian. co. uk/ science/ 2008/ jun/ 19/ chemistry. agriculture)
[25] Synthetic biology at Berkeley Lab (http:/ / pbd. lbl. gov/ synthbio/ aims. htm)
[26] National Renewable Energy Laboratory 2003 Research Review: "New Horizons for Hydrogen." (http:/ / www. nrel. gov/ research_review/
pdfs/ 2003/ 36178b. pdf)
External links
• U.S. DOE 2008-Technical progress in hydrogen production (http://www.hydrogen.energy.gov/
annual_progress08_production.html)
• U.S. NREL article on hydrogen production (http://www.nrel.gov/hydrogen/proj_production_delivery.html)
• Genetically engineered blood protein can be used to produce hydrogen gas from water (http://www3.imperial.
ac.uk/newsandeventspggrp/imperialcollege/newssummary/news_1-12-2006-11-4-23?newsid=3016)
Hydrogen infrastructure 118
Hydrogen infrastructure
A hydrogen infrastructure is the infrastructure of pipes and stations for distribution and sale of hydrogen fuel.
Network
Hydrogen highway
A hydrogen highway is a chain of hydrogen-equipped filling stations and other infrastructure along a road or
highway which allow hydrogen vehicles to travel.
Hydrogen stations
Hydrogen stations which are not situated near a hydrogen pipeline get supply via hydrogen tanks, compressed
hydrogen tube trailers, liquid hydrogen trailers, liquid hydrogen tank trucks or dedicated onsite production. Some
firms as ITM Power are also providing solutions to make your own hydrogen (for use in the car) at home.[4]
South Carolina also has a hydrogen freeway in the works. There are currently two hydrogen fueling stations, both in
Aiken and Columbia, SC. Additional stations are expected in places around South Carolina such as Charleston,
Myrtle Beach, Greenville, and Florence. According to the South Carolina Hydrogen & Fuel Cell Alliance, the
Columbia station has a current capacity of 120 kg a day, with future plans to develop on-site hydrogen production
from electrolysis and reformation. The Aiken station has a current capacity of 80 kg. There is extensive funding for
Hydrogen fuel cell research and infrastructure in South Carolina. The University of South Carolina, a founding
member of the South Carolina Hydrogen & Fuel Cell Alliance, received 12.5 million dollars from the Department of
Energy for its Future Fuels Program.[5]
The California Hydrogen Highway is an initiative by the California Governor to implement a series of hydrogen
refueling stations along that state. These stations are used to refuel hydrogen vehicles such as fuel cell vehicles and
hydrogen combustion vehicles. As of July 2007 California had 179 fuel cell vehicles and twenty five stations were in
operation,[6] and ten more stations have been planned for assembly in California. However, there have already been
three hydrogen fueling stations decommissioned.[7]
In May 2010, UNIDO has launched, on behalf of the International Centre for Hydrogen Energy Technologies, a call
for tender related to the supply and installation by the end of 2011 of a hydrogen production, storage and filling
facility on the Golden Horn, in Istanbul. This station will be used for the refueling of a hydrogen fuel cell driven
passenger boat as well as for that of a hydrogen internal combustion bus.[8]
Hydrogen infrastructure 119
See also
• HCNG dispenser
• Hydrogen piping
• Hydrogen economy
• Underground hydrogen storage
References
[1] Compressorless Hydrogen Transmission Pipelines (http:/ / www. leightyfoundation. org/ files/ WHEC16-Lyon/ WHEC16-Ref022. pdf)
[2] DOE Hydrogen Pipeline Working Group Workshop (http:/ / www1. eere. energy. gov/ hydrogenandfuelcells/ pdfs/ hpwgw_airprod_remp.
pdf)
[3] Every 50 to 100 miles (http:/ / www. hydrogenforecast. com/ ArticleDetails. php?articleID=250)
[4] Running on home-brewed hydrogen (http:/ / news. bbc. co. uk/ 2/ hi/ technology/ 7496644. stm)
[5] Cluster Successes in South Carolina (http:/ / www. schydrogen. org/ documents/ Reports/ Cluster_Successes. pdf)
[6] "California Fuel Cell Partnership" (http:/ / www. cafcp. org). .
[7] "Hydrogen Fueling Stations" (http:/ / www. cafcp. org/ fuel-vehl_map. html). .
[8] "Golden Horn Refuelling Station" (http:/ / www. unido-ichet. org. org/ index. php?lang=en& Itemid=42& option=com_content&
id=401:golden-horn-refuelling-station& view=article). .
