Liquid hydrogen

Last updated
Liquid hydrogen
Dihydrogen-2D-dimensions.png
Dihydrogen-3D-vdW.png
Liquid hydrogen bubblechamber.jpg
Names
IUPAC name
Hydrogen
Systematic IUPAC name
Liquid hydrogen
Other names
Hydrogen (cryogenic liquid), Refrigerated hydrogen; LH2, para-hydrogen
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
KEGG
PubChem CID
RTECS number
  • MW8900000
UNII
UN number 1966
  • InChI=1S/H2/h1H Yes check.svgY
    Key: UFHFLCQGNIYNRP-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/H2/h1H
  • [H][H]
Properties
H2(l)
Molar mass 2.016 g·mol−1
AppearanceColorless liquid
Density 0.07085 g/cm3 (4.423 lb/cu ft) [1]
Melting point −259.14 °C (−434.45 °F; 14.01 K) [2]
Boiling point −252.87 °C (−423.17 °F; 20.28 K) [2]
Hazards
GHS labelling: [3]
GHS-pictogram-flamme.svg GHS-pictogram-bottle.svg
Danger
H220, H280
P210, P377, P381, P403
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard CRYO: Cryogenic
3
4
0
571 °C (1,060 °F; 844 K) [2]
Explosive limits LEL 4.0%; UEL 74.2% (in air) [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Liquid hydrogen (H2(l)) is the liquid state of the element hydrogen. Hydrogen is found naturally in the molecular H2 form. [4]

Contents

To exist as a liquid, H2 must be cooled below its critical point of 33  K. However, for it to be in a fully liquid state at atmospheric pressure, H2 needs to be cooled to 20.28 K (−252.87 °C; −423.17 °F). [5] A 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. Storing it as liquid takes less space than storing it as a gas at normal temperature and pressure. However, the liquid density is very low compared to other common fuels. Once liquefied, it can be maintained as a liquid for some time in thermally insulated containers. [6]

There are two spin isomers of hydrogen; whereas room temperature hydrogen is mostly orthohydrogen, liquid hydrogen consists of 99.79% parahydrogen and 0.21% orthohydrogen. [5]

Hydrogen requires a theoretical minimum of 3.3 kWh/kg to liquefy, and 3.9 kWh/kg including converting the hydrogen to the para isomer, but practically generally takes 10–13 kWh/kg compared to a 33 kWh/kg heating value of hydrogen. [7]

History

The global headquarters of Air Products in Trexlertown, Pennsylvania, a leading global supplier of liquid hydrogen Air Products Headquarters, Trexlertown.JPG
The global headquarters of Air Products in Trexlertown, Pennsylvania, a leading global supplier of liquid hydrogen
Liquid hydrogen bubbles forming in two glass flasks at the Bevatron laboratory in 1955 Liquid hydrogen bubblechamber.jpg
Liquid hydrogen bubbles forming in two glass flasks at the Bevatron laboratory in 1955
A large hydrogen tank in a vacuum chamber at the Glenn Research Center in Brook Park, Ohio, in 1967 Hydrogen Tank - GPN-2000-001458.jpg
A large hydrogen tank in a vacuum chamber at the Glenn Research Center in Brook Park, Ohio, in 1967
A Linde AG tank for liquid hydrogen at the Museum Autovision in Altlussheim, Germany, in 2008 Linde-Wasserstofftank.JPG
A Linde AG tank for liquid hydrogen at the Museum Autovision in Altlußheim, Germany, in 2008
Two U.S. Department of Transportation placards indicating the presence of hazardous materials, which are used with liquid hydrogen DOT Hazardous Material Placard liquid hydrogen.jpg
Two U.S. Department of Transportation placards indicating the presence of hazardous materials, which are used with liquid hydrogen

In 1885, Zygmunt Florenty Wróblewski published hydrogen's critical temperature as 33 K (−240.2 °C; −400.3 °F); critical pressure, 13.3 standard atmospheres (195 psi); and boiling point, 23 K (−250.2 °C; −418.3 °F).

Hydrogen was liquefied 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.

Spin isomers of hydrogen

The two nuclei in a dihydrogen molecule can have two different spin states. Parahydrogen, in which the two nuclear spins are antiparallel, is more stable than orthohydrogen, in which the two are parallel. At room temperature, gaseous hydrogen is mostly in the ortho isomeric form due to thermal energy, but an ortho-enriched mixture is only metastable when liquified at low temperature. It slowly undergoes an exothermic reaction to become the para isomer, with enough energy released as heat to cause some of the liquid to boil. [8] To prevent loss of the liquid during long-term storage, it is therefore intentionally converted to the para isomer as part of the production process, typically using a catalyst such as iron(III) oxide, activated carbon, platinized asbestos, rare earth metals, uranium compounds, chromium(III) oxide, or some nickel compounds. [8]

Uses

Liquid hydrogen is a common liquid rocket fuel for rocketry application and is used by NASA and the U.S. Air Force, which operate a large number of liquid hydrogen tanks with an individual capacity up to 3.8 million liters (1 million U.S. gallons). [9]

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, 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, which can increase specific impulse, despite the incomplete combustion.

