Nascent hydrogen is an outdated concept in

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, ...

that was once invoked to explain dissolving-metal reactions, such as the

Clemmensen reduction Clemmensen reduction is a chemical reaction described as a reduction of ketones (or aldehydes) to alkanes using zinc amalgam and concentrated hydrochloric acid. This reaction is named after Erik Christian Clemmensen, a Danish chemist. The orig ...

and the

Bouveault–Blanc reduction The Bouveault–Blanc reduction is a chemical reaction in which an ester is reduced to primary alcohols using absolute ethanol and sodium metal. It was first reported by Louis Bouveault and Gustave Louis Blanc in 1903. Bouveault and Blanc demon ...

. 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 (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...

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 atom contains a single positively charged proton and a single negatively charged electron bound to the nucleus by the Coulomb force. Atomic hydrogen constit ...

is largely invoked in inorganic chemistry 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 engi ...

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 permeate solid metals. Once absorbed ...

s exposed to electrolysis and anaerobic corrosion (e.g., dissolution of

zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc 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 periodi ...

in strong acids ( HCl) and

aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...

in strong bases (

NaOH Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkali ...

). 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 (s) (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 ...

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 of common metals ( steel,

titanium Titanium is a chemical element with the Symbol (chemistry), 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, resista ...

) different from these of the platinoid group ( Pt, Pd, Rh, Ru, Ni) which are well known to dissociate molecular

dihydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, a ...

( H) into atomic hydrogen.

History

The idea of hydrogen in the nascent state having chemical properties different from those of

molecular hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, ...

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 with hydrogen to form products such as chloroform and dichloromethane 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 substa ...

. 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 Devarda's alloy (CAS # 8049-11-4), is an alloy of aluminium (44% – 46%), copper (49% – 51%) and zinc (4% – 6%). Devarda's alloy is used as reducing agent in analytical chemistry for the determination of nitrat ...

(

alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductilit ...

(~45%),

copper Copper is a chemical element with the symbol Cu (from la, cuprum) 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 pinkis ...

(~50%) and

(~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 commonly reducing agents include the Earth me ...

that was commonly used in wet

analytical chemistry Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separati ...

to produce ''in situ'' so-called nascent hydrogen under alkaline conditions for the determination of nitrates () after their reduction into

ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous wa ...

(). In the

Marsh test The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The metho ...

, used for

arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, ...

determination (from the reduction of

arsenate The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate res ...

() 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 ...

()), hydrogen is generated by contacting

powder with

hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...

. 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

gas (AsH₃), while under hyperalkaline solution, the degassing of the reduced

(NH₃) is greatly facilitated (the ammonium ion being soluble in aqueous solution under acidic conditions).

History

Reducing agents at low and high pH

See also

References

Further reading