External links
• The Hydrogen Infrastructure Transition (HIT) Model (http://pubs.its.ucdavis.edu/publication_detail.
php?id=140)
• Roads2HyCom Infrastructure (http://www.ika.rwth-aachen.de/r2h/index.php/
European_Hydrogen_Infrastructure_and_Production)
Hydrogen line
The hydrogen line, 21 centimeter line or HI line refers to the electromagnetic radiation spectral line that is created
by a change in the energy state of neutral hydrogen atoms. This electromagnetic radiation is at the precise frequency
of 1420.40575177 MHz, which is equivalent to the vacuum wavelength of 21.10611405413 cm in free space. This
wavelength or frequency falls within the microwave radio region of the electromagnetic spectrum, and it is observed
frequently in radio astronomy, since those radio waves can penetrate the large clouds of interstellar cosmic dust that
are opaque to visible light.
Note that the relationship between the frequency and the wavelength is found from the simple equation that says that
the wavelength equals c (the speed of light) divided by the frequency measured in hertz.
The microwaves of the hydrogen line comes from the atomic transition between the two hyperfine levels of the
hydrogen 1s ground state.[1] There is a difference in energy between these two hyperfine levels, and the frequency of
the quanta that are emitted is given by Planck's equation.
Hydrogen line 120
Cause
Origin of Neutral Hydrogen Emission
An electron orbiting a proton with parallel spins (pictured) has higher Fine and hyperfine structure in
energy than if the spins were anti-parallel. hydrogen. The hyperfine splitting
of the ground 2S state is the source
of the 21 cm hydrogen line.
Neutral hydrogen consists of a single proton orbited by a single electron. As well as their orbital motion, the proton
and electron also have spin. Classically, this is analogous to rotational motion (like the Earth rotating on its axis as it
orbits the Sun), but as they are quantum particles the concept has a slightly different meaning.
The spin of the electron and proton can be in either direction - in the classical analogy they are rotating clockwise or
anticlockwise around a given axis. They may have their spin oriented in the same direction or in opposite directions.
Because of magnetic interactions between the particles, a hydrogen atom that has the spins of the electron and proton
aligned in the same direction (parallel) has slightly more energy than one where the spins of the electron and proton
are in opposite directions (anti-parallel). The fact that the lowest-energy configuration arises in the anti-parallel spin
configuration is an inherently quantum-mechanical result. A proton and electron with anti-parallel spins have parallel
magnetic moments owing to their opposite charge. Classical mechanics would predict that this configuration should
have higher energy, but a more detailed quantum mechanical analysis shows that the opposite is true.
The lowest orbital energy state of atomic hydrogen has hyperfine splitting arising from the spins of the proton and
electron changing from a parallel to antiparallel configuration. This transition is highly forbidden with an extremely
small probability of 2.9×10−15 s−1.
This means that the time for a single isolated atom of neutral hydrogen to undergo this transition is around 10 million
(107) years and so is unlikely to be seen in a laboratory on Earth. However, as the total number of atoms of neutral
hydrogen in the interstellar medium is very large, this emission line is easily observed by radio telescopes. Also, the
Hydrogen line 121
lifetime can be considerably shortened by collisions with other hydrogen atoms and interaction with the cosmic
microwave background.
The line has an extremely small natural width because of its long lifetime, so most broadening is due to doppler
shifts caused by the motion of the emitting regions relative to the observer.
Discovery
During the 1930s, it was noticed that there was a radio 'hiss' that varied on a daily cycle and appeared to be
extraterrestrial in origin. After initial suggestions that this was due to the Sun, it was observed that the radio waves
seemed to be coming from the centre of the Galaxy. These discoveries were published in 1940 and were seen by
Professor J.H. Oort who knew that significant advances could be made in astronomy if there were emission lines in
the radio part of the spectrum. He referred this to Dr Hendrik van de Hulst who, in 1944, predicted that neutral
hydrogen could produce radiation at a frequency of 1420.4058 MHz due to two closely spaced energy levels in the
ground state of the hydrogen atom.
The 21 cm line (1420.4 MHz) was first detected in 1951 by Ewen and Purcell at Harvard University,[2] and
published after their data was corroborated by Dutch astronomers Muller and Oort,[3] and by Christiansen and
Hindman in Australia. After 1952 the first maps of the neutral hydrogen in the Galaxy were made and revealed, for
the first time, the spiral structure of the Milky Way.