Liquid hydrogen can be used as the fuel for an internal combustion engine or fuel cell. Various submarines, including the Type 212 submarine, Type 214 submarine, and others, and concept hydrogen vehicles have been built using this form of hydrogen, such as the DeepC, BMW H2R, and others. Due to its similarity, builders can sometimes modify and share equipment with systems designed for liquefied natural gas (LNG). Liquid hydrogen is being investigated as a zero carbon fuel for aircraft. Because of the lower volumetric energy, the hydrogen volumes needed for combustion are large. 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). Finally, superheated liquid hydrogen was used in many bubble chamber experiments.

The first thermonuclear bomb, Ivy Mike, used liquid deuterium, also known as Hydrogen-2, for nuclear fusion.

Properties

The product of hydrogen combustion in a pure oxygen environment is solely water vapor. However, the high combustion temperatures and present atmospheric nitrogen can result in the breaking of N≡N bonds, forming toxic NOx if no exhaust scrubbing is done. [10] Since water is often considered harmless to the environment, an engine burning it can be considered "zero emissions". In aviation, however, water vapor emitted in the atmosphere contributes to global warming (to a lesser extent than CO2). [11] Liquid hydrogen also has a much higher specific energy than gasoline, natural gas, or diesel. [12]

The density of liquid hydrogen is only 70.85 g/L (at 20  K), a relative density of just 0.07. Although the specific energy is more than twice that of other fuels, this gives it a remarkably low volumetric energy density, many fold lower.

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 at a rate of 1% per day [12] ). It also shares many of the same safety issues as other forms of hydrogen, as well as being cold enough to liquefy, or even solidify atmospheric oxygen, which can be an explosion hazard.

The triple point of hydrogen is at 13.81 K [5] 7.042 kPa. [13]

Safety

Due to its cold temperatures, liquid hydrogen is a hazard for cold burns. Hydrogen itself is biologically inert and its only human health hazard as a vapor is displacement of oxygen, resulting in asphyxiation, and its very high flammability and ability to detonate when mixed with air. Because of its flammability, liquid hydrogen should be kept away from heat or flame unless ignition is intended. Unlike ambient-temperature gaseous hydrogen, which is lighter than air, hydrogen recently vaporized from liquid is so cold that it is heavier than air and can form flammable heavier-than-air air–hydrogen mixtures.

See also

Related Research Articles

<span class="mw-page-title-main">Cryogenics</span> Study of the production and behaviour of materials at very low temperatures

In physics, cryogenics is the production and behaviour of materials at very low temperatures.

<span class="mw-page-title-main">Hydrogen</span> Chemical element, symbol H and atomic number 1

Hydrogen is a chemical element; it has symbol H and atomic number 1. It is the lightest element and, at standard conditions, is a gas of diatomic molecules with the formula H2. It is colorless, odorless, tasteless, non-toxic, and highly combustible. Hydrogen is the most abundant chemical substance in the universe, constituting roughly 75% of all normal matter. Stars such as the Sun are mainly composed of hydrogen in the plasma state. Most of the hydrogen on Earth exists in molecular forms such as water and organic compounds. For the most common isotope of hydrogen each atom has one proton, one electron, and no neutrons.

<span class="mw-page-title-main">Gasification</span> Form of energy conversion

Gasification is a process that converts biomass- or fossil fuel-based carbonaceous materials into gases, including as the largest fractions: nitrogen (N2), carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2). This is achieved by reacting the feedstock material at high temperatures (typically >700 °C), without combustion, via controlling the amount of oxygen and/or steam present in the reaction. The resulting gas mixture is called syngas (from synthesis gas) or producer gas and is itself a fuel due to the flammability of the H2 and CO of which the gas is largely composed. Power can be derived from the subsequent combustion of the resultant gas, and is considered to be a source of renewable energy if the gasified compounds were obtained from biomass feedstock.

<span class="mw-page-title-main">Liquid nitrogen</span> Liquid state of nitrogen

Liquid nitrogenLN2—is nitrogen in a liquid state at low temperature. Liquid nitrogen has a boiling point of about −196 °C (−321 °F; 77 K). It is produced industrially by fractional distillation of liquid air. It is a colorless, mobile liquid whose viscosity is about one tenth that of acetone. Liquid nitrogen is widely used as a coolant.

