Hydrogen history, structure, properties and uses

2163
Egbert Haynes

The hydrogen It is a chemical element that is represented by the symbol H. Its atom is the smallest of all and it is with which the periodic table begins, no matter where it is positioned. It consists of a colorless gas composed of diatomic molecules of Htwo, and not by isolated H atoms; as with the noble gases He, Ne, Ar, among others.

Of all the elements, it is perhaps the most emblematic and outstanding, not only for its properties in terrestrial or drastic conditions, but for its immense abundance and variety of its compounds. Hydrogen is a gas, although inert in the absence of fire, flammable and dangerous; while water, HtwoOr, is the universal solvent and life.

Red cylinders used to store hydrogen. Source: Famartin [CC BY-SA 4.0 (https://creativecommons.org/licenses/by-sa/4.0)]

By itself, hydrogen does not show any visual peculiarity worthy of admiration, being simply a gas that is stored in cylinders or red bottles. However, it is its properties and ability to bind with all elements, which makes hydrogen special. And all this, despite the fact that it only has one valence electron.

If the hydrogen were not stored in its respective cylinders, it would escape into space while much of it reacts on the ascent. And although it has a very low concentration in the air we breathe, outside the Earth and in the rest of the Universe, it is the most abundant element, found in the stars and considered its unit of construction..

On Earth, on the other hand, it represents about 10% of its total mass. To visualize what this means, it must be considered that the surface of the planet is practically covered with oceans and that hydrogen is found in minerals, in crude oil and in any organic compound, in addition to being part of all living beings.

Like carbon, all biomolecules (carbohydrates, proteins, enzymes, DNA, etc.) have hydrogen atoms. Therefore, there are many sources to extract or produce it; however, few represent truly profitable production methods.

Article index

  • 1 History
    • 1.1 Identification and name
    • 1.2 Electrolysis and fuel
    • 1.3 Insulation
    • 1.4 Two channels
  • 2 Structure and electronic configuration
    • 2.1 oxidation numbers
    • 2.2 Phases
  • 3 Properties
    • 3.1 Physical appearance
    • 3.2 Boiling point
    • 3.3 Melting point
    • 3.4 Flash point and stability
    • 3.5 Density
    • 3.6 Solubility
    • 3.7 Vapor pressure
    • 3.8 Autoignition temperature
    • 3.9 Electronegativity
    • 3.10 Heat of combustion
    • 3.11 Heat of vaporization
    • 3.12 Heat of fusion
    • 3.13 Isotopes
    • 3.14 Isomers of spins
  • 4 Nomenclature
  • 5 The hydrogen atom
  • 6 Where to find and production
    • 6.1 Natural
    • 6.2 Industrial
    • 6.3 In the laboratory
  • 7 Reactions
    • 7.1 Redox
    • 7.2 Absorption
    • 7.3 Addition
    • 7.4 Hydride formation
  • 8 Uses
    • 8.1 Raw material
    • 8.2 Reducing agent
    • 8.3 Oil industry
    • 8.4 Fuel
  • 9 References

Story

Identification and name

Although in 1671 Robert Boyle first witnessed a gas that was formed when iron filings reacted with acids, it was the British scientist Henry Cavendish, in 1766, who identified it as a new substance; the "flammable air".

Cavendish found that when this supposedly flammable air burned, water was generated. Based on his work and results, the French chemist Antoine Lavoisier gave this gas the name of hydrogen in 1783. Etymologically its meaning derives from the Greek words 'hydro' and 'genes': forming water.

Electrolysis and fuel

Shortly after, in 1800, American scientists William Nicholson and Sir Anthony Carlisle discovered that water can decompose into hydrogen and oxygen; they had found the electrolysis of water. Later, in 1838, the Swiss chemist Christian Friedrich Schoenbein introduced the idea of ​​taking advantage of the combustion of hydrogen to generate electricity.