Uses in cosmology
The line is of great interest in big bang cosmology because it is the only known way to probe the "dark ages" from
recombination to reionization. Including the redshift, this line will be observed at frequencies from 200 MHz to
about 9 MHz on Earth. It potentially has two applications. First, by mapping redshifted 21 centimeter radiation it
can, in principle, provide a very precise picture of the matter power spectrum in the period after recombination.
Second, it can provide a picture of how the universe was reionized, as neutral hydrogen which has been ionized by
radiation from stars or quasars will appear as holes in the 21 centimeter background.
However, 21 centimeter experiments are very difficult. Ground based experiments to observe the faint signal are
plagued by interference from television transmitters and the ionosphere, so they must be very secluded and careful
about eliminating interference if they are to succeed. Space based experiments, even on the far side of the moon
(which should not receive interference from terrestrial radio signals), have been proposed to compensate for this.
Little is known about other effects, such as synchrotron emission and free-free emission on the galaxy. Despite these
problems, 21 centimeter observations, along with space-based gravity wave observations, are generally viewed as the
next great frontier in observational cosmology, after the cosmic microwave background polarization.
Hydrogen line 122
See also
• H-alpha, the visible red spectral line with wavelength of 6562.8 Ångstroms
• Hydrogen spectral series
• Hydrogen Atom
• Radio astronomy
• Rydberg formula
• Spectral line
References
[1] "The Hydrogen 21-cm Line" (http:/ / hyperphysics. phy-astr. gsu. edu/ hbase/ quantum/ h21. html). Hyperphysics. Georgia State University.
2004-10-30. . Retrieved 2008-09-20.
[2] Ewan, H.I.; E.M. Purcell (September 1951). "Observation of a line in the galactic radio spectrum" (http:/ / www. nature. com/ nature/ journal/
v168/ n4270/ pdf/ 168356a0. pdf). Nature 168 (4270): 356. doi:10.1038/168356a0. . Retrieved 2008-09-21.
[3] Muller, C.A.; J.H. Oort (September 1951). "The Interstellar Hydrogen Line at 1,420 Mc./sec., and an Estimate of Galactic Rotation" (http:/ /
www. nature. com/ nature/ journal/ v168/ n4270/ pdf/ 168356a0. pdf). Nature 168 (4270): 357–358. doi:10.1038/168357a0. . Retrieved
2008-09-21.
[4] {cite book |last=Basalla |first=George |date=2006 |title=Civilized Life in the Universe |publisher=Oxford University Press |isbn=0195171810
|pages=133–135}}
[5] Makovetsky P. Smotri v koren' (http:/ / n-t. ru/ ri/ mk/ sk109-4. htm) (in Russian)
Hydrogen line 123
Cosmology
• P. Madau, A. Meiksin and M. J. Rees, "21-cm Tomography of the Intergalactic Medium at High Redshift",
Astrophysical Journal 475, 429 (1997) arXiv:astro-ph/9608010.
• B. Ciardi, P. Madau, "Probing Beyond the Epoch of Hydrogen Reionization with 21 Centimeter Radiation",
Astrophysical Journal 596, 1 (2003) arXiv:astro-ph/0303249.
• M. Zaldarriaga, S. Furlanetto and L. Hernquist, "21 Centimeter Fluctuations from Cosmic Gas at High Redshifts",
Astrophysical Journal 608, (2004) 608 arXiv:astro-ph/0311514.
• X. Chen and J. Miralda-Escudé, "Observing the Reionization Epoch Through 21 Centimeter Radiation", Mon.
Not. Roy. Astron. Soc. 347, 187 (2004) arXiv:astro-ph/0303395.
• A. Loeb and M. Zaldarriaga, "Measuring the Small-Scale Power Spectrum of Cosmic Density Fluctuations
Through 21 cm Tomography Prior to the Epoch of Structure Formation", Phys. Rev. Lett. 92, 211301 (2004)
arXiv:astro-ph/0312134.
• M. G. Santos, A. Cooray and L. Knox, "Multifrequency analysis of 21 cm fluctuations from the Era of
Reionization", Astrophysical Journal 625, 575 (2005) arXiv:astro-ph/0408515.
• R. Barkana and A. Loeb, "Detecting the Earliest Galaxies Through Two New Sources of 21cm Fluctuations",
Astrophysical Journal 626, 1 (2005) arXiv:astro-ph/0410129.