<span class="mw-page-title-main">Liquid oxygen</span> One of the physical forms of elemental oxygen

Liquid oxygen, sometimes abbreviated as LOX or LOXygen, is the liquid form of molecular oxygen. It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an application which has continued to the present.

<span class="mw-page-title-main">RP-1</span> Highly refined form of kerosene used as rocket fuel

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<span class="mw-page-title-main">Liquid fuel</span> Liquids that can be used to create energy

Liquid fuels are combustible or energy-generating molecules that can be harnessed to create mechanical energy, usually producing kinetic energy; they also must take the shape of their container. It is the fumes of liquid fuels that are flammable instead of the fluid. Most liquid fuels in widespread use are derived from fossil fuels; however, there are several types, such as hydrogen fuel, ethanol, and biodiesel, which are also categorized as a liquid fuel. Many liquid fuels play a primary role in transportation and the economy.

Cryogenic fuels are fuels that require storage at extremely low temperatures in order to maintain them in a liquid state. These fuels are used in machinery that operates in space where ordinary fuel cannot be used, due to the very low temperatures often encountered in space, and the absence of an environment that supports combustion. Cryogenic fuels most often constitute liquefied gases such as liquid hydrogen.

Liquid air is air that has been cooled to very low temperatures, so that it has condensed into a pale blue mobile liquid. It is stored in specialized containers, such as vacuum flasks, to insulate it from room temperature. Liquid air can absorb heat rapidly and revert to its gaseous state. It is often used for condensing other substances into liquid and/or solidifying them, and as an industrial source of nitrogen, oxygen, argon, and other inert gases through a process called air separation.

<span class="mw-page-title-main">Spin isomers of hydrogen</span> Spin states of hydrogen

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<span class="mw-page-title-main">Liquefaction of gases</span>

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<span class="mw-page-title-main">Bivalent (engine)</span>

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<span class="mw-page-title-main">Cryogenic rocket engine</span> Type of rocket engine which uses liquid fuel stored at very low temperatures

A cryogenic rocket engine is a rocket engine that uses a cryogenic fuel and oxidizer; that is, both its fuel and oxidizer are gases which have been liquefied and are stored at very low temperatures. These highly efficient engines were first flown on the US Atlas-Centaur and were one of the main factors of NASA's success in reaching the Moon by the Saturn V rocket.

<span class="mw-page-title-main">Rocket propellant</span> Chemical or mixture used as fuel for a rocket engine

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References

  1. Thermophysical Properties of Hydrogen, nist.gov, accessed 2012-09-14
  2. 1 2 3 4 Information specific to liquid hydrogen Archived 2009-07-17 at the Wayback Machine , harvard.edu, accessed 2009-06-12
  3. GHS: GESTIS 007010
  4. "We've Got (Rocket) Chemistry, Part 1". NASA Blog. 15 April 2016. Retrieved 3 October 2021.
  5. 1 2 3 IPTS-1968, iupac.org, accessed 2020-01-01
  6. "Liquid Hydrogen Delivery". Energy.gov. Retrieved 2022-07-30.
  7. Gardiner, Monterey (2009-10-26). DOE Hydrogen and Fuel Cells Program Record: Energy requirements for hydrogen gas compression and liquefaction as related to vehicle storage needs (PDF) (Report). United States Department of Energy.
  8. 1 2 "Liquefaction of "Permanent" Gases" (PDF of lecture notes). 2011. Retrieved 2017-10-16.
  9. Flynn, Thomas (2004). Cryogenic Engineering, Second Edition, Revised and Expanded. CRC Press. p. 401. ISBN   978-0-203-02699-1.
  10. Lewis, Alastair C. (2021-07-22). "Optimising air quality co-benefits in a hydrogen economy: a case for hydrogen-specific standards for NOx emissions". Environmental Science: Atmospheres. 1 (5): 201–207. doi: 10.1039/D1EA00037C . ISSN   2634-3606. S2CID   236732702.
  11. Nojoumi, H. (2008-11-10). "Greenhouse gas emissions assessment of hydrogen and kerosene-fueled aircraft propulsion". International Journal of Hydrogen Energy. 34 (3): 1363–1369. doi:10.1016/j.ijhydene.2008.11.017.
  12. 1 2 Hydrogen As an Alternative Fuel Archived 2008-08-08 at the Wayback Machine . Almc.army.mil. Retrieved on 2011-08-28.
  13. Cengel, Yunus A. and Turner, Robert H. (2004). Fundamentals of thermal-fluid sciences, McGraw-Hill, p. 78, ISBN   0-07-297675-6