The popularity of hydrogen was so great that even the writer Jules Verne referred to it as the fuel of the future in his book The mysterious Island (1874).

Isolation

In 1899, the Scottish chemist James Dewar was the first to isolate hydrogen as a liquefied gas, being himself the one who was able to cool it enough to obtain it in its solid phase..

Two channels

From this point on, the history of hydrogen presents two channels. On the one hand, its development within the field of fuels and batteries; and on the other, the understanding of the structure of its atom and how it represented the element that opened the doors to quantum physics.

Structure and electronic configuration

Diatomic hydrogen molecule. Source: Benjah-bmm27 [Public domain]

Hydrogen atoms are very small and have only one electron to form covalent bonds. When two of these atoms join, they give rise to a diatomic molecule, Htwo; this is molecular hydrogen gas (top image). Each white sphere corresponds to an individual H atom, and the global sphere to the molecular orbitals.

So, hydrogen actually consists of H moleculestwo very small that interact by means of London dispersion forces, since they lack a dipole moment because they are homonuclear. Therefore, they are very "restless" and spread rapidly in space as there are not intermolecular forces strong enough to slow them down..

The electron configuration of hydrogen is simply 1s1. This orbital, 1s, is the product of solving the famous Schrödinger equation for the hydrogen atom. In the Htwo two 1s orbitals overlap to form two molecular orbitals: one bonding and one anti-bonding, according to molecular orbital theory (TOM).

These orbitals allow or explain the existence of H ionstwo+ or Htwo-; however, the chemistry of hydrogen is defined under normal conditions by Htwo or H ions+ or H-.

Oxidation numbers

From the electron configuration for hydrogen, 1s1, its possible oxidation numbers are very easy to predict; bearing in mind, of course, that the higher-energy 2s orbital is not available for chemical bonds. Thus, in the basal state, hydrogen has an oxidation number of 0, H0.

If it loses its only electron, the 1s orbital remains empty and the hydrogen cation or ion, H, is formed+, highly mobile in almost any liquid medium; especially the water. In this case its oxidation number is +1.

And when the opposite happens, that is, gaining an electron, the orbital will now have two electrons and will become 1stwo. Then the oxidation number becomes -1, and corresponds to the hydride anion, H-. It is worth noting that the H- it is isoelectronic to the noble gas helium, He; that is, both species have the same number of electrons.

In summary, the oxidation numbers for hydrogen are: +1, 0 and -1 and the H moleculetwo counts as having two hydrogen atoms H0.

Phases

The preferred phase of hydrogen, at least in terrestrial conditions, is the gaseous one, due to the reasons previously exposed. However, when temperatures decrease in the order of -200 ° C, or if the pressure increases hundreds of thousands of times that of the atmospheric one, hydrogen can condense or crystallize into a liquid or solid phase, respectively..

Under these conditions the molecules Htwo they can be aligned in different ways to define structural patterns. The London dispersion forces now become highly directional and hence geometries or symmetries adopted by pairs H appear.two.

For example, two pairs Htwo, it is that equal to write (Htwo)two define a symmetric or asymmetric square. Meanwhile, three pairs Htwo, or (Htwo)3 they define a hexagon, much like those of carbon in graphite crystals. In fact, this hexagonal phase is the main or most stable phase for solid hydrogen..

But what if the solid was made up not of molecules but of H atoms? Then we would deal with metallic hydrogen. These H atoms, recalling the white spheres, can define both a liquid phase and a metallic solid..

Properties

Physical appearance

Hydrogen is a colorless, odorless, and tasteless gas. Therefore, if there is a leak, it represents a risk of explosion..

Boiling point

-253 ºC.

Melting point

-259 ºC.

Flash point and stability

It explodes at virtually any temperature if there is a spark or heat source close to the gas, even sunlight can ignite hydrogen. However, as long as it is well stored, it is a poorly reactive gas..

Density

0.082 g / L. It is 14 times lighter than air.