External links
• The story of Ewen and Purcell's discovery of the 21 cm line (http://www.nrao.edu/whatisra/hist_ewenpurcell.
shtml)
• Ewen and Purcell's original paper in Nature (http://www.nature.com/physics/looking-back/ewen/index.html)
• PAST experiment, arXiv:astro-ph/0404083.
• LOFAR experiment (http://www.lofar.org/)
• Mileura Widefield Array experiment (http://web.haystack.mit.edu/MWA)
• Square Kilometer Array experiment (http://www.skatelescope.org/)
Hydrogen purity 124
Hydrogen purity
Hydrogen purity or hydrogen quality is a term to describe the lack of impurities in hydrogen as a fuel gas. The
purity requirement varies with the application, for example a H2 ICE can tolerate low hydrogen purity where a
hydrogen fuel cell requires high hydrogen purity to prevent catalyst poisoning[1] .
See also
• Glossary of fuel cell terms
• Katharometer
References
[1] 2007-DOE-Hydrogen Fuel Quality (http:/ / www. nrel. gov/ docs/ fy07osti/ 41541. pdf)
[2] Issues in hydrogen purity detection and monitoring (http:/ / www. ottawapolicyresearch. ca/ OPRA_Brief_H2PurityDetectionMonitoring.
pdf)
External links
• H2 Quality (http://www.fuelcellstandards.com/H2Quality.ppt)
• 2004-Hydrogen Purity Standard (http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/
fp_workshop_smith.pdf)
• 2004-Fuel Purity Specifications Workshop (http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/
fuel_purity_notes.pdf)
Article Sources and Contributors 125
Antihydrogen Source: http://en.wikipedia.org/w/index.php?oldid=396629215 Contributors: 84user, Almightymasteroftheuniverse, Andre Engels, Angr, Antandrus, Astiburg, AxelBoldt,
Bambaiah, BenRG, Bob Saint Clar, Bobblewik, CCK, Carlog3, Chronitis, Chrumps, CosineKitty, Curlymeatball38, Dobromila, Domitori, Eclecticology, Enochlau, EoGuy, Eric119, Feezo,
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Malcolm Farmer, Marj Tiefert, Massen, Materialscientist, Mike Rosoft, Mion, NClement, Nergaal, Newone, Nuujinn, OMenda, Omegatron, Pedrocelli, Pichote, Pizza1512, Qblik, Revth, Ross
Burgess, Rreagan007, SigPig, SkyLined, Smoggyrob, Spacepotato, Terbospeed, Therearewaytoomanybooksinhere, VKokielov, Van helsing, Vortexrealm, Wrightbus, Zachwoo, 43 anonymous
edits
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Appleyard, Anville, Aquilosion, Army1987, Arnero, Art LaPella, Ashill, AstroNomer, Barbara Shack, BenRG, Bensaccount, BernardH, Bevo, Bgamari, Bkkbrad, BlazerKnight, Bobrayner,
Bogey97, Borowsky, Brandonrush, Brownsteve, Bryan Derksen, CYD, Catgut, Chairman S., Charles Matthews, Christopher.Gordon3, Ciaccona, Cometstyles, Complexica, Conversion script,
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Hydrogen-like atom Source: http://en.wikipedia.org/w/index.php?oldid=386237051 Contributors: Achoo5000, Akesich, Barticus88, Bgamari, Chuunen Baka, Dan Gluck, Eequor, Eroica,
Feezo, Fresheneesz, Granolanifa, GregRM, HappyCamper, Henrygb, Incnis Mrsi, Iridescent, Itub, Jacopo Werther, Jeppesn, JimR, John C PI, Karol Langner, Linas, Mion, Nergaal, OMCV, Out
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Hydrogen spectral series Source: http://en.wikipedia.org/w/index.php?oldid=392812384 Contributors: Anna Lincoln, Bender235, DVdm, Dan East, Ducks boy, Headbomb, Karol Langner,
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Liquid hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=396508382 Contributors: 4RM0, 8472, AGK, Awanta, Badocter, Beaber, Beamjockey, Beetstra, BenFrantzDale, Bird of
paradox, Bob Saint Clar, Bryan Derksen, CanOfWorms, Canonymous, CommonsDelinker, Dammit, Edgar181, Enenn, Fangfufu, Frank101, Gene Nygaard, Graham87, Greg L, Grylliade, HalJor,
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Article Sources and Contributors 126
