Nascent hydrogen
Disputed concept in chemistry
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Through Organic chemistry, Metal and Corrosion
History
The idea of hydrogen in the nascent state having chemical properties different from those of molecular hydrogen 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. 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.
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Reducing agents at low and high pH
Devarda's alloy (alloy of aluminium (~45%), copper (~50%) and zinc (~5%)) is a reducing agent that was commonly used in wet analytical chemistry to produce in situ so-called nascent hydrogen under alkaline conditions for the determination of nitrates (NO−
3) after their reduction into ammonia (NH
3).
In the Marsh test, used for arsenic determination (from the reduction of arsenate (AsO3−
4) and arsenite (AsO3−
3) into arsine (AsH
3)), hydrogen is generated by contacting zinc powder with hydrochloric acid.
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 gas (AsH3), while under hyperalkaline solution, the degassing of the reduced ammonia (NH3) is greatly facilitated (the ammonium ion NH+
4 being soluble in aqueous solution under acidic conditions).