Solubility

1.62 mg / L at 21 ºC in water. It is, in general terms, insoluble in most liquids.

Vapor pressure

1.24 106 mmHg at 25 ° C. This value gives an idea of ​​how closed the hydrogen cylinders must be to prevent gas from escaping..

Autoignition temperature

560vºC.

Electronegativity

2.20 on the Pauling scale.

Heat of combustion

-285.8 kJ / mol.

Heat of vaporization

0.90 kJ / mol.

Heat of fusion

0.117 kJ / mol.

Isotopes

The “normal” hydrogen atom is the protium, 1H, which makes up about 99.985% of hydrogen. The other two isotopes for this element are deuterium, twoH, and tritium, 3H. These differ in the number of neutrons; deuterium has one neutron, while tritium has two.

Spin isomers

There are two types of molecular hydrogen, Htwo: the ortho and the para. In the first, the two spins (of the proton) of the H atoms are oriented in the same direction (they are parallel); while in the second, the two spins are in opposite directions (they are antiparallel).

Hydrogen-para is the more stable of the two isomers; but with increasing temperature, the ortho: para ratio becomes 3: 1, which means that the hydrogen-ortho isomer predominates over the other. At very low temperatures (remotely close to absolute zero, 20K), pure hydrogen samples can be obtained-for.

Nomenclature

The nomenclature to refer to hydrogen is one of the simplest; although it is not the same way for its inorganic or organic compounds. The Htwo It can be called by the following names in addition to 'hydrogen':

-Molecular hydrogen

-Dihydrogen

-Diatomic Hydrogen Molecule.

For the H ion+ their names are proton or hydrogen ion; and if it is in an aqueous medium, H3OR+, hydronium cation. While the H ion- is the hydride anion.

The hydrogen atom

The hydrogen atom represented through Bohr's planetary model. Source: Pixabay.

The hydrogen atom is the simplest of all and is normally represented as in the image above: a nucleus with a single proton (for the 1H), surrounded by an electron that draws an orbit. All the atomic orbitals for the other elements of the periodic table have been constructed and estimated on this atom..

A more faithful representation to the current understanding of atoms would be that of a sphere whose periphery is defined by the electron and probabilistic cloud of the electron (its 1s orbital).

Where it is located and production

A field of stars: inexhaustible source of hydrogen. Source: Pixabay.

Hydrogen is, though perhaps to a lesser degree compared to carbon, the chemical element that can be said without doubt to be everywhere; in the air, forming part of the water that fills the seas, oceans and our bodies, in crude oil and minerals, as well as in the organic compounds that are assembled to originate life.

One only has to skim any library of compounds to find hydrogen atoms..

The question is not so much how much but how it is present. For example, the molecule Htwo it is so volatile and reactive under the incidence of solar rays, that it is very scarce in the atmosphere; therefore, it reacts to join other elements and thus gain stability.

While higher up in the cosmos, hydrogen is predominantly found as neutral atoms, H.

In fact, hydrogen is considered, in its metallic and condensed phase, as the building block of stars. As there are immeasurable quantities of them and, due to its robustness and colossal dimensions, they make this element the most abundant in the entire universe. It is estimated that 75% of known matter corresponds to hydrogen atoms.

natural

Collecting hydrogen atoms loose in space sounds impractical and extracting them from the Sun's peripheries, or nebulae, unattainable. On Earth, where its conditions force this element to exist as Htwo, can be produced by natural or geological processes.

For example, hydrogen has its own natural cycle in which certain bacteria, microbes and algae can generate it through photochemical reactions. The scaling of natural and parallel processes includes the use of bioreactors, where bacteria feed on hydrocarbons to release the hydrogen contained in them..

Living things are also producers of hydrogen, but to a lesser degree. If this were not the case, it would not be possible to explain how it constitutes one of the gaseous components of flatulence; which have been excessively shown to be flammable.