Veraladeramanera, Vortexrealm, WAS 4.250, Wikibob, Wikiborg, Wolfkeeper, Woohookitty, 94 anonymous edits
Solid hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=336326340 Contributors: Carcharoth, Mion, Moralis, Nickosaurr, Pstanton, Skier Dude, Stone, Underpants, 2 anonymous
edits
Metallic hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=383247016 Contributors: Aerobird, Agd1, Alan Peakall, AndrewBuck, Anthony Appleyard, Ary29, Ase1e1, Ataru,
Attilios, Axl, BD2412, Barhamd, Bendzh, Bkell, Bryan Derksen, Calcwatch, Can't sleep, clown will eat me, CarlFeynman, Carlos84, Chemninja, CosineKitty, Crispmuncher, DMacks,
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Nascent hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=357113164 Contributors: Abhishek191288, After Midnight, Cryptic C62, Doug butler, DragonflySixtyseven, Georgebts,
Headbomb, Kbh3rd, Kku, Mac Davis, Michaf, Mion, Securiger, Shaddack, Shadowjams, Shinkolobwe, SiliconDioxide, Sillybilly, Smokefoot, The way, the truth, and the light, TubularWorld,
X42bn6, 14 anonymous edits
Isotopes of hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=396800418 Contributors: (jarbarf), 13mullja, AdjustShift, Ardric47, BiT, Blacklemon67, Blue520, Castorquinn,
DabMachine, Daigaku2051, Dirac66, Donarreiskoffer, Driedshroom, EdC, Eric119, Evil Monkey, Femto, Gamer007, Gene Nygaard, Glane23, Greater mind, Headbomb, JFreeman, Jared Preston,
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आशीष भटनागर, 102 anonymous edits
Deuterium Source: http://en.wikipedia.org/w/index.php?oldid=395716394 Contributors: 128.59.51.xxx, 130.225.29.xxx, 16@r, 203.109.250.xxx, A2-computist, Adam Conover, Agesworth,
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Yamaguchi先生, Zeimusu, 253 anonymous edits
Tritium Source: http://en.wikipedia.org/w/index.php?oldid=396546936 Contributors: 128.59.51.xxx, 300840da, ARC Gritt, Aarchiba, Ahoerstemeier, Allissonn, Alvis, An Unknown Person,
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Hydrogen-4 Source: http://en.wikipedia.org/w/index.php?oldid=384719175 Contributors: Antonio Lopez, DabMachine, Eric119, Gamer007, Headbomb, Ice Ardor, JWB, John, Karol Langner,
Kbdank71, Keenan Pepper, LeonWhite, Mattd4u2nv, Maximaximax, Mewaqua, Mike Rosoft, Mike40033, Oo64eva, OrangeDog, Pamputt, Smith609, Spacepotato, Wang Ivan, 9 anonymous
edits
Hydrogen-5 Source: http://en.wikipedia.org/w/index.php?oldid=296211195 Contributors: Ardric47, Bryan Derksen, DabMachine, Eric119, Hellbus, Ice Ardor, JWB, Karol Langner, Kbdank71,
Keenan Pepper, Mattd4u2nv, Mike Rosoft, Mike40033, Mike4ty4, Oliphaunt, Oo64eva, Sceptre, Smith609, Spacepotato, Valodzka, 5 anonymous edits
Spin isomers of hydrogen Source: http://en.wikipedia.org/w/index.php?oldid=395497029 Contributors: Aditya.m4, Ascentury, Dirac66, Doradus, Gadolinist, Headbomb, Hellbus, IceKarma,
Jaeljojo, Mikespedia, Mion, Nergaal, Opabinia regalis, OrangeDog, Peregrinoerick, SilverStar, Stone, Terrek, Urhixidur, Vertovian, Whiner01, Wolfkeeper, Wyang, Xaa, 22 anonymous edits
Bosch reaction Source: http://en.wikipedia.org/w/index.php?oldid=379704231 Contributors: CharlesC, Chem-awb, Choij, Headbomb, Icer CRO, Marcelo-Silva, Mion, Peter.steier, Silvonen,
Tomasz Dolinowski, Treehill, V8rik, ~K, 18 anonymous edits
Hydrogen cycle Source: http://en.wikipedia.org/w/index.php?oldid=379094852 Contributors: 1ForTheMoney, Anxietycello, Atif.t2, Conrad.Irwin, Cpl Syx, Dendlai, Discospinster,
Hamburgerman, Headbomb, Jrockley, Karol Langner, Katoa, Keenan Pepper, Michael Hardy, Mikenorton, Onco p53, Orbst, Papodelwiken, Pb30, Poppy, Prashant.ashley, Shrumster, Skiff,
Smartse, Snaxe920, Supten, TAS, The Thing That Should Not Be, Vortexrealm, Vsmith, Zawer, 27 anonymous edits
