Nascent Hydrogen
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Nascent hydrogen is an outdated concept in
organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...
that was once invoked to explain dissolving-metal reactions, such as the Clemmensen reduction and the Bouveault–Blanc reduction. Since organic compounds do not react with H2, a special state of hydrogen was postulated. It is now understood that dissolving-metal reactions occur at the
metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...
surface, and the concept of nascent hydrogen has been discredited in organic chemistry. However, the formation of
atomic hydrogen A hydrogen atom is an atom of the chemical element hydrogen. The electrically neutral hydrogen atom contains a single positively charged proton in the nucleus, and a single negatively charged electron bound to the nucleus by the Coulomb for ...
is largely invoked in
inorganic chemistry Inorganic chemistry deals with chemical synthesis, synthesis and behavior of inorganic compound, inorganic and organometallic chemistry, organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subj ...
and
corrosion Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
sciences to explain
hydrogen embrittlement Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), is a reduction in the ductility of a metal due to absorbed hydrogen. Hydrogen atoms are small and can Permeation, permeate solid metals. O ...
in
metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...
s exposed to
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
and anaerobic corrosion (e.g., dissolution of
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
in strong
acid An acid is a molecule or ion capable of either donating a proton (i.e. Hydron, hydrogen cation, H+), known as a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis ...
s ( HCl) and
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
in strong bases (
NaOH Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base and alkali t ...
)). The mechanism of hydrogen embrittlement was first proposed by Johnson (1875). The inability of hydrogen atoms to react with organic reagents in
organic solvent A solvent (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for p ...
s does not exclude the transient formation of hydrogen atoms capable to immediately
diffuse Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
into the
crystal lattice In crystallography, crystal structure is a description of ordered arrangement of atoms, ions, or molecules in a crystal, crystalline material. Ordered structures occur from intrinsic nature of constituent particles to form symmetric patterns that ...
of common metals (
steel Steel is an alloy of iron and carbon that demonstrates improved mechanical properties compared to the pure form of iron. Due to steel's high Young's modulus, elastic modulus, Yield (engineering), yield strength, Fracture, fracture strength a ...
,
titanium Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
) different from these of the platinoid group ( Pt, Pd, Rh, Ru, Ni) which are well known to dissociate molecular
dihydrogen Hydrogen is a chemical element; it has symbol H and atomic number 1. It is the lightest and most abundant chemical element in the universe, constituting about 75% of all normal matter. Under standard conditions, hydrogen is a gas of diatom ...
( H) into atomic hydrogen.


History

The idea of hydrogen in the nascent state having chemical properties different from those of
molecular hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
developed the mid-19th century. Alexander Williamson repeatedly refers to nascent hydrogen in his textbook ''Chemistry for Students'', for example writing of the substitution reaction of
carbon tetrachloride Carbon tetrachloride, also known by many other names (such as carbon tet for short and tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC), is a chemical compound with the chemical formula CCl4. It is a n ...
with hydrogen to form products such as
chloroform Chloroform, or trichloromethane (often abbreviated as TCM), is an organochloride with the formula and a common solvent. It is a volatile, colorless, sweet-smelling, dense liquid produced on a large scale as a precursor to refrigerants and po ...
and
dichloromethane Dichloromethane (DCM, methylene chloride, or methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odor is widely used as a solvent. Although it is not miscible with ...
that the "hydrogen must for this purpose be in the nascent state, as free hydrogen does not produce the effect". Williamson also describes the use of nascent hydrogen in the earlier work of
Marcellin Berthelot Pierre Eugène Marcellin Berthelot (; 25 October 1827 – 18 March 1907) was a French chemist and Republican politician noted for the ThomsenBerthelot principle of thermochemistry. He synthesized many organic compounds from inorganic substance ...
. Franchot published a paper on the concept in 1896, which drew a strongly worded response from Tommasi who pointed to his own work that concluded "nascent hydrogen is nothing else than H + ''x'' calories". The term "nascent hydrogen" continued to be invoked into the 20th century.


Reducing agents at low and high pH

Devarda's alloy (
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
of
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
(~45%),
copper Copper is a chemical element; it has symbol Cu (from Latin ) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orang ...
(~50%) and
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
(~5%)) is a
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are common reducing agents include hydrogen, carbon ...
that was commonly used in wet
analytical chemistry Analytical skill, Analytical chemistry studies and uses instruments and methods to Separation process, separate, identify, and Quantification (science), quantify matter. In practice, separation, identification or quantification may constitute t ...
to produce ''in situ'' so-called nascent hydrogen under alkaline conditions for the determination of
nitrate Nitrate is a polyatomic ion with the chemical formula . salt (chemistry), Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are solubility, soluble in wa ...
s () after their reduction into
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
(). In the Marsh test, used for
arsenic Arsenic is a chemical element; it has Symbol (chemistry), symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is not ...
determination (from the reduction of
arsenate The arsenate is an ion with the chemical formula . Bonding in arsenate consists of a central arsenic atom, with oxidation state +5, double bonded to one oxygen atom and single bonded to a further three oxygen atoms. The four oxygen atoms orien ...
() and
arsenite In chemistry, an arsenite is a chemical compound containing an arsenic oxyanion where arsenic has oxidation state +3. Note that in fields that commonly deal with groundwater chemistry, arsenite is used generically to identify soluble AsIII anions ...
() into
arsine Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in th ...
()), hydrogen is generated by contacting
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
powder with
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
. So, hydrogen can be conveniently produced at low or high pH, according to the volatility of the species to be detected. Acid conditions in the Marsh test promote the fast escape of the
arsine Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in th ...
gas (AsH3), while under hyperalkaline solution, the degassing of the reduced
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
(NH3) is greatly facilitated (the
ammonium Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) polyatomic ion, molecular ion with the chemical formula or . It is formed by the protonation, addition of a proton (a hydrogen nucleu ...
ion being soluble in
aqueous solution An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, also known as sodium chloride (NaCl), in water ...
under acidic conditions).


See also

* Atomic hydrogen welding


References


Further reading

* *{{Cite journal , last = Meija , first = Juris , author2=Alessandro D’Ulivo , year = 2008 , title = Solution to nascent hydrogen challenge , journal = Analytical and Bioanalytical Chemistry , volume = 392 , issue = 5 , pages = 771–772 , doi = 10.1007/s00216-008-2356-6 , issn = 1618-2642 , pmid = 18795271 , s2cid = 206900604 Hydrogen Electrolysis
Hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
Obsolete theories in chemistry