Finally, it should be mentioned that under anaerobic conditions (without oxygen), for example in underground layers, minerals can react slowly with water to produce hydrogen. Fayelita's reaction proves it:

3FetwoYes4 + 2 htwoO → 2 Fe3OR4 + 3 SiOtwo + 3 Htwo

Industrial

Although biohydrogen is an alternative to generate this gas on an industrial scale, the most used methods practically consist of “removing” the hydrogen from the compounds that contain it, so that its atoms unite and form Htwo.

The least environmentally friendly methods of producing it consist of reacting coke (or charcoal) with superheated steam:

C (s) + HtwoO (g) → CO (g) + Htwo(g)

Likewise, natural gas has been used for this purpose:

CH4(g) + HtwoO (g) → CO (g) + 3Htwo(g)

And because the amounts of coke or natural gas are vast, it is profitable to produce hydrogen by either of these two reactions..

Another method of obtaining hydrogen is to apply an electrical discharge to water to break it down into its elemental parts (electrolysis):

2 htwoO (l) → 2 Htwo(g) + Otwo(g)

At the laboratory

Molecular hydrogen can be prepared in small quantities in any laboratory. To do this, an active metal must be reacted with a strong acid, either in a beaker or in a test tube. The observable bubbling is a clear sign of hydrogen formation, represented by the following general equation:

M (s) + nH+(ac) → Mn+(ac) + Htwo(g)

Where n is the valence of the metal. For example, magnesium reacts with H+ to produce Htwo:

Mg (s) + 2H+(ac) → Mgtwo+(ac) + Htwo(g)

Reactions

Redox

The oxidation numbers by themselves offer a first glimpse of how hydrogen participates in chemical reactions. The Htwo when reacting it can remain unchanged, or split into the H ions+ or H- depending with which species it is linked; if they are more or less electronegative than him.

The Htwo it is not very reactive due to the strength of its covalent bond, H-H; However, this is not an absolute impediment for it to react and form compounds with almost all the elements of the periodic table..

Its best known reaction is with that of oxygen gas to produce water vapors:

Htwo(g) + Otwo(g) → 2HtwoO (g)

And such is its affinity for oxygen to form the stable water molecule that it can even react with it as an O anion.two- in certain metal oxides:

Htwo(g) + CuO (s) → Cu (s) + HtwoO (l)

Also silver oxide reacts or is "reduced" by the same reaction:

Htwo(g) + AgO (s) → Ag (s) + HtwoO (l)

These hydrogen reactions correspond to the redox type. That is, reduction-oxidation. Hydrogen oxidizes both in the presence of oxygen and of the metal oxides of metals less reactive than it; for example, copper, silver, tungsten, mercury, and gold.

Absorption

Some metals can absorb hydrogen gas to form metal hydrides, which are considered to be alloys. For example, transition metals such as palladium absorb significant amounts of Htwo, being similar to metallic sponges.

The same happens with more complex metal alloys. In this way hydrogen can be stored by means other than its cylinders..

Addition

Organic molecules can also “absorb” hydrogen through different molecular mechanisms and / or interactions..

For metals, the H moleculestwo they are surrounded by the metallic atoms within their crystals; while in organic molecules, the H-H bond breaks to form other covalent bonds. In a more formalized sense: hydrogen is not absorbed, but is added to the structure.

The classic example is the addition of the Htwo to the double or triple bond of the alkenes or alkynes, respectively:

C = C + Htwo  → H-C-C-H

C≡C + Htwo → HC = CH

These reactions are also called hydrogenation..

Hydride formation

Hydrogen reacts directly with elements to form a family of chemical compounds called hydrides. There are mainly of two types: saline and molecular.

Likewise, there are the metallic hydrides, which consist of the metallic alloys already mentioned when these metals absorb hydrogen gas; and the polymeric ones, with networks or chains of links E-H, where E denotes the chemical element.

Saline

In saline hydrides, hydrogen participates in ionic bonding as the hydride anion, H-. For this to form, the element must necessarily be less electronegative; otherwise it wouldn't give up its electrons to hydrogen.