Hydrogenation Source: http://en.wikipedia.org/w/index.php?oldid=396262832 Contributors: 168..., 19vwishart, 2261Daryl, AJim, AThing, Altenmann, AndrewHowse, Antandrus, Beagel,
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Dehydrogenation Source: http://en.wikipedia.org/w/index.php?oldid=395537881 Contributors: Bob, Bobo192, Carlog3, Craptree, Edgar181, Fermi121, Ideal gas equation, Itub, Jmendez,
Keenan Pepper, Mion, Nirmos, Rifleman 82, Smaljers, Vortexrealm, 15 anonymous edits
Transfer hydrogenation Source: http://en.wikipedia.org/w/index.php?oldid=396153470 Contributors: Andrewpmk, Beagel, Keenan Pepper, Mion, Nuklear, OMCV, Smokefoot, Stone,
Takometer, V8rik, Vortexrealm, 10 anonymous edits
Hydrogenolysis Source: http://en.wikipedia.org/w/index.php?oldid=376574197 Contributors: Adkins, CatherineMunro, Edgar181, Gnostic804, Kostisl, Mion, Nseidm1, Rifleman 82,
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Hydron Source: http://en.wikipedia.org/w/index.php?oldid=381012749 Contributors: Armando-Martin, Chotu21, December21st2012Freak, Firq, Itub, Julianonions, Mikespedia, Okedem,
Puppy8800, Reindra, Rifleman 82, Stone, Whiner01, Wickey-nl, 9 anonymous edits
Sabatier reaction Source: http://en.wikipedia.org/w/index.php?oldid=391814198 Contributors: Antaeus Feldspar, Benjamindees, BiggKwell, Ceyockey, Charles Matthews, DanPope,
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Hydrogen damage Source: http://en.wikipedia.org/w/index.php?oldid=393031210 Contributors: Bleh999, Craig Pemberton, Eastlaw, Edward, Element16, FCYTravis, Hkhenson, John, John
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Rhun, Rudyh01, Shaddack, Snezzy, StaticGull, Stephenb, TheNewPhobia, Tkgnamboodhiri, Trisino, Turboragtop, Vortexrealm, Vsmith, Wavelength, Wizard191, ZorbaTHut, یکیو یلع, 51
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Hydrogen leak testing Source: http://en.wikipedia.org/w/index.php?oldid=351505588 Contributors: Aardvarktesting, Cgarber, FayssalF, Headbomb, Lambdacore, Maseracing, Mion, Nergaal,
Quantumobserver, Trentool2, Vortexrealm, 11 anonymous edits
Hydrogen safety Source: http://en.wikipedia.org/w/index.php?oldid=395812143 Contributors: Iridescent, Jjhamilton, Mion, Nergaal, NuclearWarfare, Pbspbs, R'n'B, Rei, Robbin' Knowledge,
Sergey bloomkin, Shoefly, Tkma, Xenonice, 8 anonymous edits
Timeline of hydrogen technologies Source: http://en.wikipedia.org/w/index.php?oldid=393572682 Contributors: Cromwellt, Daniel Christensen, FiggyBee, Gerhard51, Giovanni-P,
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Biohydrogen Source: http://en.wikipedia.org/w/index.php?oldid=393581157 Contributors: 3l1t1st, Appeltree1, C777, ChildofMidnight, Dancter, Erud, Freewaay, Gmohanakrishna, Gobonobo,
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Hydrogen production Source: http://en.wikipedia.org/w/index.php?oldid=396126029 Contributors: ABF, Aaadddaaammm, Acdx, Alagiah, Alan Liefting, Alansohn, AlexH555, AndrewBuck,
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Hydrogen infrastructure Source: http://en.wikipedia.org/w/index.php?oldid=389491417 Contributors: Appeltree1, Daduck08, Geologyguy, Gregory Dziedzic, Headbomb, Hmains, KVDP,
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Hydrogen line Source: http://en.wikipedia.org/w/index.php?oldid=396203548 Contributors: 0xFFFF, 84user, Adaminstalbans, Binksternet, Bowlhover, Camouflage55, CapitalR, Charles
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File:Algae hydrogen production.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Algae_hydrogen_production.jpg License: Public Domain Contributors: EERE
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MichaelFrey, Mion, Petri Krohn, Saupreiß
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