Therefore, saline hydrides are only formed when hydrogen reacts with highly electropositive metals, such as alkali and alkaline earth metals..

For example, hydrogen reacts with metallic sodium to produce sodium hydride:

2Na (s) + Htwo(g) → 2NaH (s)

Or with barium to produce barium hydride:

Ba (s) + Htwo(g) → BaHtwo(s)

Molecular

Molecular hydrides are even better known than ionic ones. They are also called hydrogen halides, HX, when hydrogen reacts with a halogen:

Cltwo(g) + Htwo(g) → 2HCl (g)

Here hydrogen participates in the covalent bond as H+; since, the differences between the electronegativities between both atoms is not very large.

The same water can be considered as an oxygen hydride (or hydrogen oxide), the formation reaction of which has already been discussed. Very similar is the reaction with sulfur to give hydrogen sulfide, a foul-smelling gas:

S (s) + Htwo(g) → HtwoS (g)

But of all the molecular hydrides the most famous (and perhaps the most difficult to synthesize) is ammonia:

Ntwo(g) + 3Htwo(g) → 2NH3(g)

Applications

In the previous section, one of the main uses of hydrogen was already addressed: as a raw material for the development of synthesis, inorganic or organic. Controlling this gas usually has no other purpose than to make it react to create other compounds different from those from which it was extracted..

Raw material

- It is one of the reagents for the synthesis of ammonia, which in turn has endless industrial applications, starting with the production of fertilizers, even as a material to nitrogenate drugs..

- It is intended to react with carbon monoxide and thus massively produce methanol, a reagent that is highly important in biofuels..

Reducing agent

- It is a reducing agent for certain metal oxides, so it is used in metallurgical reduction (already explained in the case of copper and other metals).

- Reduce fats or oils to produce margarine.

Oil industry

In the oil industry, hydrogen is used to “hydrotreat” crude oil in refining processes..

For example, it seeks to fragment large and heavy molecules into small molecules with greater demand in the market (hydrocracking); release the metals trapped in the petroporphyrin cages (hydrodemetallization); remove sulfur atoms like HtwoS (hydrodesulfurization); or reduce double bonds to create paraffin-rich mixtures.

Fuel

Hydrogen itself is an excellent fuel for rockets or spacecraft, since small amounts of it, when reacting with oxygen, release huge amounts of heat or energy.

On a smaller scale, this reaction is used for the design of hydrogen cells or batteries. However, these cells face the difficulties of not being able to store this gas properly; and the challenge of becoming completely independent from burning fossil fuels.

On the positive side, hydrogen used as fuel releases only water; instead of gases that represent means of pollution for the atmosphere and ecosystems.

References

  1. Shiver & Atkins. (2008). Inorganic chemistry. (Fourth edition). Mc Graw Hill.
  2. Hanyu Liu, Li Zhu, Wenwen Cui and Yanming Ma. (S.f.). Room-Temperature Structures of Solid Hydrogen at High Pressures. State Key Lab of Superhard Materials, Jilin University, Changchun 130012, China.
  3. Pierre-Marie Robitaille. (2011). Liquid Metallic Hydrogen: A Building Block for the Liquid Sun. Department of Radiology, The Ohio State University, 395 W. 12th Ave, Columbus, Ohio 43210, USA.
  4. The Bodner Group. (s.f.). The Chemistry of Hydrogen. Recovered from: chemed.chem.purdue.edu
  5. Wikipedia. (2019). Hydrogen. Recovered from: en.wikipedia.org
  6. Hydrogen Europe. (2017). Hydrogen Applications. Recovered from: hydrogeneurope.eu
  7. Foist Laura. (2019). Hydrogen: Properties & Occurrence. Study. Recovered from: study.com
  8. Jonas James. (January 4, 2009). The history of hydrogen. Recovered from: altenergymag.com

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